干酪根化学降解产物的碳同位素组成研究

采用一系列温和的化学降解法对松辽盆地南部嫩江组烃源岩的干酪根进行连续的选择性化学降解，并对不同降解产物进行色谱—同位素比值质谱分析。研究表明碱性水解和脱硫产物以一元脂肪酸和正构烷烃为主，其中正构烷烃碳同位素分布曲线呈现一定的“负倾”（即随碳数增加呈现逐渐贫13C）趋势；一元脂肪酸以C16和C18为主，具有明显的偶碳优势，与同碳数的正构烷烃具有相似的碳同位素组成。氧化产物则以一元脂肪酸和α,ω 二元脂肪酸为主，一元脂肪酸低碳数部分呈现“负倾”趋势，高碳数部分则呈现“正倾”的趋势；α,ω 二元脂肪酸与低碳数的一元脂肪酸具有相似的分布，表明它们可能具有相同的母源。对比研究表明JL 30抽提物中正构烷烃可能存在混源的影响，其碳同位素组成是多源混合的结果。     

湖北清江和尚洞洞顶植物叶片和土壤的类脂物对比及其意义

用GC-MS对湖北清江岩溶地区和尚洞洞顶植物叶片与该洞上覆土壤层中的类脂物进行了分析和对比。在植物叶片中检测出了一系列直链烷烃、脂肪酸、以及丙三醇、植醇和甾醇等类脂物,其中直链烷烃的碳数分布范围大体在C21～C36之间,以C29或C31为主峰且具有奇偶优势;脂肪酸的分布主要集中在中、短链脂肪酸内（C数<23）,以C16为主峰呈单峰型分布且具有偶奇优势;醇的分布很不规则,仅检测出丙三醇,植醇和三种甾醇,没有检测到脂肪酮类化合物。与之相比,洞顶上覆土壤层中检测出更加丰富的类脂物。类脂物具有如下特征:正构烷烃以C31为主峰,还存在低碳数正构烷烃和异构烷烃,如2-甲基、3-甲基、4-甲基、5-甲基、6-甲基、7-甲基、8-甲基等一系列的单甲基支链烷烃,这些支链烷烃显示了微生物的贡献;脂肪酸分布也以低碳数的C16为主峰,且低碳数脂肪酸的含量较植物叶片中明显的增加,同时一些异构和反异构脂肪酸（C14∶0,C15∶0和C17∶0）以及一些单不饱和脂肪酸（C16∶1,C17∶1,C18∶1和C20∶1）也被检测到,也表明土壤中的脂肪酸不仅存在高等植物的贡献,还存在微生物的来源;没有植醇,但出现姥鲛烷和植烷并检测到了一系列脂肪醇化合物,碳数分布在C21～C36之间;检测到一系列的酮,具有奇偶优势,碳数分布范围在C23～C30和C33。高等植物叶片和土壤的差异反映了微生物对高等植物类脂物输入到土壤过程的重要贡献。本研究工作不仅提供了该岩溶地区植物叶片的类脂物信息,还为研究土壤有机质的来源和植物叶片中类脂物在地质过程中的转变提供信息,更为研究岩溶地区滴水和石笋中类脂物的来源提供一定的参考。     

Distribution Characteristics of n-Alkanes in Surface Sediments on Lake Bottom in Koh Xil Area, Qinghai-Xizang(Tibet) Plateau

湖泊沉积物中有机质正构烷烃分布特征对有机质母源、沉积环境等有较好的指示作用.本文通过对青藏高原高寒地区可可西里不同盐度的现代湖泊表层沉积物样中有机质正构烷烃的分析,表明正构烷烃分布主要受陆生植被、水生植物和水体盐度的控制.结果表明,有机质以眼子菜为主的沉水植物来源的正构烷烃有较高的C23正构烷烃峰和高丰度中等链长正构烷烃,以及高丰度C31、C29、C27正构烷烃峰;而没有C23正构烷烃峰,仅有高丰度C31、C29、C27正构烷烃峰,代表了陆生草本植物来源的特征.咸水、微咸水还原环境有明显高Ph丰度.C17的高丰度代表了藻类植物来源特征.不同的中等碳数正构烷烃、高盐度沉积物中未见偶碳数正构烷烃特征表明有机母质的差异是沉积物中正构烷烃组成和分布差异的主要原因.同时,C27、C29的存在不一定就是陆生木本植物来源有机质,水生植物也具有相似的特征.     

银川盆地35ka以来古植被演化的类脂分子记录

为了更好地了解干旱-半干旱区的植被类型及其演化规律,利用气相色谱仪对银川盆地冰沟剖面河湖相沉积物中的正构烷烃进行了检测,结果显示其正构烷烃碳数分布范围为C15~C34,奇碳优势明显,以C29或C31为主峰的单峰型为主,但少量样品也出现双峰型分布模式。通过对冰沟剖面正构烷烃分布特征、碳优势指数CPI和L/H（ΣC21-/ΣC22+）指标的详细分析得知其有机质来源以陆生高等植物占主导优势。结合年代数据、有机碳同位素、长链正构烷烃平均链长ACL和C33/(C33+C27)值重建出35.0ka以来银川盆地植被类型以 C3植物为主,并且C3和C4植物的相对比例变化主导受温度制约,而木本和草本植被的演化主要受控于水分条件。     

青藏高原可可西里地区湖泊沉积物中有机质正构烷烃分布特征

湖泊沉积物中有机质正构烷烃分布特征对有机质母源、沉积环境等有较好的指示作用。本文通过对青藏高原高寒地区可可西里不同盐度的现代湖泊表层沉积物样中有机质正构烷烃的分析,表明正构烷烃分布主要受陆生植被、水生植物和水体盐度的控制。结果表明,有机质以眼子菜为主的沉水植物来源的正构烷烃有较高的C23正构烷烃峰和高丰度中等链长正构烷烃,以及高丰度C31、C29、C27正构烷烃峰;而没有C23正构烷烃峰,仅有高丰度C31、C29、C27正构烷烃峰,代表了陆生草本植物来源的特征。咸水、微咸水还原环境有明显高Ph丰度。C17的高丰度代表了藻类植物来源特征。不同的中等碳数正构烷烃、高盐度沉积物中未见偶碳数正构烷烃特征表明有机母质的差异是沉积物中正构烷烃组成和分布差异的主要原因。同时,C27、C29的存在不一定就是陆生木本植物来源有机质,水生植物也具有相似的特征。     

东北地区五大连池湖相沉积物正构烷烃和单体碳同位素特征及其古植被意义

对中国东北地区小兴安岭与松嫩平原过渡带五大连池青石钻孔湖相沉积物进行了有机地球化学分析,检测出丰富的正构烷烃生物标志化合物.本文主要讨论了正构烷烃的分布及其单体碳同位素组成特征.正构烷烃具有前峰型和双峰型两种分布特征,表明其有机质为混合来源,包括低等菌藻类生物和陆生高等植物输入.正构烷烃的分布特征表明,自35.2ka B.P.以来,nC27/nC31和ACL指标共同记录了东北地区小兴安岭与松嫩平原过渡带的植被以草本为主.对C27、C29和C31长链正构烷烃进行了单体碳同位素测定,并利用二元模式估算了C3和C4植物相对生物量,结果表明,自35.2ka B.P.以来,研究区的植被以C3植物为主.期间在典型冷暖气候事件中,受温度变化的影响,C3/C4植物的相对生物量有明显的变化,在全新世大暖期(6.0ka B.P.),受温度升高影响,C3植物的生物量显著减少,C4植物的生物量则明显增加;而在两次典型冷气候事件(中全新世降温事件8.2ka B.P.和新仙女木事件12.9ka B.P.)时期,受温度降低影响,C3植物的生物量有增加的趋势,C4植物的生物量则相对呈减少的趋势;在末次冰盛期21.0ka B.P.时,受明显低温特征的影响,C3植物生物量高达80.0％,这可能是当时低温的气候特征抑制了C4植物的生长.研究结果对探索我国东北地区C3/C4植物分布格局,并为评估未来气候演化对该地区植被格局和农业生产的影响提供科学依据.     

安徽宣城更新世红土正构烷烃分布特征及其古植被意义

利用气相色谱一质谱联用仪(GC-MS)在安徽宣城更新世红土中检测出了微量的分子化石,包括正构烷烃、一元正脂肪酸、一元正脂肪醇以及α-正构脂肪酮等．正构烷烃的分布型式表明其来源于低等菌藻类生物和陆生高等植物,其中高碳数正构烷烃主要以C29为主峰,显示流域中的植被类型以木本植物为主;(C27 C29)／(C31 C33)比值的变化反映出,在以木本植物占优势的背景下,流域中草本植物的相对比例也发生了多次变化．这一比值在本剖面上表现出多阶段的变化．而且这种变化与岩性、粒度变化密切相关,反映出这些参数可能还蕴涵着古气候信息．     

末次盛冰期以来泸沽湖沉积记录的正构烷烃分布特征和单体碳同位素组成及其古植被意义

泸沽湖是云贵高原上典型西南季风区的一半封闭湖泊,本文通过研究水深69.3m处长度为18.3m岩芯中15个样品的陆源高等植物正构烷烃分布特征及碳同位素组成,揭示了湖区木本/草本植被和C3/C4植被的变化历史,并试图探讨C3/C4植被变化的可能影响机制.在末次盛冰期至全新世早期,正构烷烃含量及(C27+C29)/2C31比值逐渐增加,正构烷烃(碳数＞C25)的平均碳链长度(ACL)值逐渐减少,指示木本植物比例相比草本植物较多且呈逐渐增加态势,表明气候逐渐向暖湿方向发展;而同一时期,陆源高等植物正构烷烃(C27、C29和C31)δ13C值均逐渐偏正,无法用气候变化来解释,应该反映了C3/C4植被变化,由此,通过二元模式计算得出的C4植物比例从19.6％逐渐增加至31.9％,上述结果表明该时期温度升高对C4植物增多起了主要作用.到全新世中期,正构烷烃分布特征表明木本植物比例依然较高,表明此时气候温暖湿润,而δ13C值则呈偏负的趋势,我们认为这是降雨增加和C4植物减少协同导致的.在全新世晚期,正构烷烃分布特征指出草本植物比例相对增加,而该时期的δ13C值则稍微偏正,这可能是因为气候变干所导致的.陆源高等植物正构烷烃分布特征所揭示的植被变化可以与研究区域孢粉记录进行较好对比.研究进一步明确了温度是C4植物出现的主控因素,而在温度满足要求时降雨的增多会降低C4对C3植物的竞争优势.     

柴达木盆地昆特依地区晚更新世正构烷烃分布特征及其环境变迁

为探讨柴达木盆地晚更新世的环境变迁,同时为青藏高原隆升对气候变化的影响提供基础资料,对柴达木盆地昆特依地区ZK1404钻孔沉积物中的正构烷烃分布特征以及ASM~(14)C测年数据进行了分析。结果显示,昆特依地区晚更新世沉积物的正构烷烃总体上呈现以高碳数为主的分布特征,多数样品以nC_(27)、nC_(29)为主峰,部分以nC_(31)为主峰,呈现出显著的奇碳优势。少数样品中低于nC_(21)的短链正构烷烃相对丰度较高,主要以nC_(17)、nC_(20)为主峰碳数,无明显的奇偶优势。根据正构烷烃分布特征、AMS~(14)C测年数据、区域地质调查资料及沉积环境判断,柴达木盆地昆特依地区晚更新世(33600～26370a B.P.)气候环境以温凉干旱与温凉干旱偏湿交替出现为特征,与现代大陆性干旱荒漠气候截然不同。     

天目山泥炭类脂物记录的微生物特征和植被演替

为进一步了解泥炭中微生物特征和植被的变化,对采自浙江天目山的样品进行了类脂生物标志物与有机碳同位素(δ13Corg)的测定。有机碳δ13Corg值整体偏负,显示C3植物占优势的特点。正构烷烃的分布特征表明,大多数样品来源于陆生高等植物和低等菌藻类生物,其中高碳数正构烷烃主要以C29为主峰,显示植被类型以木本植物为主,但草本植物的相对比例也发生了多次变化,且这种变化与有机质的相对贡献量密切相关。在深度100~68cm,不同来源的有机质,特别是低等菌藻类的相对贡献量都相对较少;在深度68~30cm,低等菌藻类生物的贡献逐渐变大;而表层泥炭的有机质主要来源于高等植被,菌藻类的输入较少。泥炭有机碳同位素与类脂生物标志物的综合特征表明,该区植被经历了几次明显变化,并据此可将研究区中全新世以来环境演化分为早(4100~3200aB.P.)、中(3200~700aB.P.)、晚(700aB.P.以来)三个环境演化阶段,其结论与前人的环境演化与全球气候变化研究具有较好的可比性。     

An assessment and comparison of 230Th and AMS 14C ages for lacustrine sediments from Qarhan Salt Lake area in arid western China

The age framework of Qarhan Salt Lake in arid western China is still controversial due in part to (1) age discrepancy between conventional ¹⁴C and ²³⁰Th dating results, and (2) no AMS ¹⁴C ages of organic carbon from drilling cores in Qarhan Salt Lake were reported until now. In order to discuss these chronological problems, upper 54.50 m lacustrine sediments from a drilling core (ISL1A) recovered from Qarhan Salt Lake were dated based on ²³⁰Th and AMS ¹⁴C dating techniques. Results show that (1) AMS ¹⁴C ages of total organic carbon (TOC) from 4.65 to 30.29 m are almost in stratigraphic order and consistent with ²³⁰Th ages of halite in the corresponding layers; (2) AMS ¹⁴C ages of TOC from 30.29 to 54.50 m are younger with increasing depth. This phenomenon was also found in Shell Bar in the study area, suggesting that AMS ¹⁴C ages from upper 30.29 m are more reliable while those from lower 24.21 m in ISL1A may be underestimated; (3) ²³⁰Th ages of halite from lower 24 m lacustrine sediments are obviously older than AMS ¹⁴C ages of TOC in the corresponding layers, which results into different age framework of salt lake sediments in Qarhan Salt Lake; (4) if extrapolating these reliable AMS ¹⁴C ages in ISL1A, similar age framework with ²³⁰Th ages in this core confirms that ²³⁰Th ages are much close to the true ages of these sediments, which suggests that the forming timing of the bottom salt layer is ~50 ka.     

柴达木盆地察尔汗古湖相地层正构烷烃与河蚬化石记录的古生态环境

利用常规14C、加速器(AMS)方法对柴达木盆地察尔汗湖一典型古湖相沉积剖面系统测年,并对测年结果进行不同组分和不同实验室对比,确定该剖面发育于察尔汗古湖高湖面时期(39.7 ka B.P.～17.5 ka B.P.).通过对削面沉积物正构烷烃的系统分析,结果表明正构烷烃携带了重要的湖泊演化的环境和生物信息,其中nC2...     

北京延庆古湖正构烷烃分布特征及古气候意义

为了更好地了解华北平原核心区延庆盆地古气候演化,利用气相色谱仪对北京延庆盆地阜高营剖面湖相沉积物中的正构烷烃进行了检测.结果表明其正构烷烃含量丰富且连续,碳数分布范围为C₁₆~C₃₃,高碳数奇碳优势明显,中链和短链烷烃均无奇偶优势,多以C₂₉或C₃₁为主峰的单峰分布为主,同时存在少量低碳数和高碳数并存的双峰型.延庆古湖有机质以陆生植物为主,包含少量的菌藻类和水生植物.综合ESR年代序列、有机碳同位素（δ13C_org）、长链正构烷烃平均链长（average chain length,ACL）碳优势指数（carbon preference index,CPI）和正构烷烃Paq参数,将延庆盆地晚更新世中期以来的环境演变划分为:56.8~45.6 ka,气候暖湿,湖泊发育良好,湖面较高;45.6~31.5 ka,气候温湿,湖泊发育缓慢,水位略有下降;31.5~20.0 ka,气候冷干,湖泊水位严重下降;20.0~13.4 ka,气候较为干冷,有转暖趋势;13.4~9.2 ka,气候转暖,湖泊有所发育,但水位较低;9.2 ka至今,气候变干,湖泊萎缩.延庆古湖沉积物中正构烷烃参数的变化与古里雅冰心、李家塬黄土、深海氧同位素反映的气候变化较为一致,呈现冰期-间冰期旋回,且受控于同纬度太阳辐射量的变化.      

40～30ka B.P.中国西北地区暖湿气候的地质记录及成因探讨

新疆艾丁湖与柴窝堡湖记录、玛纳斯湖记录、巴里坤湖记录、伊犁黄土-古土壤记录、罗布泊沉积记录和塔里木盆地南缘克里雅河流阶地钙质结核层记录,青海察尔汗盐湖以及内蒙古古居延海沉积记录、白碱湖和吉兰泰盐湖、巴丹吉林沙漠钙质胶结层等记录均显示40～30kaB.P.时期整个西北地区气候温暖湿润.其中,内蒙古西部温度较现代高2.～3℃,西北大部分地区降水量成倍增加,气候显著湿润化.其成因可能是由于当时中、低纬度岁差周期高辐射所造成的海洋表面温度升高,蒸发加强,西风环流和夏季风为西北提供的水汽大幅度增多的缘故.     

Magnetostratigraphy and ~(230)Th dating of a drill core from the southeastern Qaidam Basin:Salt lake evolution and tectonic implications

The Qarhan Salt Lake area is the Quaternary depocenter of the Qaidam Basin, and carries thick lacustrine sediments, as well as rich potassium and magnesium salt deposits. The abundant resources and thick sediments in this lake provide an ideal place for the study of biogas formation and preservation, salt lake evolution, and the uplift of the Tibetan Plateau. In this study, we attempt to construct a paleomagnetic and ~(230)Th age model and to obtain information on tectonic activity and salt lake evolution through detailed studies on a 1300-m-long drill core(15DZK01) from the northwestern margin of the Qarhan Salt Lake area(Dongling Lake). Based on gypsum ~(230)Th dating, the age of the uppermost clastic deposit was calculated to be around 0.052 Ma. The polarity sequence consist of 13 pairs of normal and reversed zones,which can be correlated with subchrons C2r.1r-C1n of the geomagnetic polarity timescale(GPTS 2012)(from ~2.070 Ma to ~0.052 Ma). Sedimentary characteristics indicate that Dongling Lake witnessed freshwater environment between ~ 2.070 Ma and 1.546 Ma. During this period, the sedimentary record reflects primarily lakeshore, shallow-water and swamp environments, representing favourable conditions for the formation of hydrocarbon source rocks. Between 1.546 Ma and ~ 0.052 Ma, the Dongling Lake was in sulphate deposition stage, which contrasts with the central Qarhan Salt Lake area, where this stage did not occur in the meantime. During this stage, Dongling Lake was in a shallow saltwater lake environment, but several periods of reduced salinity occurred during this stage. During the late Pleistocene at ~0.052 Ma, the Dongling Lake experienced uplift due to tectonic activity, and saltwater migrated through the Sanhu Fault to the central Qarhan Salt Lake area, resulting in the absence of halite deposition stage. The residual saline water was concentrated into magnesium-rich brine due to the lack of freshwater, and few potassium salt deposits occur in the Dongling Lake area.     

太湖YLL1孔沉积特征揭示的全新世太湖演化史

本文通过对太湖西山岛衙甪里孔(YLL1)沉积物的粒度、总有机碳含量(TOC)、质量磁化率、元素含量及沉积年代等进行测试分析,探讨了全新世以来太湖湖盆的演化历史。根据沉积特征,可将4m深的YLL1孔分为上、中、下三段明显不同的沉积层。中段(153~231cm)沉积物平均粒径为7.65φ,粘土级颗粒含量高达48.78%,对比上段(0~153cm,6.29φ,21.77%)和下段(231~400cm,6.91φ,30.88%)为全孔最细;并且中段粒径随深度变化很小,平均粒径标准偏差为0.13,明显低于上段的0.70和下段的0.38;中段TOC和质量磁化率平均值分别为0.78%和19.41×10^-8m^3/kg,为全孔最高;XRF扫描数据显示元素含量在三段中变化显著:中段Al、K、Fe等元素含量相对上段和下段为最高,而Si含量最低。YYL1孔沉积特征参数显示,近80cm厚的中段泥质层与上下段截然不同,是一段标志性沉积层。该标志层广泛存在于太湖及其周边地区的地层中,并且该层位含有大量的富铁质小球粒结核和菱铁矿结核,AMS14C显示该层位年龄约为7kaB.P.。研究表明,太湖YLL1孔沉积记录了湖盆环境的3个不同阶段:下段对应末次冰期后期11kaB.P.左右的风成硬黄土层沉积,此时太湖尚未完全形成;中段泥质沉积标志层代表太湖第一次大水面形成,时代在7kaB.P.左右;上段对应5kaB.P.左右以来的湖相沉积。     

Numerical Modelling of Dissolving and Driving Exploitation of Potash Salt in the Qarhan Playa ? A Coupled Model of Reactive Solute Transport and Chemical Equilibrium in a Multi-component Underground Brine System

Firstly, the macroscopic chemical equilibrium state of a series of chemical reactions between intercrystal brine and its media salt layer （salt deposit） in Qarhan Salt Lake was studied by using the Pitzer theory. The concept of macroscopic solubility product and its relation with accumulated ore dissolving ratio were presented, which are used in the numerical model of dissolving and driving exploitation of potassium salt in Qarhan Salt Lake. And secondly, with a model forming idea of transport model for reacting solutes in the multi-component fresh groundwater system in porous media being a reference, a two-dimensional transport model coupled with a series of chemical reactions in a multi-component brine porous system （salt deposits） was developed by using the Pitzer theory. Meanwhile, the model was applied to model potassium/magnesium transport in Qarhan Salt Lake in order to study the transfer law of solid and liquid phases in the dissolving and driving process and to design the optimal injection/abstraction strategy for dissolving and capturing maximum Potassium/ Magnesium in the mining of salt deposits in Qarhan Salt Lake.     

Numerical Modelling of Dissolving and Driving Exploitation of Potash Salt in the Qarhan Playa——A Coupled Model of Reactive olute Transport and Chemical Equilibrium in a Multi-component Underground Brine System

Firstly, the macroscopic chemical equilibrium state of a series of chemical reactions between intercrystal brine and its media salt layer (salt deposit) in Qarhan Salt Lake was studied by using the Pitzer theory. The concept of macroscopic solubility product and its relation with accumulated ore dissolving ratio were presented, which are used in the numerical model of dissolving and driving exploitation of potassium salt in Qarhan Salt Lake. And secondly, with a model forming idea oftransport model for reacting solutes in the multi-component fresh groundwater system in porous media being a reference, a two-dimensional transport model coupled with a series of chemical reactions in a multi-component brine porous system (salt deposits) was developed by using the Pitzer theory.Meanwhile, the model was applied to model potassium/magnesium transport in Qarhan Salt Lake in order to study the transfer law of solid and liquid phases in the dissolving and driving process and to design the optimal injection/abstraction strategy for dissolving and capturing maximum Potassium/Magnesium in the mining of salt deposits in Qarhan Salt Lake.     

Evaluation of boron isotopes in halite as an indicator of the salinity of Qarhan paleolake water in the eastern Qaidam Basin,western China

In this study, nineteen brine samples from the Qarhan Salt Lake (QSL) in western China were collected and analyzed for boron (B) and chlorine (Cl) concentrations, total dissolved solids (TDS), pH values and stable B isotopic compositions. The B concentrations and δ¹¹B values of brines in the QSL range from 51.6 mg/L to 138.4 mg/L, and from +9.32‰ to +13.08‰, respectively. By comparison of B concentrations and TDS of brines in QSL with evaporation paths of brackish water, we found that B enrichment of brines primarily results from strong evaporation and concentration of Qarhan lake water. Combining with comparisons of B concentrations, TDS, pH values and δ¹¹B values of brines, previously elemental ratios (K/Cl, Mg/Cl, Ca/Cl, B/Cl) and δ¹¹B values of halite from a sediment core (ISL1A), we observe good correlations between B concentrations and TDS, TDS and pH values, pH and δ¹¹B values of brines, which demonstrate that higher B concentrations and more positive δ¹¹B values of halite indicate higher salinity of the Qarhan paleolake water as well as drier paleoclimatic conditions. Based on this interpretation of the δ¹¹B values of halite in core ISL1A, higher salinity of the Qarhan paleolake occurred during two intervals, around 46–34 ka and 26–9 ka, which are almost coincident with the upper and lower halite-dominated salt layers in core ISL1A, drier climate phases documented from the δ¹⁸O record of carbonate in core ISL1A and the paleomoisture record in monsoonal central Asia, and a higher solar insolation at 30°N. These results demonstrate that the δ¹¹B values of halite in the arid Qaidam Basin could be regarded as a new proxy for reconstructing the salinity record of paleolake water as well as paleoclimate conditions.