样品前处理过程中多环芳烃的稳定碳同位素分馏

利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。     

塔里木盆地寒武系层状硅质岩与硅化岩的元素、δ~(30)Si、δ~(18)O地球化学研究

塔里木盆地寒武系发育层状硅质岩和硅化岩,层状硅质岩主要发育于塔东下寒武统深水沉积相区;硅化岩发育于塔东上寒武统斜坡沉积区与西部台地区寒武系白云岩中。根据显微结构特征,可将硅化岩分为放射状硅化岩与交代残余结构硅化岩两种。分析结果表明,层状硅质岩在Al—Fe-Mn三元图中位于正常海水沉积硅质岩区内,在微量元素平均地壳标准化图解上显示平缓右倾的特征;层状硅质岩Si同位素组成护。δ30Si为0．99‰～1．4‰,O同位素组成δ18O为21．4‰～24．4‰,与沉积型硅质岩相吻合,指示了正常海水沉积成因。硅化岩区别于层状硅质岩的典型特征是具有高U异常的特征;罗西斜坡放射状硅化岩具有较高的微量元素和稀土元素含量（∑REE为18．8～96．9μg／g）与较低的Si、O同位素值（δ18O和δ30Si值分别为15．8‰和1．7‰）;西部台地区交代残余结构硅化岩具有较低微量元素和稀土元素含量（∑REE为0．58～2．61μg／g）与较高的δ30Si（1．0‰～3．8‰）、δ18O（21．6‰～27．0‰）值特征。盆地东西部硅化岩的地球化学差异可能与硅化流体的温度差异有关,罗西斜坡放射状硅化岩硅化温度相对更高;另一方面,硅化过程对h430SiO4选择性较高,因而形成的交代石英具有较高的铲勘值。根据古城4井硅化岩包裹体均一温度与交代石英的O同位素值计算得到交代流体的δ18O值为9．1‰,该值与酸性岩浆水的δ18O值相似,指示了硅化流体可能来自于岩浆或变质水;以δ18O值（9．1‰）作为西部台地区硅化流体的O同位素值,计算得到西部台地区硅化岩硅化流体温度为101．3～158．5℃。根据石英O同位素温度计计算的硅化流体温度呈东高西低的趋势,指示了硅化流体可能来自台地东部。     

塔里木盆地塔中-巴楚地区上奥陶统良里塔格组米兰科维奇旋回性沉积记录研究

通过露头、钻井岩芯沉积相观察及高频旋回识别,结合全岩碳氧同位素旋回、自然伽玛能谱测井ln(Th/K)值频谱分析及地震反射特征,研究了塔里木盆地塔中—巴楚地区分布的上奥陶统良里塔格组开阔台地及外缓坡相碳酸盐岩中发育的四～六级高频层序(旋回)特征及其叠置关系。认为其六级米级旋回、五级准层序及四级准层序组可能分别与20～40ka、100ka及400ka周期的Milankovitch日-地轨道气候旋回有关,并识别出该区良里塔格组由11～12个400ka周期的准层序组构成。提出海相碳酸盐岩全岩或生物壳碳同位素值可作为反映全球海平面相对变化的指标及识别形成三级层序的主控因素(全球海平面变化、地区性构造沉降-抬升运动)的方法——碳同位素-沉积旋回对比分析法。晚奥陶世良里塔格组沉积时期,塔中台地北缘总体表现为向上变浅的加积型沉积叠置型式,主要与塔中I号断裂活动控制形成的高陡型镶边台地边缘有关;巴楚台地西北缘则表现为向上变浅的加积-进积复合型沉积叠置型式,主要与其断裂活动弱、受沉积作用控制为主的缓坡台地边缘有关。塔中-巴楚台地良里塔格组表现为一个完整三级层序的形成与演化,主要受控于该台地的构造(沉降-抬升)运动而不是全球海平面变化,属于典型的地区性构造层序及不具有全球对比意义。     

钾稳定同位素在水文地球化学领域的研究进展与展望

地表硅酸盐岩矿物风化通常是水体中钙、镁、钠、钾等元素的重要来源,然而相比于水体中的钙、镁和钠,目前对钾的水文地球化学行为的认识仍十分有限。表生地球化学领域最新研究证明风化、吸附等多种水岩反应伴随着较大的钾同位素分馏,表明钾同位素技术可以用于示踪地下水中钾的来源及迁移转化。文章通过系统总结上地壳、水圈和其他地表储库（植物、肥料）的钾同位素组成,发现水圈普遍比大陆上地壳富集41K,为识别地下水的钾来源提供了基础;通过总结钾同位素在常见的水岩作用过程（硅酸盐岩矿物溶解、次生黏土形成、吸附作用、离子交换反应）中的分馏行为,发现硅酸盐岩矿物溶解分馏有限,次生黏土矿物形成引起水体富集41K,表面吸附和离子交换使水体富集39K,不同水岩反应中K同位素行为差异为示踪地下水中钾的迁移转化过程提供了基础;列举了应用钾同位素示踪硅酸盐岩风化和水体污染的最新研究成果。由于钾同位素是硅酸盐岩风化的良好示踪剂,可以利用钾同位素揭示CO2较充足含水层中钾元素释放及迁移转化机理;由于表面吸附和离子交换控制的钾同位素分馏方向与风化控制的钾同位素分馏方向不同,可以利用钾同位素识别出地下水循环过程中多种水岩反应对钾迁移转化的共同控制。在此基础上,对钾同位素在水文地球化学领域的应用进行了展望：（1）开展研究区多端元控制下地下水钾来源贡献的研究;（2）开展地下水漫长循环过程中钾迁移转化的定量研究;（3）联合使用多种同位素示踪碳循环相关的过程。     

西秦岭八卦庙金矿床原位S-Pb同位素组成对成矿物质来源和成矿过程的指示意义

八卦庙金矿床位于西秦岭造山带凤太多金属矿田北部,已探明金储量约106 t(平均金品位1.56 g/t),属于特大型金矿。金矿体受脆韧性剪切带控制,总体走向NWW,倾向北,赋矿地层为上泥盆统星红铺组下段。文章在成矿期次研究基础上,采用硫化物原位S-Pb同位素分析方法,对八卦庙金矿成矿过程和成矿物质来源进行了约束。基于详细的野外观察和矿相学研究,矿区识别出了2个金成矿期：顺层磁黄铁矿-石英成矿期和NE向黄铁矿-石英成矿期。顺层磁黄铁矿-石英成矿期可划分为自形黄铁矿-石英(Ⅰ)、磁黄铁矿-自然金-铁白云石(Ⅱ)、白云母-绿泥石-绿帘石-石英(Ⅲ)3个阶段;NE向黄铁矿-石英成矿期由自形磁黄铁矿-黄铁矿-粗粒石英(Ⅳ)、他形黄铁矿-细粒石英(Ⅴ)、他形磁黄铁矿-自然金-铁白云石(Ⅵ)和石英-黑云母(Ⅶ)4个阶段构成。顺层磁黄铁矿-石英成矿期硫化物的δ³⁴S值集中在1.60‰～5.89‰和14.07‰～16.87‰两个区间;NE向黄铁矿-石英成矿期硫化物的δ³⁴S值也集中在2.77‰～5.52‰和9.11‰～15.9‰两个区间,通过与围岩和区内岩浆岩对...     

Microscale Simultaneous Measurement of Carbon and Nitrogen Isotopes on Natural Diamond

Simultaneous analysis of carbon and nitrogen isotope ratios by SIMS was applied for the first-time to a natural diamond from the Kelsey Lake kimberlite, State Line Distinct, Colorado (UWD-1). This in situ procedure is faster, reduces sample size for analysis, and measures both isotope ratios from a single ~ 10 μm diameter pit, a critical advantage for zoned diamonds. The carbon isotope ratio (expressed as δ¹³C_VPDB) of the bulk UWD-1 crystal, determined by the conventional combustion method in the present study, is -5.9‰ ± 0.2‰ (VPDB, 2s). Nitrogen mass fraction ([N]) and isotope ratio (expressed as δ¹⁵N_Air) were determined by stepwise combustion and gas-source mass-spectrometry, resulting in 553 ± 64 μg g^-1 and -6.7‰ ± 1.1‰ (Air, 2s), respectively. Secondary ions of ¹²C₂^-, ¹²C¹³C^-, ¹²C¹⁴N^-, and ¹²C¹⁵N^- were simultaneously measured by SIMS using three Faraday cups and one electron multiplier. The spot-to-spot reproducibility of δ¹³C and δ¹⁵N values for the UWD-1 (178 spots on sixteen chips, 10 μm spots), were 0.3‰ and 1.6‰, respectively (2s). While ¹²C¹⁴N^-/¹²C₂^- ratios, which are an indicator for [N], varied up to 12% among these sixteen chips, such variation did not correlate with either δ¹³C or δ¹⁵N values. We propose that UWD-1 is a suitable reference sample for microscale in situ analysis of δ¹³C and δ¹⁵N values in diamond samples.     

山西太原盆地龙山文化时期的生业经济——以阳曲县西殿南遗址人和动物骨骼的C、N稳定同位素分析为例

以山西太原阳曲西殿南遗址(38°03′45″N,112°45′55″E)出土的3例人骨和34例动物骨骼(3例鹿、3例狗、5例牛、6例羊、17例猪)为研究对象,运用AMS-¹⁴C测年与C、N稳定同位素分析的研究方法,研究该遗址所处的年代、动物和人的食物结构以及先民对家畜的饲喂方式,进而还原龙山文化时期太原盆地的生业经济。AMS-¹⁴C测年结果显示,M1墓主人骨骼的¹⁴C年代为4200±30 a B. P.,树轮校正后的年代范围为4844~4620 cal.a B. P.,结合该遗址遗存及其组合群特征初步判断其应为一处龙山文化时期遗址。C、N稳定同位素测试结果显示,鹿(δ¹³C：-20.8‰ ~-18.7‰,均值-19.6‰ ±1.1‰;δ¹⁵N：2.9‰ ~3.6‰,均值3.3‰ ±0.4‰,n=3)主要以C₃类食物为生,说明当地野生植被主要为C₃类植物;与鹿不同,羊的δ¹³C值和δ¹⁵N值(δ¹³C：-17.2‰ ~-14.3‰,均值-16.2‰ ±1.0‰;δ¹⁵N：6.7‰ ~9.6‰,均值8.1‰ ±1.2‰,n=6)明显高于鹿,其内部存在一些差异性,可分为A、B、C三组：A组羊(YQ17和YQ19)的δ¹³C值偏高(分别为-16.4‰和-16.3‰),δ¹⁵N值(分别为9.3‰和9.6‰)较高,其年龄较小,食物中包含较多的羊奶或生活于缺水的环境中,抑或被投喂了高蛋白的饲料;B组羊(YQ16、YQ18、YQ20)的δ¹³C值偏低(分别为-16.8‰、-14.3‰和-17.2‰),但δ¹⁵N值(分别为8.3‰、7.4‰和7.2‰)偏高,其受到人工干扰的可能性最大,特别是在冬春季节,野外植被较少,羊群很可能无法自行获得充足的食物资源,这时人为投放的饲料(如粟黍的秸秆等)可能作为其食物的补充;C组羊(YQ15)的δ¹³C值(-16.3‰)和δ¹⁵N值(6.7‰)都较低,其食物来源以C₃类植物为主,也有少量C₄类食物,其数值符合羊作为食草动物的特征,同时反映出当地野生植被主要以C₃类植物为主。显然,以野外放养为主的羊,它们的食物结构仍然受到粟黍农业的强烈影响。大部分牛(δ¹³C：-20.2‰ ~-14.6%,均值-16.4‰ ±2.6‰;δ¹⁵N：3.5‰ ~6.8‰,均值5.3‰ ±1.6‰,n=4)的食物主要以C₃类植物为主,但也添加了少量的C₄类食物;家猪(δ¹³C：-7.5‰ ~-6.3‰,均值-6.9‰ ±0.3‰;δ¹⁵N：6.1‰ ~8.4‰,均值7.5‰ ±0.6‰,n=17)、家犬(δ¹³C：-7.3‰ ~-6.8‰,均值-7.0‰ ±0.3‰;δ¹⁵N：6.6‰ ~7.9‰,均值7.1‰ ±0.7‰,n=3)及牛YQ13(δ¹³C：-10.7‰;δ¹⁵N：8.7‰)主要以C₄类食物为生。其中,猪和狗则主要以粟黍及其副产品为生,并食用了较多先民食物残余和/或残羹冷炙,甚至先民的粪便等;牛YQ13可能受到先民的特殊饲喂,其食物中添加了大量的粟黍及其副产品。先民(δ¹³C：-8.6‰ ~-7.1‰,均值-7.7‰ ±0.8‰,δ¹⁵N：9.5‰ ~10.3‰,均值10.0‰ ±0.4‰,n=3)主要以C₄类食物为生,即粟黍及其副产品饲喂的家猪和家犬。因此,西殿南遗址所在太原盆地龙山文化时期先民的生业经济以粟黍农业及家猪饲喂业为主,也对外来的牛和羊进行放养和饲喂;与处于同时期且邻近的中原腹地新砦遗址、临汾盆地的陶寺遗址和清凉寺墓地、忻定盆地的辛章遗址以及陕北地区的神圪垯梁遗址已发表的人和动物骨骼的C、N稳定同位素相关数据进行单因素方差分析发现,西殿南遗址所在太原盆地的生业经济相比略显单一,社会复杂化程度有限。

     

Combined Trace Element and Pb-Nd-Sr-O Isotope Evidence for Recycled Oceanic Crust (Upper and Lower) in the Iceland Mantle Plume

We present the results of a comprehensive major element, traceelement and Sr–Nd–Pb–O isotopic study of post-glacialvolcanic rocks from the Neovolcanic zones on Iceland. The rocksstudied range in composition from picrites and tholeiites, whichdominate in the main rift systems, to transitional and alkalicbasalts confined to the off-rift and propagating rift systems.There are good correlations of rock types with geochemical enrichmentparameters, such as La/Sm and La/Yb ratios, and with long-termradiogenic tracers, such as Sr–Nd–Pb isotope ratios,indicating a long-lived enrichment/depletion history of thesource region. ⁸⁷Sr/⁸⁶Sr vs ¹⁴³Nd/¹⁴⁴Nd defines a negative array.Pb isotopes define well-correlated positive arrays on both ²⁰⁶Pb/²⁰⁴Pbvs ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb diagrams, indicating mixing ofat least two major components: an enriched component representedby the alkali basalts and a depleted component represented bythe picrites. In combined Sr–Nd–Pb isotopic spacethe individual rift systems define coherent mixing arrays withslightly different compositions. The enriched component hasradiogenic Pb (²⁰⁶Pb/²⁰⁴Pb > 19·3) and very similargeochemistry to HIMU-type ocean island basalts (OIB). We ascribethis endmember to recycling of hydrothermally altered upperbasaltic oceanic crust. The depleted component that is sampledby the picrites has unradiogenic Pb (²⁰⁶Pb/²⁰⁴Pb < 17·8),but geochemical signatures distinct from that of normal mid-oceanridge basalt (N-MORB). Highly depleted tholeiites and picriteshave positive anomalies in mantle-normalized trace element diagramsfor Ba, Sr, and Eu (and in some cases also for K, Ti and P),negative anomalies for Hf and Zr, and low ¹⁸O_olivine values(4·6–5·0) below the normal mantle range.All of these features are internally correlated, and we, therefore,interpret them to reflect source characteristics and attributethem to recycled lower gabbroic oceanic crust. Regional compositionaldifferences exist for the depleted component. In SW Icelandit has distinctly higher Nb/U (68) and more radiogenic ²⁰⁶Pb/²⁰⁴Pbratios (18·28–18·88) compared with the NErift (Nb/U 47; ²⁰⁶Pb/²⁰⁴Pb = 18·07–18·47).These geochemical differences suggest that different packagesof recycled oceanic lithosphere exist beneath each rift. A thirdand minor component with relatively high ⁸⁷Sr/⁸⁶Sr and ²⁰⁷Pb/²⁰⁴Pbis found in a single volcano in SE Iceland (Öræfajökullvolcano), indicating the involvement of recycled sediments inthe source locally. The three plume components form an integralpart of ancient recycled oceanic lithosphere. The slope in theuranogenic Pb diagram indicates a recycling age of about 1·5Ga with time-integrated Th/U ratios of 3·01. Surprisingly,there is little evidence for the involvement of North AtlanticN-MORB source mantle, as would be expected from the interactionof the Iceland plume and the surrounding asthenosphere in formof plume–ridge interaction. The preferential samplingof the enriched and depleted components in the off-rift andmain rift systems, respectively, can be explained by differencesin the geometry of the melting regions. In the off-rift areas,melting columns are truncated deeper and thus are shorter, whichleads to preferential melting of the enriched component, asthis starts melting deeper than the depleted component. In contrast,melting proceeds to shallower depths beneath the main rifts.The longer melting columns also produce significant amountsof melt from the more refractory (lower crustal/lithospheric)component. KEY WORDS: basalts; trace element and Sr, Nd, Pb, O isotope geochemistry; Iceland plume; isotope ratios; oceanic crustal recycling; partial melting; plume–ridge interaction     

吸水剖面综合解释方法及应用

吉林油田同位素吸水剖面测井采用~(113)In同位素追踪技术,根据同位素追踪过程解释基本可以判断配水层段吸水情况。但是在注水井存在沾污、大孔道以及串槽等影响时,吸水面积确定比较困难。在同位素测井中增加井温、流量参数,通过多参数综合解释,不仅可以对沾污影响进行合理校正,确定准确的小层吸水量,而且能够正确判断各级封隔器、配水器的工作情况,在地层存在大孔道的情况下,确定地层的吸水面积。吸水剖面综合解释方法在吉林油田已普遍应用,见到明显的效果。     

Are the South and North Liaohe Groups of North China Craton different exotic terranes? Nd isotope constraints

The Liaohe Group is an important Paleoproterozoic stratigraphic unit in the northeastern part of the North China Craton and is traditionally subdivided into the North and South Liaohe Groups. Associated with both the North and South Liaohe Groups are voluminous Paleoproterozoic granitoid rocks, named the Liaoji granitoids. Different tectonic models, including terrane amalgamation, continent–arc collision and rift closure, have been proposed to interpret the tectonic setting and evolution of the North and South Liaohe Groups and associated Liaoji granitoids. At the centre of the controversy between these models is whether or not the North and South Liaohe Groups developed on the same Archean basement. Nd isotopic geochemistry of the Liaoji granitoids provides important constraints on this controversial issue. The Liaoji granitoids associated with the North and South Liaohe Groups display similar ε_Nd values, restricted to a narrow range from 0 to 2, implying that these granitoid rocks were derived from the same or a similar magma source. Moreover, the Liaoji granitoids associated with the North and South Liaohe Groups have similar Nd model ages (T_DM), ranging from 2.4 to 2.6 Ga, suggesting that the protoliths of the Liaoji granitoids associated with both groups may have formed simultaneously, and that the basement rocks underneath the Liaoji granitoids and associated North and South Liaohe Groups belong to the same continental block rather than two different blocks. Combining lithological, structural and geochronological considerations, we interpret the North and South Liaohe Groups as having developed on a single late Archean basement that underwent Paleoproterozoic rifting associated with the intrusion of the Liaoji granitoids and the formation of the Liaohe Group, and closed upon itself in the Paleoproterozoic.