A simultaneous determination method for diamondoids and thiadiamondoids in condensate oil and its geological significance: taking condensate oil from central Tarim Basin as an example
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摘要: 原油中的金刚烷类和硫代金刚烷类化合物具有相似的类金刚石笼状结构，可以反映地质过程中的热裂解作用和热化学硫酸盐还原反应（TSR）作用，因此两者的同步检出，不仅可以提高样品的分析测试效率和硫代金刚烷类化合物的定量结果准确性，还可以为样品提供更加可靠和广泛的地球化学分析解释。该文利用气相色谱-三重四级杆串联质谱仪（GC-MS-MS），确定了目标化合物的母离子和子离子、扫描时间、碰撞能等仪器参数，建立了塔里木盆地塔中地区凝析油中金刚烷类化合物和硫代金刚烷类化合物的同步定量检测方法，并通过定量检测结果发现，塔中地区金刚烷类化合物的含量虽有差异，但是成熟度相近，都处于过成熟阶段，且部分样品曾经历过TSR作用。Abstract: Diamondoids and thiadiamondoids in crude oil samples have the similar diamond-like cage structures, which can reflect the thermal cracking and thermochemical sulfate reduction(TSR) effect during geological processes. Therefore, the simultaneous monitoring of diamondoids and thiadiamondoids cannot only improve the efficiency of sample analysis and the accuracy of quantitative results of thiadiamondoids, but also provide more reliable and extensive geochemical interpretation for the samples. In this paper, a simultaneous quantitative detection method of diamondoids and thiadiamondoids was proposed by the means of gas chromatography-triple quadrupole mass spectrometer (GC-MS-MS). By determining the parameters of precursor and product ions, scanning time and collision energy of the target compound, a simultaneous quantitative detection method was established for diamondoids and thiadiamondoids in condensate from the central Tarim Basin. Results showed that despite the contents of diamondoids of oils from the central Tarim Basin were different, the maturity degree on the other hand, were comparable as over mature, and some samples have experienced TSR.
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Key words:
- diamondoids /
- thiadiamondoids /
- maturity /
- thermochemical sulfate reduction (TSR) /
- central Tarim /
- Tarim Basin
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图 1 塔里木盆地塔中地区样品TZ103中单金刚烷类化合物(a)、双金刚烷类化合物(b)、2-硫代单金刚烷类化合物(c)的色谱图
图中峰号代表的化合物见表 3。
Figure 1. Chromatograms of adamantanes (a), diamantanes (b) and thiaadamantanes (c) in sample TZ103 from central Tarim Basin
图 2 塔里木盆地塔中地区凝析油样品中金刚烷类化合物的浓度
Figure 2. Concentration of diamondoid compounds in condensate oil samples from central Tarim Basin
图 3 塔里木盆地塔中地区凝析油样品中的金刚烷参数
Figure 3. Diamondoid parameters of condensate oil samples from central Tarim Basin
图 4 塔里木盆地塔中地区凝析油样品中单金刚烷类化合物浓度和双金刚烷类化合物浓度(a)、硫代单金刚烷类化合物浓度(b)的关系
Figure 4. Correlation between the concentration of adamantanes and diamantanes (a) and thiaadamantanes (b) of condensate oil samples from central Tarim Basin
表 1 塔里木盆地塔中地区凝析油样品基本信息
Table 1. Basic information of condensate oil samples from central Tarim Basin
井号 层位 井深/m 密度/(kg·m-3) 黏度/(mm2·s-1) 含硫量/(mg·L-1) TZ103 C 3 755.0~3 756.5 835.76 2.483 2 380 TZ83-3 O1y 5 580.00~5 648.53 807.57 3.041 2 420 TZ86 O 6 273~6 320 820.75 4.530 3 170 TZ451 C 6 090.50~6 297.62 802.86 2.743 1 350 TZ823 5 369~5 490 824.77 5.032 1 750 TZ82-1H O1y 5 247.36~6 280.00 809.01 3.270 1 470 TZ162 O 5 048~5 070 835.38 3.851 1 440 玛4-H4 O 2 086~2 840 785.81 1.103 2 240 TZ62-H14 O3z 4 764~5 163 789.82 1.959 1 160 
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表 2 金刚烷类化合物及硫代金刚烷类化合物同时检测的参数设置
Table 2. Parameter setting for simultaneous detection of diamondoids and thiadiamondoids
片段 时长/min 扫描时间/s 母离子(m/z) 子离子(m/z) 碰撞能/V 1 16.5 0.500 136 93.2 13 2 0.70 0.500 150 135 6 3 0.60 0.500 164 149 6 4 1.60 0.250 178 163 6 192 177 6 5 0.60 0.500 150 135 9 6 1.60 0.150 164 149 8 178 163 6 196.4 82.1 5 7 0.50 0.500 164 149 6 8 2.90 0.100 164 149 6 164 135 6 178 163 6 178 149 6 192 177 6 192 163 6 9 1.15 0.050 192 177 6 154 79 13 168 93 6 182 93 6 196 107 6 10 9.65 0.050 168 93 6 182 93 6 196 107 6 210 121 6 11 9.20 0.100 188.1 131.3 13 202 187 6 216 201 6 230 215 6 260.7 82.1 7
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峰号 化合物 分子式 英文名称 缩写 1 单金刚烷 C10H16 adamantane A 2 1-甲基单金刚烷 C11H18 1-methyladamantane 1-MA 3 1, 3-二甲基单金刚烷 C12H20 1, 3-dimethyladamantane 1, 3-DMA 4 1, 3, 5-三甲基单金刚烷 C13H22 1, 3, 5-trimethyladamantane 1, 3, 5-TMA 5 1, 3, 5, 7-四甲基单金刚烷 C14H24 1, 3, 5, 7-tetramethyladamantane 1, 3, 5, 7-TeMA 6 2-甲基单金刚烷 C11H18 2-methyladamantane 2-MA 7 1, 4-二甲基单金刚烷(顺式) C12H20 1, 4-dimethyladamantane(cis) 1, 4-DMA(cis) 8 1, 4-二甲基单金刚烷(反式) C12H20 1, 4-dimethyladamantane(trans) 1, 4-DMA(trans) 9 1, 3, 6-三甲基单金刚烷 C13H22 1, 3, 6-trimethyladamantane 1, 3, 6-TMA 10 1, 2-二甲基单金刚烷 C12H20 1, 2-dimethyladamantane 1, 2-DMA 11 1, 3, 4-三甲基单金刚烷(顺式) C13H22 1, 3, 4-trimethyladamantane(cis) 1, 3, 4-TMA(cis) 12 1, 3, 4-三甲基单金刚烷(反式) C13H22 1, 3, 4-trimethyladamantane(trans) 1, 3, 4-TMA(trans) 13 1, 2, 5, 7-四甲基单金刚烷 C14H24 1, 2, 5, 7-tetramethyladamantane 1, 2, 5, 7-TeMA 14 1-乙基单金刚烷 C12H20 1-ethyladamantane 1-EA 15 2, 6-+2, 4-二甲基单金刚烷 C12H20 2, 6+2, 4-dimethyladamantane 2, 6+2, 4-DMA 16 1-乙基-3-甲基单金刚烷 C13H22 1-E-3-methyladamantane 1-E-3-MA 17 1, 2, 3 -三甲基单金刚烷 C13H22 1, 2, 3-trimethyladamantane 1, 2, 3-TMA 18 1-乙基-3, 5-二甲基单金刚烷 C14H24 1-E-3, 5-dimethyladamantane 1-E-3, 5-DMA 19 2-乙基单金刚烷 C12H20 2-ethyladamantane 2-EA 20 1, 3, 5, 6-四甲基单金刚烷 C14H24 1, 3, 5, 6-tetramethyladamantane 1, 3, 5, 6-TeMA 21 1, 2, 3, 5-四甲基单金刚烷 C14H24 1, 2, 3, 5, -tetramethyladamantane 1, 2, 3, 5-TeMA 22 1-乙基-3, 5, 7-三甲基双金刚烷 C15H26 1-E-3, 5, 7-trimethyladamantane 1-E-3, 5, 7-TMA 23 双金刚烷 C14H20 diamantane D 24 4-甲基双金刚烷 C15H22 4-methyldiamantane 4-MD 25 4, 9-二甲基双金刚烷 C16H24 4, 9-dimethyldiamantane 4, 9-DMD 26 1-甲基双金刚烷 C15H22 1-methyldiamantane 1-MD 27 1, 4-+2, 4-二甲基双金刚烷 C16H24 1, 4+2, 4-dimethyldiamantane 1, 4+2, 4-DMD 28 4, 8-二甲基双金刚烷 C16H24 4, 8-dimethyldiamantane 4, 8-DMD 29 1, 4, 9-三甲基双金刚烷 C17H26 1, 4, 9-trimethyldiamantane 1, 4, 9-TMD 30 3-甲基双金刚烷 C15H22 3-methyldiamantane 3-MD 31 3, 4-二甲基双金刚烷 C16H24 3, 4-dimethyldiamantane 3, 4-DMD 32 3, 4, 9-三甲基双金刚烷 C16H24 3, 4, 9-trimethyldiamantane 3, 4, 9-TMD 33 2-硫代单金刚烷 C9H14S 2-thiaadamantane TA 34 5-甲基-2-硫代单金刚烷 C10H16S 5-methyl-2-thiaadamantane 5-MTA 35 1-甲基-2-硫代单金刚烷 C10H16S 1-methyl-2-thiaadamantane 1-MTA 36 5, 7-二甲基-2-硫代单金刚烷 C10H16S 5, 7-dimethyl-2-thiaadamantane 5, 7-DMTA 37 1, 5-二甲基-2-硫代单金刚烷 C11H18S 1, 5-dimethyl-2-thiaadamantane 1, 5-DMTA 38 1, 3-二甲基-2-硫代单金刚烷 C11H18S 1, 3-dimethyl-2-thiaadamantane 1, 3-DMTA 39 3, 5, 7-三甲基-2-硫代单金刚烷 C12H20S 3, 5, 7-trimethyl-2-thiaadamantane 3, 5, 7-TMTA 40 1, 5, 7-三甲基-2-硫代单金刚烷 C12H20S 1, 5, 7-trimethyl-2-thiaadamantane 1, 5, 7-TMTA 41 1, 3, 7-三甲基-2-硫代单金刚烷 C12H20S 1, 3, 7-trimethyl-2-thiaadamantane 1, 3, 7-TMTA 42 1, 3, 5-三甲基-2-硫代单金刚烷 C12H20S 1, 3, 5-trimethyl-2-thiaadamantane 1, 3, 5-TMTA 43 1, 3, 5, 7-四甲基-2-硫代单金刚烷 C13H22S 1, 3, 5, 7-tetramethyl-2-thiaadamantane 1, 3, 5, 7-TeMTA 44~48 四甲基-2-硫代单金刚烷 C13H22S tetramethyl-2-thiaadamantanes TeMTAs
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