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1.
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 总被引：4，自引：0，他引：4
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。 相似文献
2.
为探明不同的样品前处理方法对水中溶解无机碳同位素的影响,寻找最佳的样品前处理方法,本文系统研究了不同样品采集方法（顶空样品瓶和聚乙烯瓶）和保存方法（不同的温度和是否加饱和氯化汞）以及储存时间对不同类型水样溶解无机碳同位素值的影响。结果表明:在水样类型相同的情况下,顶空瓶法较聚乙烯瓶法采集的水样δ13CDIC值更稳定;用聚乙烯瓶采集水样,加入饱和氯化汞能抑制微生物生长,不加饱和氯化汞的水样δ13CDIC值变化无规律且幅度大,而加了饱和氯化汞的水样δ13CDIC值更接近初始值,但随保存温度的升高和保存时间的推移,其δ13CDIC值逐渐偏重,主要受温度升高有利于HCO3-水解并释放CO2的影响;不同类型水样在不加饱和氯化汞条件下,随保存时间加长,岩溶水的δ13CDIC值较初始值偏重,混合水和非岩溶区水δ13CDIC值较初始值偏轻。实验表明,用顶空样品瓶采集的水样保存100天,δ13CDIC最大变化值为0.42‰;用顶空样品瓶采集的水样保存时间长,δ13CDIC值变化小,最能反映样品的初始值,是最佳的样品前处理方法。用聚乙烯瓶采集的水样加饱和氯化汞并保存在5 ℃能满足样品短时间的保存。 相似文献
3.
GasBench Ⅱ-IRMS水平衡氢氧同位素分析方法研究 总被引：10，自引：5，他引：5
考察了参考气信号强度、样品水体积和水平衡时间对水平衡氢、氧同位素组成分析的影响,建立了GasBench Ⅱ-IRMS连续流稳定同位素质谱仪、CO2-H2O平衡在线连续分析水样中氧同位素组成、疏水铂催化H2-H2O平衡在线连续分析水样中氢同位素组成的分析方法。分析实验室和标准水样,测量值在误差允许范围内与推荐值一致;实验室水标准氢同位素组成分析精度(1σ)为1‰,氧同位素组成分析精度(1σ)为0.1‰。方法能减少样品的损失,提高分析速度和稳定性。 相似文献
4.
GasBenchⅡ-连续流稳定同位素质谱仪(IRMS)联用在线分析已成为碳酸盐碳氧同位素分析测试的常用方法,已有研究认为不同的实验条件直接影响δ13C和δ18O同位素测试结果的准确性。但这些报道未对该联用方法所涉及的实验条件进行综合分析。本文系统研究了GasBenchⅡ-IRMS法中各种实验条件(包括排空时间、反应温度、反应时间和色谱分离温度)对碳氧同位素测试结果的综合影响。结果表明:排空时间大于9 min可有效消除空气对测试结果的干扰,不同的反应温度和时间对碳氧同位素分析结果均有一定影响,经条件优化确定反应温度为72℃,反应时间为60 min,色谱分离温度为60℃。在优化的实验条件下,碳氧同位素分析精度分别优于0.03‰和0.05‰,达到了国际分析测试水平。同时,选择合适的同位素数据归一化方法可以进一步保证碳氧同位素测试结果的准确性和可靠性。通过分析近4000件实际样品,对比单一标准物质校准和双标准物质校准同位素归一化方法的计算结果,发现双标准物质校准偏差小于单一标准物质校准偏差,因此建议采用双标准物质校准法进行样品同位素标准化计算。本研究为GasBenchⅡ-IRMS联用技术中实验条件的选取提供了一定的参考,保证碳氧同位素测试结果的可靠性和准确性。同时提出,由于样品成分复杂且不均一,在分析实际样品时需要根据样品的性质进一步对实验条件进行考察。 相似文献
5.
2003年4月至2004年5月,笔者对贵州七星洞(QXD)进行了较为详细的监测,逐月采集了土壤水和洞穴滴水等样品,分别测定了样品的稳定碳同位素组成和水文地球化学参数。结果显示,9个滴水点同期的溶解无机碳同位素值(δ13CDIC)之间存在着大的差异,最大达6.9‰;δ13CDIC值偏重的Ⅰ组滴水,其Ca、Sr、HCO3、电导率(EC)和方解石饱和指数(SIC)等水文地球化学指标偏小,而Mg/Ca比值偏大,Ⅱ组则相反;不同滴水点的δ13CDIC值分别与相应滴水的Ca、Sr、HCO3、EC、Mg/Ca和SIC等水文地球化学指标之间存在较好的相关关系。进一步分析表明,与土壤水δ13CDIC平均值-9.9‰相比,Ⅰ组1#、2#、6#、7#和8#滴水点δ13CDIC值偏重4.5‰～5.7‰,主要是由大量的基岩溶解以及前期方解石沉积(prior calcite precipitation,PCP)共同作用的结果;Ⅱ组3#、4#、5#和9#滴水点δ13CDIC值偏重0.6‰～1.6‰,受基岩溶解和PCP过程影响较小,尤其是9#滴水点受影响最小。因此,若不考虑基岩溶解和PCP过程影响作用,将会极大地影响洞穴化学沉积物碳同位素记录的准确解释。 相似文献
6.
重庆芙蓉洞洞穴沉积物δ13C、δ18O特征及意义 总被引：14，自引：0，他引：14
利用重庆芙蓉洞内各种新老沉积物的δ13C、δ18O以及对洞穴内的滴水、池水和洞外泉水的长期观测结果,发现芙蓉洞内的次生沉积物中氧同位素变化整体一致,处于稳定温度下(16℃)的平衡分馏状态。而且洞内滴水和池水的氧同位素也相当一致,反映了外界大气降水中氧同位素的年平均状态。芙蓉洞内各种沉积物中碳同位素变化范围很大,从0‰~-11‰均有分布。由于芙蓉洞内各种滴水以及池水中溶解无机碳(DIC)的δ13C变化约在-8‰~-11‰,显著偏轻于部分洞穴沉积物中的δ13C。通过研究从洞穴滴水到形成次生化学沉积物这个过程中的可能影响洞穴沉积物中碳同位素变化的因素,例如：洞穴温度、滴水高度和速率、CO2脱气、生物作用、矿物同质异相转换等,同时参考芙蓉洞内连续生长达37 ka的FR5石笋的碳同位素记录,发现以上可能的影响因素都不能完全解释芙蓉洞内次生沉积物中碳同位素的异常偏重现象。虽然芙蓉洞内广泛存在文石与方解石共存的次生沉积物,但是综合分析表明这些沉积物的氧同位素处于平衡分馏状态,可以用来进行古气候研究。不过在利用石笋碳同位素解释古环境变化时需要慎重,特别是在讨论由文石或文石—方解石混合构成的次生沉积物时。 相似文献
7.
海洋沉积物孔隙水中溶解无机碳(DIC)的碳同位素分析方法 总被引：1，自引：0，他引：1
海水中往往含有一定量的溶解CO2（以HCO-3存在），其δ13C值组成十分恒定，一般在0‰值附近。赋存在海底沉积物中的孔隙水往往含有比海水更高的溶解CO2含量，且其碳同位素组成变化极大。对这些溶解CO2的碳同位素组成进行分析，能够为我们了解海底沉积物沉积-成岩过程和生物地球化学过程提供十分丰富的信息。为此，开展了沉积物孔隙水中溶解CO2 (DIC)的碳同位素分析方法的研究。 采用的仪器为德国Finnigan公司生产的连续流质谱仪（Delta Plus XP）及与之联机的多功能制样装置(Gas Bench)。 Delta Plus XP为稳定同位素比值质谱仪，可以进行C、H、O、S、N等稳定同位素比值的测定，内精度小于0.1‰，外精度为0.1‰,稳定性好于0.03×10-6nA/h。Gas Bench为多功能在线制样装置，可进行CO2-H2O平衡法氧同位素，溶解二氧化碳碳同位素，碳酸盐碳氧同位素，空气中氮同位素及氮总量的前期制样，由于使用自动制样系统，具有处理时间短，效率高的优点。 样品分析过程：首先在自动进样器中对样品管进行烘烤(45℃)，然后拧紧瓶盖向样品管中充入氦气（16 min/管），充气完毕之后开始加人样品，使用注射器向管中注射0.5 mL样品，下一步使用加酸装置向管中注人磷酸反应平衡，磷酸用量大约0.3 mL左右，反应式如下： H3PO4＋HCO-3 aq===CO2(g)+H2PO- 4…+H2O…… 平衡1h后利用氦气将反应生成的气体CO2送人Delta Plus XP质谱仪测试。 实验过程中，制备了3个水样标准。NJWCS-l为直接取自实验室的Mill-Q纯净水，NJWCS-2为Mill-Q纯净水经蒸沸再冷却后，装人一密封的瓶子中，并向瓶中通人实验室用超纯钢瓶CO2气约4h，使CO2气充分溶解在水中并达到平衡。该瓶气体的δ13C值为-21.85‰。NJWCS-3为南京大学的自来水。 在不同时间对上述标准水样进行碳同位素组成测试结果表1。 实验过程中，选取3个采自南海北部某区海底沉积物孔隙水样品，进行了多次重复测试。结果表明，测试结果十分稳定。其中S-1的δ13C值（-5.11±0.12)‰( n=4); S-2的梦δ13C值（-27.13±0. 02)‰( n=2);S-3的δ13C值（-29.34±0.37)‰（n＝2)。 综上所述，通过笔者建立的分析方法，可对沉积物中孔隙水溶解无机碳碳同位素组成进行准确测试。这一方法的建立，有利于对海洋沉积物孔隙水中可能存在的碳同位素组成异常及其与天然气水合物的关系进行深人探讨。同时，该方法也完全适合于测定自然界中其他水体（如湖水、河水、油田卤水、地下水等）的溶解无机碳的碳同位素组成，因而该方法有着广泛的应用前景。 相似文献
8.
重庆地区岩溶地下河水溶解无机碳及其稳定同位素特征 总被引：6，自引：3，他引：3
稳定碳同位素是指示岩溶动力系统碳来源及转化的重要指标。为揭示重庆地区岩溶地下水中溶解无机碳基本特征和碳来源,本文对该地区63条岩溶地下河水样进行了水化学和碳同位素分析。研究结果表明,重庆地区地下河水溶解无机碳主要表现形式为HCO3-,雨季由于稀释作用其浓度低于旱季。重庆岩溶地下河水δ13C-DIC（V-PDB）旱季变化范围为-15.34 ‰～-5.89 ‰,雨季变化范围为-17.40 ‰～-4.23 ‰。根据δ13C同位素质量平衡方法,计算得到重庆地下河旱季碳酸盐岩溶蚀对DIC贡献为45.1 % ～79.7 %,雨季平均为34.6 %～82.1 % 。计算结果表明,在人类活动不断增强的情况下,岩溶水体DIC通量中碳酸盐岩溶解来源的DIC和其参与岩溶地下水δ13C值的形成并不一定是岩溶作用理论方程中所计算的50 %,而是有一定的变化范围。因此在计算岩溶作用碳汇时,建议通过δ13C值扣除碳酸盐岩溶蚀形成DIC的通量后再来推算岩溶作用形成的碳汇量。 相似文献
9.
为了研究芙蓉洞滴水和池水中溶解无机碳碳同位素(DICδ13C)的变化特征、影响因素及其气候环境指示意义,于2013年5月-2014年5月对芙蓉洞进行了洞穴监测。结果显示芙蓉洞山体土壤CO2浓度和洞内空气CO2浓度均表现出明显的季节变化特征,夏半年浓度偏高,冬半年浓度偏低,受温度和降水量的共同影响。芙蓉洞5个滴水点的DICδ13C平均值为-8.98 ‰,两个池水点的DICδ13C平均值为-6.98 ‰,池水的DICδ13C比滴水的重2 ‰。对应2013年7月的干旱气候,洞穴水DICδ13C在10月相应出现明显偏重值,偏轻的DICδ13C值则是对湿润气候的滞后响应。洞穴水的DICδ13C变化对地表气候的响应具有明显的滞后期。洞穴水DICδ13C主要受土壤CO2的影响,基岩溶解作用、包气带的开放性等因素也会对洞穴水DICδ13C造成一定的影响。研究结果表明在短时间尺度上,洞穴水DICδ13C变化响应了当地降水量以及地表湿润状况的变化。 相似文献
10.
GasBenchⅡ顶空瓶内空气背景对<100μg碳酸盐中碳氧同位素在线测定的影响及校正方法初探 总被引：3，自引：2，他引：1
较为系统地研究了在特定排空时间下GasBenchⅡ顶空瓶内背景CO2的量和同位素组成变化,并检查了该空白CO2组分对碳酸盐C、O同位素在线测定的影响。结果发现,由于排空时间较短所导致的顶空瓶内剩余的空气CO2或由于排空方法不当所导致的外部空气少量回流都会对小样品量(100μg)碳酸盐C、O同位素测定结果产生显著影响。其影响程度取决于空白CO2的量和空白CO2与碳酸盐样品之间C、O同位素的差别大小。由此,对小样品量碳酸盐C、O同位素的测定结果进行了空白校正。当碳酸盐样品质量在20~100μg,校正后δ13C和δ18O值的标准偏差分别小于0.12‰和0.13‰,这证明了该空白校正方法的可行性。由于顶空瓶中空白CO2的量很小,所以对痕量CO2的量、δ13C和δ18O测定值的测定会存在一定波动,这对碳酸盐δ13C和δ18O校正值产生小于0.2‰的不确定度。采用准确测定的实验室空气CO2的δ13C和δ18O值则会大大减少该不确定度的影响。 相似文献
11.
William Cory Beck Ethan L. Grossman John W. Morse 《Geochimica et cosmochimica acta》2005,69(14):3493-3503
In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO3− and CO32− concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO3−, CO32−, and CO2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO3−, CO32−, and H2O, NaHCO3 solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl2 was added to the NaHCO3 solutions. This resulted in immediate BaCO3 precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO3− and H2O as a function of temperature is governed by the equation:
12.
Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China 总被引：2，自引：0，他引：2
Si-Liang Li Cong-Qiang Liu Yun-Chao Lang Faxiang Tao Zhiqi Zhao Zhihua Zhou 《Aquatic Geochemistry》2008,14(3):211-221
Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition
of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The
waters can be mainly characterized as HCO3–Ca type, HCO3 · SO4–Ca type, or HCO3 · SO4–Ca · Mg type, according to mass balance considerations. It is found that the average δ13CDIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved
inorganic carbon (DIC) and lower values of δ13CDIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an
important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO2 makes a larger contribution to the DIC in summer than in winter. The range of δ13CDIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations
of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L−1 and 0.5 mg C L−1, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents
are generally located in the urban area where lower δ13CDIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality. 相似文献
13.
The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ13CDIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO3−-rich, SO42−-rich and Cl−-rich. The HCO3−-rich groundwater is undergoing closed system carbonate evolution from soil CO2(g) and weathering of aquifer carbonates. The SO42−-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl−-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ13CDIC of the HCO3−-rich groundwater was controlled by nearly equal contribution of carbon from soil CO2(g) and the aquifer carbonates, such that the δ13C of carbon added to the groundwater was −11.6‰. In the SO42−-rich groundwater, gypsum induced dedolomitization increased the 13C such that the δ13C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl−-rich groundwater, common ion induced precipitation of calcite depleted the 13C such that the δ13C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution. 相似文献
14.
Makoto Yamada Shinji Ohsawa Kohei Kazahaya Masaya Yasuhara Hiroshi Takahashi Kazuhiro Amita Hideo Mawatari Shin Yoshikawa 《Journal of Geochemical Exploration》2011
To understand deep groundwater flow systems and their interaction with CO2 emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ13CDIC) and DIC concentrations of the sampled waters show that magma-derived CO2 mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ13CDIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ18O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ13CDIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO2 is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO2 mixes into deeper groundwater flowing nearer the magma conduit or chamber. 相似文献
15.
The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ13CDIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO3 ?, Ca2+ and Mg2+ originating from carbonate dissolution. The Mg2+/Ca2+ and Mg2+/HCO3 ? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO2 concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO2 downstream. The δ13C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO2, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO2 has minor influence on the inorganic carbon pool in the Krka River. 相似文献
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不同方法萃取的溶解无机碳的δ13C值比较分析 总被引：1，自引：0，他引：1
为了测定水中溶解无机碳的δ13C值,通常可以利用两种方法对水中的DIC进行萃取:沉淀法和脱气法。但是,一直以来未有研究对这两种方法萃取同一水样DIC的δ13C值之间的差异进行对比分析,尤其是对于具有高CO2分压(pCO2)的水样。本文对两组分别代表深部岩溶系统(高pCO2)和表层岩溶系统(低pCO2)的水样分别同时利用这两种萃取方法萃取其DIC然后测定δ13CDIC值。对比发现利用脱气法萃取物测定得到的δ13CDIC值要显著高于利用沉淀法萃取物测定得到的δ13CDIC值。这是因为在脱气法萃取DIC的过程中,由于水的pCO2高于大气的pCO2,水中富含12C的CO2通过扩散作用逃逸到大气中,从而使δ13CDIC值偏正。这表明利用沉淀法萃取物测定的δ13CDIC值的精度要高于脱气萃取法的精度。对两种DIC萃取方法萃取物测定的δ13CDIC值之间的差与水样和大气之间的CO2分压差进行分析后发现,两者之间具有较好的正相关关系。由于深部岩溶系统的水样具有很高的pCO2,富含12C的CO2向大气逸出的量相对较多,从而导致相应的深部岩溶系统线性关系的斜率和截距均比表层岩溶系统的线性关系的斜率和截距为大。文中所建立的这些线性关系为校正脱气法萃取物测定得到的δ13CDIC值提供了一个可能的经验校正公式。 相似文献
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Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls 总被引：2，自引：0，他引：2
Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ18O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ18O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO2 and aqueous HCO?3. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ18O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate. 相似文献