湖泊沉积物中有机碳稳定同位素测定及其古气候环境意义

１９９１年５月，利用澳大利亚转动式采样器在江苏固城湖获得总长６．２ｍ的完整柱状岩芯，以５ｃｍ间隔采样，对样品中有机质的稳定碳同位素研究表明。     

酸化过程对海洋沉积物中有机碳同位素分析的影响

海洋沉积物中有机碳同位素(δ13C)可以示踪海洋生态系统中有机质来源,对环境研究具有重要意义。分析沉积物中有机物的δ13C,需要对样品进行酸化,以去除无机碳的影响。由于不同来源的沉积物中无机碳的含量和组份存在差异,需要针对样品性质,优化酸化处理过程。本研究分别选取了无机碳含量不同的温带与热带河口、海湾沉积物样品,比较了3种不同酸化过程对有机物δ13C分析的影响。研究结果表明:方法1(酸洗法)中6%H_2SO_3和1mol/L H_3PO_4对无机碳含量较高的热带河口、海湾样品去除效率较低,而2mol/L HCl去除无机碳酸盐的效果较理想。方法2(酸蒸法)并不适用于无机碳含量较高的热带河口、海湾样品;而对于无机碳含量相对较低的温带河口、海湾样品,9h酸蒸较为适宜。方法3(非原位酸洗)的结果较方法1和方法2偏正,表明其对含13C丰富的有机组分破坏较小,且方法3中残留的酸对δ13C的分析没有影响。因此,方法3是去除海洋沉积物中无机碳较理想的方法。     

北冰洋西部沉积物有机碳、氮同位素特征及其环境指示意义

通过对楚科奇海及邻近的北冰洋深水区表层沉积物中有机碳同位素含量(δ13C)、氮同位素含量(δ15N)及生物成因SiO₂(BSiO₂)含量分析,结果表明海源和陆源有机质的分布受海区环流结构和营养盐结构所制约.楚科奇海中西部和楚科奇海台受太平洋富营养盐海水的影响,海洋生产力高,沉积物中海源有机质和BSiO₂含量高;靠阿拉斯加一侧海域海水的营养盐含量和生产力都偏低,沉积物中陆源有机质比重增加;在研究区北部和东北部的楚科奇高地和加拿大海盆,冰封时间较长,营养盐供应少,海洋生产力低,但来自马更些河和阿拉斯加北部的陆源有机质增多,沉积物中BSiO₂含量小于5%,海源有机质百分含量小于40%.由于亚北极太平洋水通过楚科奇海向北冰洋海盆输送,研究区营养盐池表现为开放系统,营养盐的利用率与它的供应成反比,与海洋生产力成反比.     

南日群岛东部海域岩芯沉积物有机碳含量和δ13CTOC值的变化特征及古气候环境意义

2008年在南日群岛东部海域用钻机采集长度为1 004 cm的岩芯样品,测试沉积物中总有机碳（TOC）含量、稳定碳同位素比值（δ13CTOC）、碳氮比值（C/N）、碳酸盐含量以及14C数据,分析其垂直剖面上的变化特征,阐明其沉积环境和古气候的指示意义.沉积物TOC含量变化范围为0.44%～0.74%,垂直剖面上总体显示出末次冰期和全新世中期TOC含量较高,全新世早期相对稳定,而全新世中后期TOC波动范围明显增大.C/N值在5.3～14.9之间变化,平均值为8.1;δ13CTOC值范围为-23.07‰～-21.04‰,表明沉积物中的有机质以海洋自生为主,同时混有部分陆源有机质.碳酸盐含量在3.3%～10.9%之间.TOC含量、C/N比值、δ13CTOC值在岩芯垂直剖面上具有很好的相关性.14C测年数据以及各要素测值在垂直剖面上的变化特征表明：自11 250 aBP以来该海域附近古气候有可能经历了以下4个演化阶段：①11 500～9 000 aBP期间气候寒冷、海平面下降,采样点可能为浅水区或潮间带;②9 000～8 000 aBP期间为升温期,气候由寒冷转向温暖;③8 000～4 300 aBP期间,为相对稳定的暖湿期,在后期气候出现小幅的波动;④4 300 aBP至今,气候进入明显的周期性波动期,暖湿和干冷气候多次交替变化;4 300～3 000 aBP期间为相对寒冷的时期;3 000～1 800 aBP期间为较稳定温暖期,1 800～1 000 aBP期间气温快速降低,标志着研究区进入一个新的寒冷阶段,但是自1 000 aBP以来,气候又再次出现转暖的趋势.     

由东海、黄海沉积物中有机碳含量及稳定同位素组成重建200a以来初级生产力历史记录

从20世纪80年代以来古生产力的重建研究一直是国内外海洋生态学研究的热点,但已有的大多数研究是在深海区;而陆架区的特点是来自陆源物质的影响往往比较明显,因此,研究难度远较深海区大。利用现代沉积物中的有机碳稳定同位素组成来估算海源碳的含量,在此基础上,结合调查区域表层沉积物中的几个初级生产力的代表性指标(浮游植物总量、叶绿素a浓度以及硅藻含量)的调查资料,寻求岩心中海源碳与古生产力指标的相关关系,再由南黄海冷涡沉积区3个典型柱状沉积物中海源碳重建了200a以来高分辨率的古生产力记录,这对陆架海生态环境演变规律的研究有重要意义。对重建所得到的南黄海近代初级生产演化因素的初步探讨表明,近200a来初级生产力波动升高与海水表层温度的升高趋势是一致的,但其最主要的控制因素还是营养盐的供应,其中陆源营养物质和污染物质的影响起到了重要的作用。     

南极罗斯海柱样沉积物中有机碳和氮元素地球化学特征及其来源

南极周边海域沉积物中的有机碳和氮元素地球化学特征对于深入研究全球碳循环和海洋生态环境演变具有重要意义。本文对取自南极罗斯海的RBA08C柱状样沉积物进行了有机碳和氮元素地球化学特征分析。结果表明：RBA08C柱样中TOC含量在顶部0~12cm呈现随柱深增加而降低的趋势, 自12cm以深含量总体相对稳定; TN总体具有与TOC相同的变化趋势, 两者含量变化呈现较强正相关性, 说明可能具有相同来源; 沉积物TOC/TN比值和δ13C值揭示RBA08C柱样有机质主要为海洋生源沉积, 其含量变化应主要受控于上层水体生产力、沉积速率和氧化还原环境等因素的共同作用; RBA08C柱样的TOC埋藏率约为50%, 与位于普里兹湾埃默里冰架边缘的IS-4站柱样相同, 加之较为相近的TOC和TN含量及变化趋势, 表明两者可能具有相近的沉积速率, 其所在的海区是南极海域较重要的碳循环和碳储区。     

Organic carbon stable isotope ratios of continental margin sediments

Stable isotope ratios (δ¹³C) of total organic carbon were measured in surface sediments from the continental margins of the northern and western Gulf of Mexico, the north coast of Alaska and the Niger Delta. Gulf of Mexico outer-shelf isotope ratios were in the same range as has been reported for Atlantic coastal shelf sediments, ?21.5 to ?20‰. Off large rivers including the Mississippi, Niger and Atchafalaya (Louisiana), δ¹³C values increased from terrigenous-influenced (around ?24‰) to typically marine ($\text{～?20‰}$) within a few tens of kilometers from shore. This change was accompanied by a decrease in the amount of woody terrigenous plant remains in the sediment. Alaskan continental margin samples from the cold Beaufort Sea had isotopically more negative carbon (?25.5 to ?22.6‰) than did warmer-water sediments. The data indicate that the bulk of organic carbon in Recent sediments from nearshore to outer continental shelves is marine derived.     

Radiocarbon and stable carbon isotope compositions of organic compound classes in sediments from the NE Pacific and Southern Oceans

Radiocarbon (Δ¹⁴C) abundance and stable carbon isotope (δ¹³C) compositions were measured for total lipid, total hydrolyzable amino acids (THAA), total carbohydrates (TCHO), and acid-insoluble organic fractions separated from phytoplankton, zooplankton, and sediment cores collected from two abyssal sites, one in the northeast (NE) Pacific Ocean and one in the Southern Ocean. These results are compared with those obtained for a separate core from the NE Pacific and reported by Wang et al. [Geochim. Cosmochim. Acta 62 (1998) 1365.]. An uncharacterized acid-insoluble fraction dominated (43–57%) the sediment TOC pool at both sites. Sediment collected from the NE Pacific exhibited higher TOC, TN. and higher Δ¹⁴C values and contained both labile (THAA and TCHO) and refractory (lipid and acid-insoluble) fractions. In contrast, sediment from the Southern Ocean had much lower TOC and Δ¹⁴C values, which indicated that organic matter was extremely refractory. Sedimentation rates calculated from ¹⁴C ages of TOC for both sites indicate that the differences in the organic composition and Δ¹⁴C signatures of organic matter in the sediments likely resulted from the differences in production and deposition of organic matter to the sediment, and the diagenetic stages of sedimentary organic matter in the two oceans.Unlike Δ¹⁴C, stable carbon isotopic (δ¹³C) compositions of TOC in the sediments of the two oceans had similar values, which reflect not only the organic matter input from marine-derived sources but also the nature of degraded, predominately uncharacterized organic fraction in these sediments. The differences in δ¹³C values among the compound classes in sediments at both sites can be attributed to the carbon isotopic signatures in original sources during photosynthesis and associated environmental factors. Preferential degradation of organic matter and heterotrophic effects may also play important roles for the observed δ¹³C variations and these effects need to be further investigated.     

A comparison of lignin and stable carbon isotope compositions in quaternary marine sediments

Organic matter in four Quaternary sediment cores from the Gulf of Mexico and one core from the Washington State coast have been analyzed for lignin and stable carbon isotope compositions. Holocene sequences of all five cores contain organic matter with high relative abundances of ¹³C ($\text{δ}{}^{13}\text{C = ?19.0 to ?22.5\% versus PDB}$) and low lignin concentrations, both of which are consistent with a marine origin. Distinctly lower ¹³C concentrations ($\text{δ}{}^{13}\text{C = ?24.0 to ?25.5\%}$) occur in underlying glacial-age sequences from four of the five cores, including the core from the Washington coast where such trends are previously unreported. Although the carbon isotopic compositions of these Pleistocene sediments are typical of predominantly land-derived organic matter, they contain only about 5% of the lignin found in modern sediments of similar $\text{δ}{}^{13}\text{C}$ from adjacent continental shelves. The lignin-poor organic matter in the glacial-age deposits appears to be either marine-derived or terrigenous material that likely was depleted in vascular plant debris at the time of deposition.     

TOC-IRMS联用在线高温氧化测定溶解有机碳稳定同位素组成的方法研究

本研究利用总有机碳分析仪联用稳定同位素质谱仪(TOC-IRMS)技术,探讨了高温氧化法测试水体中溶解有机碳(Dissolved Organic Carbon, DOC)含量及稳定碳同位素组成。根据溶解有机碳的组成特征,从氧化难易程度、分子结构等方面选取5种可溶于水的化合物：咖啡因、葡萄糖、邻苯二甲酸、乙酸钾和腐殖酸钠,配置成DOC溶液。通过改变溶液碳含量、氧化温度、通氧量大小,载气流速等参数,研究不同实验条件对DOC碳转化率及δ¹³C值的影响。TOC-IRMS在氧化温度850℃,通氧时长20 s(流速10 cm³/min),载气流速80 cm³/min的条件下,测得5种化合物不同浓度DOC溶液的平均碳转化率为95.69%～103.57%;δ¹³C值与标定参考值基本一致,差值范围为-0.82‰～0.55‰。在上述实验条件下,测得不同类型水样的DOC含量相对标准偏差小于3.7%,δ¹³C值的标准偏差小于0.2‰,结果表明TOC-IRMS联用在线高温氧化法测定不同类型水样的DOC含量...     

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO₂ evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1–5 μmol of carbon and has an associated blank of 0.1–0.2 μmol of carbon.Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO₂ as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3.. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The δ¹³C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC.The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average δ¹³C = −12.4.). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and δ¹³C of pore-water DOC was nearly 8. lighter at 1.5–2.0-cm depth than in the mat surface layer (0–0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and δ¹³C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.     

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (δ¹³C) compositions and n-alkane (nC_16–38) concentrations were measured for Spartina alterniflora, a C₄ marsh grass, Typha latifolia, a C₃ marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. δ¹³C values of organic matter preserved in the upper fresh water site sediment were more negative (−23.0±0.3‰) as affected by the C₃ plants than the values of organic matter preserved in the sediments of middle (−18.9±0.8‰) and mud flat sites (−19.4±0.1‰) as influenced mainly by the C₄ marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC₂₁ to nC₃₃ long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC₂₉ was the most abundant homologue in all samples measured. Both δ¹³C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters.     

Identification of Pb sources in Yellow Sea sediments using stable Pb isotope ratios

Rapid economic developments in East Asian countries have inevitably resulted in environmental degradation in the surrounding seas, and concern for both the environment and protection from pollutants is increasing. Identification of sources of contaminants is essential to environmental pollution management. In this study, the provenance of anthropogenic lead (Pb), a major pollutant of Yellow Sea sediments, was determined for river mouth sediments, including those of the Changjiang, Huanghe, Han, and Geum Rivers, and for age-determined shelf core sediments through the measurement of Pb isotope ratios in the HCl-leached fraction using multi-collector inductively coupled plasma-mass spectrometry (MC ICP/MS). Anthropogenic Pb has accumulated in shelf core sediments since 1910, and its isotope ratios were estimated as 0.863–0.866 and 2.119–2.125 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively, from the mixing relationships of the two endmembers. River mouth sediments exhibited enough distinction in anthropogenic Pb isotope ratios to be discriminated: 0.874 (2.144) in the Huanghe, 0.856 (2.129) in the Han, 0.857 (2.122) in the Geum, and 0.854 (2.101) in the Changjiang for ²⁰⁷Pb/²⁰⁶Pb (²⁰⁸Pb/²⁰⁶Pb), respectively. Although isotope ratios of geogenic Pb in sediments dating before 1910 showed narrow ranges (0.842–0.845 and 2.088–2.100 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), distinct isotope ratios in each core permitted source identification of sediments in the Yellow Sea based on geographic locations and the geogenic Pb of each river. By comparing the isotope ratios of the estimated anthropogenic Pb to source-related materials, the provenances of anthropogenic Pb in Chinese river sediments were presumed to be Chinese coal or ore, which is also a major source of atmospheric particulate Pb. The anthropogenic Pb in the shelf core sediments in the northern Yellow Sea originated from northern Chinese cities such as Beijing and Tianjin through atmospheric pathways. Pb isotope ratios indicated that Pb in Korean river sediments was characteristic of local Korean ores.