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摘要:
贵州下寒武统牛蹄塘组黑色页岩富集了以Ni、V为主的伴生元素，并且富有机质，目前金属元素Ni、V与有机质的共富集机制尚不清楚，但有机质在金属离子的富集、迁移和转化的过程中具有重要作用。探究金属元素作用对有机质结构的影响有助于准确地认识有机质和金属元素的共富集机制。本文以胡敏素为研究对象，分别与Ni、V两种金属标准溶液混合后恒温振荡，通过元素组成、X射线光电子能谱（XPS）和固体核磁共振碳谱（13C-NMR）由表到里揭示金属溶液作用前后胡敏素结构的变化特征。结果表明：胡敏素的元素组成以C、O为主，Ni、V两种金属溶液作用后，均造成胡敏素中O和S元素的相对含量减少，C和N元素的相对含量增加。XPS测试显示，胡敏素表面的C元素主要以芳香碳形态赋存，O元素则主要以羟基氧形态赋存；对于不同赋存形态的C元素，Ni、V金属溶液作用后对其影响趋势一致，均使芳香碳、羟基碳和羰基碳减少，主要破坏芳香碳(C—C/C—H)单键；而对于不同赋存形态的O元素，Ni金属溶液作用后则使羟基氧和羧基氧减少，使其中的富氢富氧官能团脱出，V金属溶液作用后则使羰基氧和羧基氧减少，破坏其中的羰基双键(C=O)。13C-NMR测试显示，作用前后的胡敏素有机质芳香结构主要以单环或者双环结构存在，两种金属溶液均能使氧接芳碳（
$f_{\rm{ar}}^{\rm{P}} $ $f_{\rm{ar}}^{\rm{B}} $ Abstract:BACKGROUND Black shales are mostly developed in special periods in geological history. They not only record the evolution characteristics of paleoenvironment, paleoclimate and paleontology, but also are carriers of organic matter, oil and gas and various metal deposits. Taking the black shale of the Lower Cambrian Niutitang Formation in Guizhou as an example, it not only shows the extraordinary enrichment of V, Ni and other metal elements, forming vanadium ore and nickel-molybdenum ore, but is also rich in organic matter, with TOC content of 0.7%-14.6% (average 5.2%). At present, the co-enrichment mechanism of metal elements Ni, V and organic matter is still unclear, but organic matter plays an important role in the enrichment, migration and transformation of metal ions.
OBJECTIVES To understand the co-enrichment mechanism of organic matter and metal elements by exploring the effect of metal elements on the structure of organic matter.
METHODS Take two groups of 50mL polypropylene centrifuge tubes A and B, and add 5g of humin to each centrifuge tube. Then add 20mL of Ni single element standard solution to the group A centrifuge tube, and 20mL of V single element standard solution to the group B centrifuge tube. Place the centrifuge tube in a constant temperature oscillator for 24h with the temperature of 298K and the speed of 220r/min. After standing for 24h, the filtered solid part is placed in a 50mL beaker and dried. The dried samples (numbered as HM-Ni and HM-V) and the original humin sample (numbered HM) are analyzed by element analyzer, X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance carbon spectroscopy (13C-NMR).
RESULTS The results show that the elemental composition of humin is mainly C and O. After the action of Ni and V metal solutions, the relative contents of O and S elements in humin decrease, and the relative contents of C and N elements increase. The ratio of H/C and O/C atoms is HM>HM-V>HM-Ni. XPS test shows that the C element on the surface of humin is mainly in the form of aromatic carbon, while the O element is mainly in the form of hydroxyl oxygen. For C with different occurrence forms, the influence trend of Ni and V metal solutions on them is the same, which reduces aromatic carbon, hydroxyl carbon and carbon-based carbon, and mainly destroys aromatic carbon (C—C/C—H) single bonds. For O with different occurrence forms, the Ni metal solution reduces hydroxyl oxygen and carboxyl oxygen, which makes the hydrogen-enriched and oxygen-enriched functional groups prolapse; the V metal solution reduces carbonyl oxygen and carboxyl oxygen, which destroys the carbonyl double bond (C=O). Solid-state nuclear magnetic resonance carbon spectroscopy (13C-NMR) tests show that the action of Ni metal solution can reduce the relative contents of bridged aromatic carbon (far B), oxygen-connected aromatic carbon (far P), carbonyl carbon (fa O), methyl and quaternary carbon (fal *), as well as methylene and methine carbon (fal H); V metal solution can reduce the relative contents of protonated aromatic carbon (far H), bridged aromatic carbon (far B), oxygen-connected aromatic carbon (far P), carbonyl carbon (fa O), methyl and quaternary carbon (fal *), as well as methylene and methine carbon (fal H). Both metal solutions can make the O-enriched and H-enriched functional groups in oxygen-linked aromatic carbon (far P) and bridged aromatic carbon (far B) prolapse from the aromatic ring, shorten the lipid chain length in humin, reduce the stability of organic carbon, reduce the content of active organic carbon and reduce the degree of hydrophobicity.
CONCLUSIONS Through comparative analysis, it is shown that humin has a certain oxidation ability to Ni and V metal elements. After the action of the two metal solutions, the occurrence morphology of C and O elements in humin can be changed. Ni metal solution mainly affects the aliphatic carbon structure, while V metal solution mainly affects the aromatic carbon structure.
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Key words:
- organic matter /
- humin /
- metal elements /
- XPS /
- 13C-NMR /
- structural characteristics
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表 1 样品元素分析结果
Table 1. Elemental analysis results of samples.
样品编号 元素组成(%) 原子比 C H N S O H/C O/C HM 40.71 2.79 0.65 0.24 55.62 0.82 1.03 HM-Ni 42.82 2.83 1.66 0.14 52.55 0.79 0.92 HM-V 41.46 2.77 1.73 0.14 53.90 0.80 0.98 
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表 2 样品的XPS宽扫分析结果
Table 2. Results of XPS wide scan analysis of samples.
样品编号 样品表面C、O元素含量（%） O/C C O HM 45.98 52.24 0.85 HM-Ni 43.80 53.43 0.92 HM-V 43.83 53.52 0.92
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表 3 胡敏素13C-NMR谱化学位移归属
Table 3. Attribution of chemical shifts in 13C-NMR spectra of huminin.
基团 结构 化学位移（×10−6） 甲基碳 
12~16 芳香甲基碳 
16~22 与脂肪族甲基相连的亚甲基碳 
23~32 亚甲基碳 
32~36 次甲基碳和季碳 
36~50 氧与甲基或亚甲基碳连接 
50~60 氧与亚甲基碳连接 
60~70 氧与季碳相连 
75~90 质子化芳碳 
100~129 桥接芳碳 
129~137 侧枝芳碳 
137~148 氧接芳碳 
148~165 羧基碳 
165~190 羰基碳 
190~220
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表 4 C1s和O1s的XPS分峰拟合结果
Table 4. XPS split peak fitting results of C1s and O1s.
元素峰 元素形态 结合能
（eV）不同元素形态的含量（%） HM HM-Ni HM-V C 1s 芳香碳 284.4 42.01 32.25 31.12 脂肪碳 285.1 30.61 35.11 38.96 羟基碳 286.0 4.34 3.51 3.90 酮基碳 286.7 8.09 9.37 10.04 羰基碳 287.8 4.50 2.41 2.47 羧基碳 288.7 10.46 17.34 13.51 O 1s 羰基氧 531.5±0.05 26.50 33.03 24.95 羟基氧 532.9 69.09 64.30 71.70 羧基氧 536.15±0.1 4.41 2.67 3.35
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表 5 样品的13C-NMR分峰拟合结构参数
Table 5. 13C-NMR split peak fitting structural parameters of samples.
样品
编号含量（%） far farH farB farS farP fa faC faO fal fal* falH falO HM 66.43 39.86 14.44 0.7 12.13 15.25 4.49 10.76 18.32 4.89 10.41 3.02 HM-Ni 67.55 42.16 12.32 8.05 5.02 17.11 7.47 9.64 15.33 3.38 8.65 3.3 趋势 +1.12 +2.3 −2.12 +7.35 −7.11 +1.86 +2.98 −1.12 −2.99 −1.51 −1.76 +0.28 HM-V 61.59 38.71 13.98 4.81 4.09 16.68 7.23 9.45 21.73 6.17 10.19 5.37 趋势 −4.84 −1.15 −0.55 +4.11 −8.04 +1.43 +2.74 −1.31 3.41 −1.28 −0.22 +2.35 注：far—芳碳； fa—羧基和羰基碳； fal—脂肪碳； farH—质子化芳碳； farB—桥接芳碳； farS—侧枝芳碳； farP—氧接芳碳； faC—羧基碳； faO—羰基碳； fal*—甲基碳和季碳； falH—亚甲基碳和次甲基碳； falO—氧接脂肪碳。
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表 6 样品部分结构参数
Table 6. Some structural parameters of samples.
样品编号 XBP Cn 脂肪碳/芳香碳 疏水碳/亲水碳 烷基碳/烷氧碳 HM 0.22 14.87 0.28 4.47 5.07 HM-Ni 0.18 1.07 0.23 3.90 3.65 HM-V 0.23 2.12 0.35 3.54 3.05 注：XBP= farB/ far； Cn= farH/ farS； 脂肪碳/芳香碳= fal/ far； 疏水碳/亲水碳=( fal*+ falH+ far)/( falO+ fa)； 烷基碳/烷氧碳=( fal*+ falH)/ falO。
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