海水溶解磷酸盐氧同位素组成的测定

生物磷酸盐和水分子间的氧同位素分馏主要受温度和生物活动控制, 因此磷酸盐氧同位素组成既可以测量古温度又可以示踪磷循环。近年来磷酸盐氧同位素研究受到较多关注, 除了传统的生物体磷灰石古温度测量外, 这些研究大多是关于磷循环的。磷酸盐的氧同位素组成可以示踪海洋中磷的源区和生物对磷的利用效率。由于海水的组成十分复杂, 测量前必须对样品进行富集、分离和纯化处理。目前, 加州大学(Santa Cruz)Paytan教授和耶鲁大学Blake教授的实验室已建立了海水溶解磷酸盐氧同位素的测量方法, 二者各有优缺点。我们结合了这两种方法的优点, 并对一些步骤进行了改进, 建立了海水溶解磷酸盐氧同位素组成的测量方法。通过向海水样品中加入NaOH, 形成Mg(OH)2来富集海水中的PO43-, 也可同时除去部分杂质离子和溶解有机质; 通过将PO43-转化为CePO4沉淀来进一步除去杂质离子, 然后用阳离子交换树脂除Ce3+, 再通过阴离子交换树脂柱来除溶解有机质。最后将磷酸盐转换为Ag3PO4沉淀, 在1350℃裂解Ag3PO4, 产生的O2和石墨反应形成CO用IRMS测定。结果显示富集、分离和纯化过程可以获得纯的Ag3PO4颗粒, 不会产生PO43-的氧同位素分馏。测量Ag3PO4用量仅为0.3 mg, 标准偏差在±0.2‰~±0.3‰之间。     

角闪石族矿物的氧同位素分馏

利用增量方法和同位素交换技术,对角闪石族矿物的氧同位素分馏进行了理论计算和实验测定。理论结果表明,不同化学成分的角闪石之间存在一定的氧同位素分馏,其13O富集顺序为:钠闪石>蓝闪石>铁闪石>阳起石=镁铁门石≥直闪石≥透闪石>普通角闪石>铝直闪石>韭闪石。高温条件下(>500℃),角闪石相对于水亏损¹⁸O达1‰至3‰。实验进行在有少量流体存在的条件下,温度为520℃至680℃。所确定的方解石-透闪石氧同位素分馏系数与理论计算值在误差范围内完全一致。理论和实验确定的石英-透闪石分馏曲线均显着低于已知的经验校准曲线,反映了变质岩中含角闪石矿物集合体内部的退化同位素再平衡。     

文石-水体系氧同位素分馏系数的低温实验研究

采用缓慢分解法和“两步法”的附晶生长法,在低温(0℃～70℃)下实验合成纯文石型碳酸 钙矿物,以XRD和SEM技术对合成矿物的相组成和形貌进行了鉴定。将XRD与SEM及氧同位素分 析技术相结合,研究了文石的生成速率与氧同位素分馏之间关系。对0℃、25℃和50℃条件 下采用缓慢分解法合成的文石进行SEM观察发现,随着温度升高,矿物生成速率加快,氧同 位素分馏逐渐趋于不平衡,导致50℃条件下获得的文石-水体系氧同位素分馏是一种不平衡 分馏,而0℃和25℃条件下获得的低值代表平衡分馏。将0℃和25℃以下采用缓慢分解法获得 的文石-水体系分馏低值与采用“两步法”的附晶生长法在50℃和70℃条件下获得的文石- 水体系平衡分馏数据相结合,得到0℃～70℃范围内文石-水体系氧同位素平衡分馏方程为 ：103lnα=20.41×103T－41.42。这个实验结果不仅与增量方法理论计算结 果一致,而且与前人低温实验获得的文石或文石与方解石混合相碳酸钙-水体系,以及生物 成因文石-水体系的氧同位素分馏结果相近。这是首次根据实验确定的无机成因文石-水体 系热力学平衡氧同位素分馏系数,因此对于无机成因文石在古沉积环境和古气候研究中的应 用具有重要参考价值。     

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

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。     

稳定同位素动力学及其地质意义

稳定同位素平衡分馏资料已广泛应用于地质研究中,对探讨成矿物质、成矿流体来源、矿床成因及成矿机理等起了重要作用。然而其应用的前提必须假设:(1)地质体系中共生矿物间及与介质流体间已达到同位素平衡;(2)矿物的形成温度作为终止同位素交换的封闭温度。但大量的资料表明,许多地质体中共生矿物间并非都达到了同位素平衡,矿物的形成温度并非就是同位素交换的封闭温度,这正是目前一些同位素资料互相矛盾,不能得到合理介释的原因所在。例如,同位素地温计与相平衡证据不符,共生矿物之间没有统一的同位素平衡关系,由共生矿物对计算的同位素温度不一致;同一矿物或共生矿物的氧、氧同位素组成之间及硫酸盐矿物中硫、氧同位素组成之间的不一致等等。这些都反映出仅用平衡分馏原理不能全面、合理地解释地质问题。地质过程是一个漫长而复杂的演化发展过程,许多矿     

水镁石—水体系氧同位素分馏系数的低温实验研究

在15—120℃的低温范围内分别应用氮化镁法、氯化镁法和氧化镁法3种化学合成方法,对水镁石-水体系氧同位素分馏系数进行了实验测定。所有合成样品的晶体结构均由XRD测定,其形貌特征则由SEM确定。应用3种不同合成方法得到了一致的水镁石—水体系氧同位素分馏系数,证明同位素平衡分馏已经达到。在实验温度范围内,水镁石—水体系氧同位素分馏系数主要决定于温度,而溶液的酸碱度、化学组分和陈化时间的影响不明显。由实验数据得到的氧同位素分馏曲线方程为:10~3Inα=1.59×10~6/T~2-14.10(r=0.9921)。结合前人对三水铝石—水体系和针铁矿—水体系氧同位素分馏系数的低温实验测定,可以得到氢氧化物中金属M—OH键的~(18)O富集顺序:Al~(3+)-OH>Fe~(3+)-OH>Mg~(2+)-OH。应用化学合成方法实验测定低温条件下水镁石—水体系氧同位素分馏系数,不仅克服了同位素交换反应实验的一些缺陷(如交换速率缓慢、仪器设备复杂昂贵等),而且可以应用不同的化学合成反应机理来检验同位素平衡是否达到,这为研究低温地球化学过程作用提供了有价值的基本参数。     

云母族矿物的氧同位素分馏

利用增量方法对云母族矿物的氧同位素分馏进行了系统的理论计算。结果表明，不同化学成分和结构状态的云母之间存在一定的氧同位素分馏，其１８Ｏ富集顺序在热力学同位素平衡时为：多硅白云母＞钠云母＞锂云母＞白云母＝珍珠云母＞海绿石＞铁云母＞金云母＞黑云母。在４００℃以上的高温条件下，云母－水体系的氧同位素分馏与温度之间的相关性不明显，并且云母相对于水亏损１８Ｏ达１‰－２．５‰。石英－云母体系的氧同位素分馏与温度之间具有显著的负相关性，因此，能够作为灵敏的同位素地质温度计。不过，石英－黑云母对的氧同位素地质测温往往给出岩石冷却过程中的退化再平衡温度，而不是岩石形成温度。     

苏州A型花岗岩氢氧同位素地球化学研究

对苏州Ａ型花岗岩氢氧同位素组成进行了系统深入的研究,其全岩δ１８Ｏ值为＋３．５‰～＋９．２‰,全岩δＤ值在－８１‰～－５９‰之间变化。主要造岩矿物对保持氧同位素平衡分馏的样品,其Ｄ亏损主要受单阶段岩浆去气机理的制约。部分全岩样品表现出不同程度Ｄ－１８Ｏ同步亏损,这种亏损要受岩浆期后固相线下与外来渗透大气降水之间进行同位素交换机理的制约。石英δ１８Ｏ值基本正常,石英与碱性长石之间氧同位素不平衡分馏特征表明,苏州Ａ型花岗岩整体上起源于亏损１８Ｏ源区物质通过地球动力学再循环产生低δ１８Ｏ岩浆的可能性不大。根据氢氧同位素实测值和理论模型计算结果,推测苏州Ａ型花岗岩浆δＤ和δ１８Ｏ初始值分别为－５０±５‰和７．５±１．０‰,这排除了岩浆起源于曾经历过化学风化循环的地壳上部岩石的可能性。     

碳酸钙-水体系氧同位素平衡及稳态分馏的低温实验研究

采用“一步”和“两步”的直接沉淀法和附晶生长法在 5 0℃和 70℃分别合成碳钡矿和文石 ,测定不同条件下合成矿物与水之间的氧同位素分馏 ,结果显示 ,文石—水体系氧同位素分馏机理分两步 :(1) [CO3 ]2 - 与H2 O的氧同位素交换和平衡 ,此过程是文石 水氧同位素平衡的决速率步骤 ;(2 )与H2 O平衡以后的 [CO3 ]2 - 与Ca2 +]结合生成文石 ,此过程体现矿物形成过程中氧同位素分馏的结构效应。在此基础上 ,采用缓慢沉淀法和“两步”的附晶生长法获得了 0～ 70℃的文石 水体系氧同位素平衡分馏方程。采用“一步”和“两步”的附晶生长法在 5 0℃和 70℃合成文石 ,文石在溶液中经同质多象转变成次生方解石 ;结合文献数据 ,获得 0～ 70℃范围内的方解石 水体系稳态氧同位素分馏方程。     

离子交换分离过程中铅同位素分馏评估及针对MC-ICPMS铅同位素测定的分离纯化方法的修正

本文对分离纯化样品过程中铅同位素的分馏进行了评估,并描述了适于MC-ICPMS同位素测定的分离纯化方法。利用AG1-X8阴离子交换树脂分离纯化样品中铅的过程确实导致了铅同位素的质量分馏。尽管分离纯化过程导致的铅同位素分馏程度较小(0.43‰amu-1),但明显超出了仪器的测试误差(0.23‰amu-1),如果样品中铅的回收率太低,会导致铅同位素测试值明显偏离真值。利用AG1-X8阴离子交换树脂,以0.2mL 1mol/L HBr溶液为上样介质,以5mL 1mol/L HBr和0.5mL 2mol/L HCl溶液为淋洗液,1.5mL 6mol/L HCl溶液为洗脱液,利用该分离流程可以保证获得样品中铅同位素的准确值。在本实验研究条件下,相对于过柱前样品,前期淋洗液富集铅的轻同位素(δ208Pb0),后期淋洗液富集铅的重同位素(δ208 Pb0),表明在该实验条件下,铅的重同位素组分比轻同位素更容易和树脂结合,AG1-X8阴离子交换树脂吸附铅的配分系数208 D/204 D大于1。解吸被树脂吸附铅的过程中,铅在不同络合形式间的交换反应可能导致了铅同位素的分馏效应,意味着无机络合物或者有机大分子参与反应的过程可能会导致铅同位素的分馏。     

Effects of speciation on equilibrium fractionations and rates of oxygen isotope exchange between (PO4)aq and H2O

The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H₃PO₄ and H₂PO₄⁻ that are dominant at relatively low pH and species like PO₄³⁻ and ion pairs like KHPO₄⁻ that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, ¹⁸O/¹⁶O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates ¹⁸O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.     

矿物-水体系氢同位素平衡分馏和动力分馏的实验研究

矿物水体系氢同位素平衡分馏系数和动力分馏系数是同位素地球化学研究中的重要参数。这些参数大多由实验测定。氢同位素分馏的实验研究主要包括矿物水体系氢同位素交换实验,交换实验前后矿物、水的氢同位素分析及分馏机理、平衡分馏、动力分馏理论研究。为确保氢同位素分馏系数和一系列动力学参数的准确可靠,实验中防止氢透过容器壁扩散,避免空气中水汽污染样品,正确控制实验温度等都很重要。本研究以石英管代替前人常用的金（银、铂）管作反应容器,建立了一套实验研究羟基矿物水体系氢同位素平衡分馏和动力分馏的新方法,并开展了电气石水、黑柱石水体系氢同位素分馏的实验研究。所得一系列参数的精度明显好于国外报道的资料。此研究方法可广泛应用于羟基矿物水体系的氢同位素分馏的实验研究。     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.     

Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag₃PO₄ in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag₃PO₄ crystals were obtained from KH₂PO₄ that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag₃PO₄. We provide a calculation sheet that computes the δ¹⁸O of precipitated Ag₃PO₄ as a function of time, temperature and δ¹⁸O of both reactants KH₂PO₄ and H₂O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ¹⁸O from ?20 to +15‰ VSMOW.     

Kinetic mechanism of oxygen isotope disequilibrium in precipitated witherite and aragonite at low temperatures: an experimental study

To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:

1.

Oxygen isotope exchange between [CO₃]²⁻ and H₂O:

(1)     

湖泊硅藻氧同位素:一种前景广阔的陆相古气候指标

硅藻氧同位素已日益成为陆相古气候重建的一种重要手段。文章在简述这一领域已取得的基本认识基础上,着重介绍了近年来的重要进展。主要进展包括: 1)在硅藻的分离纯化方面,规范了重液分离法和新的重力差异流体分离法;2)完善了分步氟化法,创生了高温碳还原法的氧同位素制取技术;3)通过实验培养和天然湖泊监测实验,证实了硅藻氧同位素与温度的分馏平衡关系;4)湖泊硅藻氧同位素可以反映古温度、气候干旱事件和大气降水来源变化。同时,对目前硅藻氧同位素在湖泊沉积古气候研究中存在的主要问题作了讨论和展望。     

物相之间氧同位素分馏的高温高压实验研究

应用理论计算、实验测定和经验估计三种方法均能获取含固体矿物体系的氧同位素分馏系数,其中高温高压实验研究不仅能够得到物相之间的同位素平衡分馏系数,而且能够提供与同位素交换动力学和机理有关的信息。同位素分馏系数的实验校准方法已经由原来的两相体系（矿物Ｈ２Ｏ、矿物ＣＯ２和矿物ＣａＣＯ３）交换发展为三相体系（ＣａＣＯ３矿物流体）交换,化学合成、重结晶和矿物反应技术得到了进一步应用。本文评述了近十年来这一领域的研究进展,着重介绍了Ｈ２Ｏ、ＣＯ２和ＣａＣＯ３作为交换介质进行氧同位素分馏系数校准的技术原理和结果,探讨了热液和碳酸盐交换实验结果不一致的原因。     

南海东北陆坡烟囱状冷泉碳酸盐岩生长剖面的碳、氧同位素特征与生长模式

 对SO177航次采集自南海东沙东北古冷泉活动区的烟囱状碳酸盐岩样品（TVG14 C1 1）进行解剖研究,探讨烟囱样品的形成机理。我们首先对烟囱样品的横截面进行高分辨率精细取样并进行碳氧同位素分析,在充分了解其矿物组成特征的前提下,利用碳酸盐岩-水体系氧同位素分馏方程计算古冷泉流体的氧同位素组成并定量分析流体的端元成分和相对贡献,然后根据它们在烟囱生长剖面上的变化特征,为碳酸盐质烟囱建立生长模式。分析表明,该样品横截面的δ13C值在-50.136‰～-43.923‰之间变化,δ18O值在2.762‰～4.848‰之间变化,由中心向外,碳氧同位素呈反向协同变化趋势,δ13C 逐渐升高而δ18O逐步降低。结合该样品的年龄和古海水的氧同位素组成,计算得到形成该样品的冷泉流体的δ18O在1.2‰~2.3‰ V SMOW之间变化,较冰期海水的更富18O。认为在形成烟囱的不同阶段,水合物分解产生的富18O流体与同期海水发生了不同程度的混合,烟囱中心部位水合物分解水的相对贡献高达53.6％,而烟囱外层,水合物分解水的贡献低至6.1‰。通过综合研究,提出了烟囱样品的生长模式。     

北大别主簿源花岗岩和片麻岩矿物的

对大别造山带北部主簿源中生代花岗岩侵入体及其围岩片麻岩进行了矿物氧同位素分析，同时对同一样品进行了矿物 Rb- Sr内部等时线定年。结果表明，花岗岩和片麻岩矿物的氧同位素温度大小顺序为：角闪石 >磁铁矿 >榍石 >石英 >黑云母 >长石，遵循缓慢冷却条件下扩散控制的氧同位素交换封闭顺序，指示这些岩石没有受到后期热液蚀变的扰动。根据黑云母-长石-磷灰石-全岩内部 Rb- Sr等时线测定，花岗岩的年龄为 (118± 3) Ma，代表了岩浆侵位冷却年龄；片麻岩的年龄为 (122± 1) Ma，代表了片麻岩受大面积燕山期岩浆侵位热烘烤达到高温同位素平衡后的冷却年龄。因此，矿物之间的氧同位素平衡与否 ,能够对矿物 Rb- Sr体系封闭后平衡状态的保存性以及矿物内部等时线定年的有效性予直接制约。