湖泊体系中长链烯酮研究进展

长链烯酮不饱和度(U37k?)作为定量反映古温度变化的重要替代指标, 已在海洋中得到广泛应用, 但在湖泊中长链烯酮不饱和度与温度的关系及其母源研究则很少。课题组研究了中国不同气候带、不同水化学环境湖泊表层沉积物中长链烯酮, 发现多数湖泊中存在2~4个不饱和键的长链烯酮, 首次报道硫酸盐型湖泊中存在长链烯酮, 总结了湖泊中长链烯酮的分布模式, 探讨了分布模式与环境、母源的关系。研究了湖泊长链烯酮不饱和度与温度的关系, 发现湖泊长链烯酮不饱和度与年均气温和春秋季节温度高度相关, 建立了中国湖泊表层沉积物中长链烯酮不饱和度与温度的经验函数关系, 结合文献中发表的数据, 建立了从热带的北缘湖光岩玛珥湖到北极的格陵兰的湖泊沉积物中长链烯酮不饱和度与温度的经验函数关系: U37k? = 0.031? T + 0.094 (n=76, r2 = 0.67)。首次发现并成功分离出湖泊中长链烯酮母源等鞭金藻Chrysotila lamellosa, 通过单藻种控温培养, 建立长链烯酮不饱和度与水温关系方程, 实验室培养公式与经验公式斜率一致, 验证了长链烯酮不饱和度温标, 表明长链烯酮是可靠的陆地温标。     

长链烯酮不饱和度温标研究进展

长链烯酮不饱和度温标是古温度研究的重要替代指标。介绍了小样量，低长链烯酮样品的分析方法，长链烯酮的来源，分布，长链烯酮的不饱和度与温度的关系及其在古环境研究中的应用。介绍海洋中长链烯酮研究最新进展的同时，着重阐述了湖泊中长链烯酮研究现状及存在的主要问题。     

长链烯酮在古大气二氧化碳分压重建的应用

大气二氧化碳浓度的变化与全球冰盖变化、温度、海平面变化密切相关,了解过去大气二氧化碳浓度的变化及对二氧化碳与气候之间关系的研究,是预测未来气候变化的重要手段。长链烯酮碳同位素是重建古大气二氧化碳分压(p CO2)的重要指标之一,广泛应用于新生代以来大气二氧化碳的重建。对长链烯酮重建大气二氧化碳的方法进行了综述,介绍了颗石藻长链烯酮的地球化学性质,回顾了二氧化碳被动扩散模型的发展、长链烯酮重建二氧化碳的指标的发展及其不确定性,颗石藻的碳浓缩机制以及新生代以来长链烯酮重建大气二氧化碳的地质记录。     

塔里木盆地海相碳酸盐岩沥青"A"的地球化学特征

塔里木盆地采集的海相碳酸盐岩样品经粉碎后在索氏抽提器中用氯仿溶液抽提,正己烷沉淀沥青质后,可溶有机质进行柱色层族组成分离,获得饱和烃、芳烃、非烃,饱和烃和芳烃直接进行气相色谱-质谱分析,非烃经三氟化硼-甲醇混合液酯化后进行气相色谱-质谱分析。结果显示,样品有机质的演化程度高,母质类型以水生生物为主,台地相成烃古环境为富含单质硫的微生物发育的咸化深水还原环境。样品有机质经历过强烈的环化-芳构化过程和去甲基化过程有利于以甲烷为主的天然气的生成。样品的芳烃馏分中检测到C31-16-one、C33-16-one和C35-18-one长链中位酮化合物,推断这些长链中位酮可能是有机酸盐存在的特征生物标识化合物。     

加速溶剂萃取提取土壤中正构烷烃的方法研究

建立了加速溶剂萃取技术提取-柱色谱分离-气相色谱分析土壤样品中正构烷烃的方法。优化了压力、温度、静态时间、循环次数等参数。随着温度、静态时间、循环次数和压力的增加,正构烷烃短碳链、长碳链和总正构烷烃的量逐渐增加。加速溶剂萃取提取土壤中正构烷烃的条件是:萃取温度150℃,萃取压力10.3 MPa,循环2次,静态提取时间10 min。加速溶剂萃取-柱色谱分离-气相色谱法测定土壤中正构烷烃的方法精密度(RSD)为8%~23%。加速溶剂萃取法提取总正构烷烃量、短碳链正构烷烃量显著高于索氏抽提法的提取量。     

南海长链烯酮化合物的检测及U37^k值的应用

首次系统地在南海大面积站位中检测出长链烯酮化合物。通过长链烯酮指标Ｕ３７ｋ与实测表层海水温度（ＳＳＴ）的对比研究,发现海洋沉积物样品在室温下长期（１７ａ）密封保存,长链烯酮指标Ｕ３７ｋ值无明显变化。Ｕ３７ｋ值在南海海区指示的表层海水温度与季节有关,主要反映秋、冬两季,即１０月至次年３月间的ＳＳＴ。     

薄层色谱-光密度法分离分析原油族组成

以微型柱色谱为基础,分离原油样的族组成。用薄层色谱扫描仪测定各组分的光密度,建立与柱色谱之间映射关系,计算出各组分的含量和原油的族组成。通过比较发现,薄层色谱测定结果与微型柱色谱吻合较好,且具有分离效果好、灵敏度高、操作简便、快速等优点。对于含蜡量较高的样品,薄层色谱一光密度法测定的原油族组成更精确。     

矿物包裹作中H_2、CO、CH_4、CO_2、H_2O的连续测定

前言 用气相色谱法测定矿物包裹体中H_2、CO、CH_4、CO_2、H_2O等气体成分,近来有些报导,但是包括H_2O在内的以上气体成分的分析都是采用两种以上的方法或一个附有两根色谱柱的切换系统才能完成。本法的特点是采用一根1米长的TDX—01色谱柱,用氩为载气,热导池检测器,仅用0.2～0.5g的样品在半小时内就可以同时完成包裹体中H_2、CO、CH_4、CO_2、H_2O的提取,分离和测定。     

电化学检测器-离子色谱法测定地下水样品中氰化物

国内对于离子色谱法测定氰化物已有报道。本文在文献[1]的基础上,改用HPIC-AS_4型色谱柱分离,使工作效率提高了4倍。采用电化学检测,可以准确地测出水样中1μg/L的氰化物。方法简便、快速、准确,测定范围宽,高达1000μg/L的氰化物也能准确定量。一般水样在进样3 min后即可得到分析结果。     

GDX—105在He、H_2、N_2、O_2、CH_4和CO_2气相色谱分析中的应用

天然水中的 He、H_2、N_2、O_2、CH_4和 CO_2等气体成分具有重要的水文地球化学意义。气相色谱法为快速准确地分析这些气体提供了有力的手段。由于 CO_2的极性较强,在5 A 分子筛柱上发生不可逆吸附,故目前多用程序升温或用两根色谱柱(一根充填5 A 分子筛,另一根充填硅胶或活性碳)来完成上述组分的分离测定。这样对测定精度有一定影响,分析周期也较长,或对仪器要求较高(具有程序升温装置或双柱双检测系统)。我们通过试验,用一根 GDX—105柱对 He、H_2、N_2、CH_4和 CO_2进行一次分离测定,取得了满意的效果。     

微波消解-气相色谱法测定沉积物中的木质素

改进了由Hedges和Ertel建立的沉积物样品中木质素碱性氧化铜氧化分解方法,研究了利用微波加热辅助氧化铜氧化分解沉积物中的木质素,然后用气相色谱法分离测定其单体分子。考察了温度和微波消解时间对木质素消解效率的影响,实验表明在150℃下消解90 min达到最高效率;建立的方法对沉积物中木质素各单体分子分析的加标回收率为91.4%～108%,平均相对标准偏差(RSD,n=5)为4.5%。改进的方法便于控制反应条件,提高分析效率,是较理想的沉积物样品中木质素组成分析的方法。     

青海湖沉积物中的长链不饱和脂肪酮（长链烯酮）

在青海湖沉积物中检出了含有２～４个双键的长链（Ｃ₃₇－Ｃ₄₀）甲基和乙基脂肪酮。这是世界沉积于碱性环境和各种不同盐度条件下（耳海，淡水；青海湖，半咸水；尕海，咸水）的近代湖泊沉积物中的长链不饱和脂肪酮的首次详细报导。许多地球化学家广泛用这些化合物经过计算公式来估算海洋沉积物的古温度。如果对这些化合物估算海洋沉积物古温度的计算公式进行适当校正，那么也可用这些化合物来推知湖泊沉积物的古温度。     

Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: implication for paleotemperature reconstruction

The successful reconstruction of sea surface temperatures using alkenone paleothermometry (U₃₇^k′) has relied on the premise that there is no significant differential degradation of alkenones with different states of unsaturation during diagenetic processes. To test this assumption, we conducted a comparative study of contemporary sediments in oxic and anoxic bottom waters from the Santa Monica Basin, offshore California. Long-chain alkenones were quantified and sea surface temperature were calculated using the calibrated U₃₇^k′–T relationship of Prahl et al. (1988). Our results show that temperature record from the oxic sediments is higher by as much as 4°C compared to those from time-equivalent anoxic sediments as a result of differential degradation of long-chain unsaturated alkenones and bioturbation mixing in the oxic sediments. The differential degradation of C_37:3 vs. C_37:2 alone could account for up to 2.5°C difference between these two records. This finding has significant implication in the interpretation of paleo–sea surface temperature data using alkenone paleothermometry.     

金川铜镍硫化物样品中锇同位素比值的高精度分析

采用两种独立的190Os稀释剂、4个不同的化学流程,用等离子体质谱仪、TRITON热表面电离质谱仪和MAT-262固体质谱仪3种质谱仪器,在4个实验室分别对采自金川铜镍硫化物样品的187Os/188Os同位素比值进行分析,样品分析数量达到56个。4个实验室获得的结果分别为0.3356±0.0018(n=12,2s)、0.3363±0.0008(n=6,2s)、0.3363±0.0010(n=18,2s)和0.3353±0.0034(n=20,2s)。采用ISOPLOT软件对所得56个数据进行加权平均计算,得到187Os/188Os同位素比值为0.33602±0.00022(置信度95%)。两台TRITON热表面电离质谱仪测量的结果几乎完全一致,且精度高于MAT-262固体质谱仪和等离子体质谱仪。比较了碱熔和Carius管两种溶样方法,结果表明,对于所研究的样品,用Carius管溶矿方式可以将含锇矿物完全溶解。     

Characteristics of alkenones synthesized by a bloom of emiliania huxleyi in the Bering Sea

We investigated the characteristics of the alkenones produced by a bloom of Emiliania huxleyi in the eastern Bering Sea in 2000. Alkenones were detected in surface waters between 57°N and 63°N, where phosphate concentrations were low and the ammonium/nitrate ratio was high. The total alkenone content (C_37:2, C_37:3, and C_37:4) ranged from 22.0 to 349 μg g⁻¹ in suspended particles and from 0.109 to 1.42 μg g⁻¹ in surface sediments. This suggests that a large proportion of the particulate alkenones synthesized in the surface water rapidly degraded within the water column and/or at the water-sediment interface of the Bering Shelf. The change in the stable carbon isotopic composition (δ¹³C) of C_37:3 alkenone could not be explained only by variation in [CO₂(aq)] in the surface water but also depended on the growth rate of E. huxleyi. The alkenone unsaturation index (U^K′₃₇) was converted into an alkenone “temperature” with three equations [Prahl et al 1988], [Sikes et al 1997] and [Müller et al 1998]; Sikes et al.’s (1997) equation gave the best correlation with the observed sea surface temperature (SST) in the eastern Bering Sea. However, some temperatures estimated by Sikes et al.’s (1997) equation from the U^K′₃₇ varied from the observed SST, possibly because of the rapidly changing rate of alkenone synthesis in the logarithmic growth stage or the low rate of alkenone synthesis when nutrients were limiting. Temperatures estimated from U^K′₃₇ in the surface sediments (6.8-8.2°C) matched the observed SST in September (7-8°C) but differed from the annual average SST of 4 to 5°C, suggesting that most of the alkenone in the eastern Bering Sea was synthesized during limited periods, for instance, in September. The relative amounts of C_37:4 alkenone as proportions of the total alkenones (referred to as C_37:4%) were high, ranging from 18.3 to 41.4%. Low-salinity water (<32 psu) within the study area would have contributed to the high C_37:4% because a negative linear relationship between C_37:4% and salinity was found in this study.     

巯基棉分离富集-原子荧光光谱法测定重晶石中痕量汞

重晶石样品研磨过筛,用EDTA-氢氧化钠混合溶液络合处理,盐酸调节至弱酸性释放出汞,处理后的样品用原子荧光光谱法测定矿样中的痕量汞。采用巯基棉分离富集有机汞及无机汞,在pH 3~4时巯基棉可充分吸附汞,分别用2 mol/L和6 mol/L盐酸洗脱有机汞和无机汞,并将有机汞转化为无机汞。对影响汞测定的实验条件及干扰元素进行探讨。方法线性范围为0.00~5.00 ng/mL,相关系数为0.999 6;加标回收率为92.0%~114.0%。方法具有简便、快速、基体干扰少、灵敏度高等优点。     

Salinity control on long-chain alkenone distributions in lake surface waters and sediments of the northern Qinghai-Tibetan Plateau, China

Long-chain alkenones in lacustrine settings are potentially excellent biomarkers for the reconstruction of past terrestrial environmental conditions, and have been found in many different types of lakes around the globe. A wider range of factors influence the occurrence and distribution of alkenones in lake sediments and waters when compared to marine systems. Lake environmental conditions, such as temperature (in particular) and salinity, are among the key factors controlling alkenone distributions in lacustrine settings. Here we investigated alkenone distribution patterns in lakes of the northern Qinghai-Tibetan Plateau, China, and their possible relationship with environmental conditions, by analyzing paired samples of suspended particulate matter in surface waters and surface sediments. Salinity of investigated lake waters ranges from almost 0 to ∼100 g/L, while temperature variation among the lakes is minimal, effectively eliminating temperature effects on the alkenone distribution patterns observed here. We show that (1) alkenone concentrations vary substantially between the lakes, yet controlling mechanisms remain elusive; (2) C₃₇/C₃₈ ratios are substantially lower in the lakes of the Qaidam Basin than in the Lake Qinghai region, probably indicating different alkenone producers in the two regions; and (3) large variations in %C_37:4 (the percentage of the C_37:4 alkenone), determined from both surface waters and sediments, are negatively correlated with salinity. We suggest that the %C_37:4 index could be used as a salinity indicator at least on a regional scale, with careful considerations of other potentially complicating factors. However, potential reasons for why salinity could significantly affect %C_37:4 values need further investigation.     

Temperature and Salinity Effects on Alkenone Ratios Measured in Surface Sediments from the Indian Ocean

We compare alkenone unsaturation ratios measured on recent sediments from the Indian Ocean (20°N–45°S) with modern sea oceanographic parameters. For each of the core sites we estimated average seasonal cycles of sea surface temperature (SST) and salinity, which we then weighted with the seasonal productivity cycle derived from chlorophyll satellite imagery. The unsaturation index (U₃₇^K′) ranges from 0.2 to 1 and correlates with water temperature but not with salinity. TheU₃₇^K′versus SST relationship for Indian Ocean sediments (U₃₇^K′= 0.033 SST + 0.05) is similar to what has been observed for core tops from the Pacific and Atlantic oceans and the Black Sea. A global compilation for core tops givesU₃₇^K′= 0.031 T + 0.084 (R= 0.98), which is close to a previously reported calibration based on particulate organic matter from the water column. For temperatures between 24° and 29°C, however, the slope seems to decrease to about 0.02U₃₇^K′unit/°C. For Indian Ocean core tops, the ratios of total C₃₇alkenones/total C₃₈alkenones and the slope of theU₃₇^K′-SST relationship are similar to those previously observed for cultures ofEmiliania huxleyibut different from those previously published forGephyrocapsa oceanica.EitherE. huxleyiis a major producer of alkenones in the Indian Ocean or strains ofG. oceanicaliving in the northern Indian Ocean behave differently from the one cultured. In contrast with coccolithophorid assemblages, the ratios of C₃₇alkenones to total C₃₈alkenones lack clear geographic pattern in the Indian Ocean.