Research progress in carbonate associated sulfate
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摘要: 碳酸盐晶格硫（CAS）是古环境恢复的重要手段之一，它系指在碳酸盐成岩过程中微量的硫酸盐离子取代碳酸盐离子并保存在晶格中的硫酸盐。CAS对矿物沉淀发生时的海水硫酸根的氧、硫同位素组成、硫酸盐浓度和当时古环境的氧化还原状态都有很好的保存和记录作用，因此引发了对其持续关注，并开展了一系列卓有成效的研究。本文综述了CAS当前的研究进展，主要从前处理方法、影响因素、同位素组成和古环境恢复等重点问题来探讨CAS的成因和CAS对不同沉积环境的恢复应用，并展望了需要进一步研究的几点研究方向，希望借此能引起广大研究者的兴趣和重视。Abstract: Carbonate associated sulfate, or CAS in brief, is one of the important indicators for paleoenvironmental restoration. Trace sulfate may enter carbonate lattice and replaces the carbonate during diagenesis. The CAS has the capability to preserve the isotopic composition of seawater sulfate and to record the sulfate concentration of seawater, as well as the changes in the paleoenvironment. In recent years, CAS has attracted great interest and attention from the geological society. In this paper, attempt has been made to address CAS with emphases on its pre-treatment methods, influencing factors, isotopic composition and its significance in paleoenvironmental reconstruction. The application of CAS to the restoration of different sedimentary environments is discussed, in addition to the future research directions. We hope that the introduction may raise interests and attentions from researchers.
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Keywords:
- CAS /
- pretreatment method /
- sulfur-oxygen isotopes /
- paleoenvironmental reconstruction /
- cold seep
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天然气水合物被视为21世纪可供开发的新能源。天然气水合物储层识别和饱和度估算是水合物资源勘探开发的重要任务之一[1-2]。近几十年来，世界范围内开展了大量的天然气水合物的实验模拟研究和现场勘探工作，致力于通过了解含天然气水合物沉积物的物性参数演化识别水合物并估算饱和度[3-12]。基于电学响应特征的储层定性与定量评价在天然气水合物的勘探开发中发挥着重要作用，是天然气水合物资源评价的重要手段之一。
随着越来越多的原位水合物样品被获取，天然气水合物在沉积物内的赋存形态已基本明确，分为孔隙型（分散状）和裂隙型（块状、脉状和层状等）。天然气水合物赋存形态多样性使得储层各向异性特征显著，现场勘探获取的水合物饱和度相近时，电阻率响应差异十分明显[13-16]，极大地影响现场基于测井资料评估储层中水合物饱和度的准确性。物理模拟实验结果同样表明，即使在相同平均水合物饱和度条件下，采用电测法获得的沉积物体系电阻率也不尽相同[17-19]。目前，水合物物理模拟实验大部分采用的是传统的电阻率点测方法，获取的是测量电极周围沉积物的综合电学响应。然而，含水合物沉积物的电阻率响应不仅受沉积物固有性质、孔隙流体和孔隙尺度上水合物的分布模式的影响，而且还受水合物宏观赋存形态的控制[20]。传统的电阻率点测不能反映水合物的赋存形态，一定程度上限制了水合物的有效识别和饱和度的准确估算。
电阻率层析成像技术（Eleactrical Resistivity Tomography，ERT）通过获取被测物体周围的电压信号，建立被测物体的电阻率分布图像，可用于直观地呈现水合物的分布情况。成像算法是电阻率层析成像技术的核心。对于非均质性和各向异性较强的水合物储层，成像算法是研究的重点，以期获得高分辨率和高准确度的水合物电阻率分布图像。目前，电阻率层析成像技术已在孔隙型水合物样品上进行应用[21-26]，而裂隙型水合物的电阻率成像还有待进一步的研究。
本文利用水合物电阻率层析成像实验装置，模拟分散状和块状水合物的生成过程；基于物理模拟实验测试结果，建立了含水合物沉积物电阻率层析成像反演方法，实现分散状和块状水合物的可视化；基于含不同赋存类型水合物沉积物的电阻率图像，揭示水合物生长规律，研究水合物赋存形态对电阻率响应特征的影响，以期为天然气水合物赋存类型识别和饱和度估算提供支持。
1. 实验
本研究采用的是青岛海洋地质研究所自主研制的水合物电阻率层析成像实验装置。实验装置可实时采集原位水合物生成和分解过程中电阻率层析成像数据。根据电阻率层析成像算法，重建不同时刻沉积物内水合物赋存形态电阻率图像。
1.1 实验装置
水合物电阻率层析成像实验装置包括水合物生成/分解和数据采集两个模块（图1）。水合物生成/分解模块主要包括高压反应釜、恒温水浴槽和内筒，是水合物生成和分解的场所。高压反应釜和恒温水浴槽用于模拟水合物生成的高压低温环境。内筒为一直径10 cm的圆柱状绝缘筒，用于承装沉积物，筒壁和筒底部均布置透气不透水通道；数据采集模块主要包括测量电极、电侨仪和控制器，采集水合物生成/分解过程中的电学参数。测量电极布设在内筒的同一高度，径向均布16个测点、间距22.5°；电侨仪与控制器的相互配合，完成电学参数的采集。水合物生成过程中电学数据的采集方式为四电极法，同一高度的16个电极中，选相邻的两个电极作为供电电极，其余电极相邻的两两一对作为测量电极，直至16个电极皆完成作为供电电极任务，每一轮次的采集可获取208个有效数据。
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图 1 水合物电阻率层析成像实验装置Figure 1. Experiment device of hydrate electrical resistivity tomography1.2 实验方法及条件
（1）分散状水合物
将充分饱水（浓度为3.5%的NaCl溶液）的石英砂（＞500 μm）填入内筒后放入高压反应釜，密封反应釜；向密封反应釜内充入甲烷气体（纯度99.99%）至实验压力；稳定后，开启水浴循环进行系统降温，开始水合物生成实验。实验过程中，实时采集含分散状水合物沉积物体系的电阻率层析成像数据。
（2）块状水合物
为提高实验效率，实验将已经制备好的圆柱状水合物装入沉积物内，以模拟块状的裂隙型水合物。参照已有的裂隙充填型水合物合成实验[27]，将去离子水冰粉装入圆柱状模具后，放入液氮中冷却；然后将其放入水合物样品制备反应釜，密闭后充入甲烷气（纯度99.99%）至水合物生成所需的压力；将反应釜放入循环水浴控温装置中进行降温，生成圆柱状水合物。水合物开始生成后，釜内的压力会不断地降低。水合物的生成是一个从成核到不断生长的过程，十分耗时。在压力下降过程中，也就是冰粉还未完全转换成水合物时，开釜后取出的圆柱状水合物样品为冰粉与水合物的混合物（图2）。
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图 2 圆柱状水合物样品（模拟块状水合物）Figure 2. Photos of cylindrical hydrate sample which simulates massive hydrate为了尽量避免圆柱状水合物与沉积物接触导致水合物分解，将充分饱水（浓度为3.5%的NaCl溶液）的石英砂（＞500 μm）放入恒温箱进行预冷，并提前开启水浴循环进行高压反应釜系统的降温。待温度稳定后，取出压力还处在下降过程中的圆柱状水合物，放入液氮中冷却，尽量降低水合物的分解。取出部分预冷后的石英砂填入内筒，将圆柱状水合物埋入石英砂中，并将内筒整体放入反应釜内，快速密封反应釜，并迅速向反应釜内充入甲烷气体至实验压力，尽量避免水合物的分解。由于装样过程和充入的室温环境下的甲烷气体导致沉积物体系温度升高，高于水合物稳定存在的温度范围，水合物将存在分解现象。维持水浴循环的低温对沉积物体系进行降温。随着温度的降低，水合物将继续生成。实验过程中，实时采集含块状水合物沉积物体系的电阻率层析成像数据。
2. 层析成像反演算法
本文电阻率层析成像图像重建算法采用引入了正则化矩阵和参数获取稳定解、收敛速度快的高斯牛顿迭代方法求解目标函数。电阻率层析成像属于非线性的不适定反问题，反问题等价于非线性最优化问题，其最小化目标函数为：
$$ S={\parallel GX-{d}\parallel }^{2}+{\mathrm{\lambda }}^{2}{\parallel {C}X\parallel }^{2} $$ (1) 其中：G为加权灵敏度矩阵；X为模型参数；
$ {d} $ 为测量数据；λ为正则化参数；C为光滑度矩阵。第
$ i+1 $ 次迭代得到的新模型为第$ i $ 次模型$ X $ 与修正量$ \Delta X $ 之和，则目标函数可写为：$$ S={\parallel F(\Delta X+{X}_{i})-{d}\parallel }^{2}+{\lambda }^{2}{\parallel C(\Delta X+{X}_{i})\parallel }^{2} $$ (2) 对目标函数进行泰勒展开后，忽略高阶项，并令其偏导为零，则有：
$$ {X}_{i+1}={X}_{i}+{({J}^{T}J+\lambda {C}^{T}C)}^{-1}{J}^{T}({X}_{i}-{ d})+\lambda {C}^{T}C{X}_{i} $$ (3) 其中，J为雅可比矩阵。
当新模型的解与测量数据的均方根误差满足精度时，迭代终止，
$ {X}_{i} $ 即所求模型。3. 实验结果
水合物物理模拟实验开展了多组重复试验，验证实验装置和层析成像反演算法的可靠性，本文选取其中的一组数据进行分析。需要说明的是，压力的变化对电阻率的影响可忽略不计[26]，而温度的变化对孔隙水中导电离子的移动影响较大，不可忽略。在层析成像反演过程中，已将常温条件下的电阻率作为参考值对测量数据进行了温度校正。因此，分散状与块状水合物生成的起始温压条件的不同不影响水合物物赋存形态差异引起的电学响应差异的研究。
对比分散状水合物和块状水合物的电阻率图像可以发现，分散状水合物的高值电阻率分布存在明显的零散性，块状水合物的高值电阻率分布则是相对比较聚集，且随着水合物的不断生成，分散状水合物的零散性和块状水合物的聚集性变得更加明显。利用二维电阻率图像上这一特性可初步判断水合物的赋存形态。
3.1 分散状水合物
实验过程中压力维持稳定10 h后，进行了一次补压和升温，使沉积物体系内的气水重新分布，促进水合物的生成（图3）。反应过程中随着水合物生成，体系压力下降明显，经补压升温后，水合物继续生成。初始状态下，各层的平均电阻率在1.55 Ω·m左右，属正常海底沉积物电阻率分布范围内（图4）。分散状水合物生成过程中内筒内不同高度沉积物介质的电阻率分布情况如图5所示。随着时间的推移，孔隙水不断固化成水合物，每层不同位置的电阻率和平均电阻率皆逐渐升高，局部电阻率升高明显，尤其是上部层位。分析认为，水合物的聚集特征受气源的供给和输导通道共同控制[28]。Chen等研究认为沉积物中水合物首先在气水接触面生长，天然气聚集区域将形成大量的水合物[29]。考虑实验装置内筒上部为开口式，上部气水接触充分，下部层位依赖内筒侧壁的气孔进气，气水接触相对较弱。从电阻率图像上可以观测到上部水合物最早生成，生成速度相对较快，且随着时间的变化，大量水合物聚集。
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图 3 分散状和块状水合物生成过程中温度和压力的变化Figure 3. Temperature and pressure during formation of dispersed hydrate and massive hydrate![]()
图 4 分散状和块状水合物生成过程每层平均电阻率的变化Figure 4. Average resistivity of each layer during formation of dispersed hydrate and massive hydrate![]()
图 5 分散状水合物生成过程中不同时刻电阻率图像Figure 5. The changes of resistivity distribution of dispersed hydrate with time从分散状水合物生成过程中电阻率图像的变化可以看出，水合物围绕水合物优先生成区域不断扩张生长；层与层之间的电阻率和层内的电阻率不同指示了水合物的生长具有明显的非均质性。国内外学者利用电阻率层析成像技术在研究水合物生成/分解规律以及物性演化规律时也曾发现了水合物的上述生长行为[22-23]。
随着时间的变化，分散状水合物部分区域（图5中椭圆形区域）电阻率明显降低，尤其是
$ {t}_{3} $ 时刻。分析认为是由于水合物生成过程中的排盐效应导致孔隙流体电阻率降低[30]。水合物生成过程中孔隙流体被水合物圈闭，被圈闭的这部分流体对含水合物沉积物的导电贡献相当于水合物[31]。也就是说，当矿化度升高的孔隙流体被水合物圈闭后，同样会呈现出高电阻率值。图5中的长方形区域，电阻率出现了升高（$ {t}_{1} $ ）-降低（$ {t}_{2} $ ）-升高（$ {t}_{3} $ ）的特征。图5中$ {t}_{3} $ 时刻方形区域周围并没有形成高电阻率值的圈闭现象，认为图5中$ {t}_{3} $ 时刻长方形区域电阻率的升高是水合物的影响。因此，不同时刻电阻率图像的对比可以明确受水合物影响引起的电阻率的变化，对水合物的有效识别十分有利。3.2 块状水合物
受实验装置硬件条件的影响，块状水合物仅成功获取2层测量数据。块状水合物生成过程中内筒内沉积物介质不同高度的电阻率分布情况如图6所示。加压稳定后，块状水合物的大小呈现准确，位置稍微有些偏差。实验发现，随着时间的变化圆柱体水合物电阻率不断增加。非圆柱体水合物区域处的电阻率值在温压条件达到后的1.5 h（
$ {t}_{1} $ 时刻），电阻率值即达到20 Ω·m，而在分散状水合物生成过程历经几十个小时后，电阻率仅有5～7 Ω·m（图3，图4）。Lei和Seol通过对热刺激法和降压法开采的实验模拟，认为外界压力会迫使水合物分解产生的气体滞留在沉积物孔隙内[32]。圆柱体水合物放入釜内后，受温度影响水合物仍在分解，分解产生的游离气被滞留在沉积物内，驱替了部分孔隙水。游离气为不导电介质，造成其他区域的电阻率值过大，进而导致圆柱体水合物的位置发生偏移。同时，孔隙内的游离气与孔隙水接触充分，促进了水合物再次生成，导致非圆柱体水合物区域处的电阻率值升高较快。![]()
图 6 块状水合物生成过程中不同时刻电阻率图像Figure 6. The changes of resistivity distribution of massive hydrate with time4. 讨论
在相同沉积物样品体积条件下，分散状水合物在压力下降0.5 MP的情况下，平均电阻率升高了1.22 Ω·m；块状水合物在压力下降约0.12 MP的情况下，平均电阻率升高了14.37 Ω·m（图3，图4）。对比分散状水合物和块状水合物，块状水合物电阻率升高较快，而从压力下降情况可知块状水合物生成量又较少。Liu等人通过数值模拟研究了水合物形态对含天然气水合物沉积物电阻率特性的影响，发现低水合物饱和度范围内裂隙型水合物电阻率同样存在急剧增加的现象[33]。
电阻率测量是经数值解法求出测量电极周围介质的电场分布，然后求取电阻率的计算公式。测量电极周围存在不同赋存形态的水合物时，电场的分布不同，求取的电阻率也将不同。分散状水合物是指水合物以颗粒形式分布于粒间孔隙内，在含量较少的情况下，对导电路径（孔隙水）的堵塞作用不明显；当大量的水合物生成后，沉积物内的导电路径将被逐渐堵塞。块状水合物模拟实验的沉积物中，圆柱体水合物为冰粉、孔隙水、水合物和气的混合。圆柱体水合物是用去离子水制成的冰粉生成的，压实后的孔隙空间也很小，可被视为体积相对较大的不导电介质，即使水合物生成量相对较低，对导电路径的阻碍作用也会比较明显，对获取的电学响应的贡献突出，电阻率升高的就会较快。
不同赋存形态的水合物饱和度估算需要采用不同的电阻率岩石物理模型[12,33-34]。对于取心难度较大的水合物储层，水合物的赋存形态很难获得。电阻率层析成像技术在孔隙尺度的微观探测与现场尺度的宏观探测中具有广阔的前景[25]。刘洋等人已研发了一种新的电阻率层析成像阵列，应用于含水合物沉积物的电阻率成像模拟实验装置[26]。结合本文研究，电阻率层析成像技术可作为识别水合物赋存形态的一种手段应用于现场水合物储层，为选取电阻率岩石物理模型提供依据，提高基于现场测井资料评估储层中水合物饱和度的准确性。
5. 结论
（1）利用电阻率层析成像结果可初步判断沉积物中水合物的赋存形态。分散状水合物的高值电阻率分布具有零散性，块状水合物的高值电阻率分布比较聚集，且随着水合物的不断生成，电阻率高值的零散性和聚集性将越加明显。
（2）分散状水合物不同时刻电阻率图像的对比，可以明确由水合物生成所引起的电阻率的变化。被滞留在沉积物内的游离气对沉积物的电阻率影响较大，影响了块状水合物电阻率层析成像的位置，多物理参数的联合探测将有助于区分游离气和水合物对沉积物电阻率响应的影响。
（3）水合物的赋存形态是影响电阻率响应特征的重要因素，分散状水合物和块状水合物的电阻率响应特征差异明显；相对于分散状水合物，块状水合物作为大体积的不导电介质，对导电路径的堵塞作用明显，导致块状水合物电阻率随着水合物的生成升高较快。
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表 1 一些典型的CAS提取方法
Table 1 Typical methods of extraction of CAS
样本时代 采样地点 主要的实验步骤 碳酸盐岩类型 文献来源 寒武纪 美国伊利诺斯（Illinois） 样品粉末用去离子水冲洗两次，持续24 h，偶尔搅拌一下，而后小心的倒掉上层液体；把样品用4%NaClO溶液处理，混合好后，持续反应48 h，并伴随偶尔的搅拌；样品再用去18 MΩ离子水冲洗两次 — [32] 古生代和中生代 — 直接用NaCl进行处理 生物成因碳酸盐岩和微晶方解石 [1] 新元古代晚期 中国宜昌市 50 g样品直接放到200 mLHCl(6 mol/L)，12 h，过滤；加入5 g/(NH4)2(OH)Cl(1%)和两滴甲基橙，用NH4OH和盐酸调节pH，至溶液变为红色的 — [30] 震旦纪晚期 纳米比亚（Namibia） 将样品浸入10%NaCl溶液中，5次，持续24 h，并且不停的搅拌，每次取出后用去离子水冲洗3次 含硅质碎屑的碳酸盐岩 [33] 上三叠纪 阿尔卑斯山脉东部和南部 把样品浸入到10%NaCl溶液中搅拌24 h，过滤 — [34] 古生代 去离子水浸泡24～36 h — [35] 元古代 中国天津蓟县 在5.25%NaClO中冲洗24 h，然后用蒸馏水冲洗 — [29] 古生代 比利时乌拉尔山脉、北美
中部和内华达州用去离子水淋洗两次，每次持续24 h；再用4% NaClO溶液处理48 h — [36] 
下载: 导出CSV
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