Characteristics of Lignin-derived Phenolic Compounds in Arid Lake, Northeastern China and Climatic Implications
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摘要:
木质素广泛分布于维管植物，经分解生成的酚类化合物可示踪有机质来源、评估木质素降解程度，进而用于反演古环境与古气候变化。采用合适的分析方法有效地分解木质素是推断母源植物类型、降解程度的技术基础，常规方法是木质素经碱(或酸)解后，利用气相色谱-质谱法(GC-MS)分析酚类单体化合物，但分解、提取过程复杂、易引入杂质。热裂解技术可在高温下快速分解有机质，裂解产物可通过GC-MS进行在线分析，具有用样量少、有机质提取比例高、重现性好、操作便捷的特点。本文选择地处亚洲夏季风影响区域的边缘的内蒙伊和沙日乌苏湖，采用热裂解GC-MS(Py-GC/MS)技术，对湖泊沉积物进行裂解分析，在对裂解温度(450℃、550℃和650℃)进行了优化的基础上，识别了21种酚类化合物，包括：4-甲基苯酚、2-乙基苯酚等9种烷基酚类(PHs)，4-乙基-2-甲氧基苯酚、4-乙烯基-2, 6-二甲氧基苯酚等9种烷基酚类(PHs)和12种甲氧基酚类(LGs)。结合沉积岩心样品AMS 14C年龄的分析结果，6.7ka以来沉积物中酚类化合物总量、PHs和LGs的变化趋势总体一致，呈现出6.7~4.0ka相对含量较高、4.0ka以来相对含量较低的特征。不同于PHs中邻(o-)-PHs、间(m-)-PHs、对(p-)-PHs的变化趋势与总量一致；但不同取代特征的LGs相对含量变化趋势存在差异，p-LGs在5.4ka前后就出现含量显著下降，3.8ka以来维持较低水平。根据微生物对木质素的“去甲基/去甲氧基”氧化反应途径，对位取代酚类化合物比值(p-PHs/p-LGs)可作为陆生高等植物降解指标，该值越大微生物降解作用越强。将p-PHs/p-LGs指标应用于伊和沙日乌苏沉积物样品结果显示，6.7ka以来p-PHs/p-LGs与正构烷烃单体碳同位素δ13C27~33变化趋势一致(R=-0.77)，间接地指示了有效降水变化。即6.7ka以来气候整体转湿，区内陆生高等植物占据优势，充足的水分和有机质为微生物提供了适宜的生存环境和相对稳定的营养来源，降解作用整体呈增强趋势；6.3~5.5ka和4.1~3.6ka期间有效湿度降低，微生物对木质素的降解作用相对减弱。p-PHs/p-LGs指标对应了呼伦贝尔地区湿度变化特征，揭示了干旱-半干旱地区微生物降解与有效湿度变化的相关性，为探讨陆地生态系统对东亚季风北部边缘区气候变化的响应提供科学依据。
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关键词:
- 热裂解-气相色谱-质谱法 /
- 伊和沙日乌苏湖 /
- 木质素酚类单体化合物 /
- 微生物降解 /
- 古气候
Abstract:BACKGROUND Lignin is widely distributed in vascular plants, and lignin-derived phenolic compounds generated by decomposition could provide information on the source of organic matter and the degradation degree of lignin. The conventional method for lignin deconstruction is complex and involves lignin hydrolysis via alkaline/acid chemical reagents. The analytical technique pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) breaks the chemical bonds of large molecule compounds by instantaneous high temperature to generate a series of small molecule compounds without introducing pretreatment methods such as chemical extractions, realizing the online analysis of complex organic matter that is not easy to be gasified. This technique is characterized by low sample volume, high organic matter extraction ratio, good reproducibility, and convenient operation. It has been shown that the high-temperature cracking products of peat and lake sediments are similar to the results of traditional CuO oxidative decomposition. The distribution characteristics of phenolic compounds indicate the vegetation type and organic matter degradation characteristics. However, the optimization of analytical methods, application of environmental indication significance, and comparative studies of different matrix samples are still needed.
OBJECTIVES (1) Investigate suitable analytical methods for decomposing lignin in lake sediment samples and identify pyrolytic phenolic compounds in the sediments of Yiheshariwusu Lake in the northeast semi-arid region of China (Fig.E.1A, B). (2)Discuss the distribution characteristics of phenolic compounds in the sediments of Yiheshariwusu Lake. (3) Reveal the correlation between pyrolytic lignin phenols and regional climate change in the study area by combining traditional climate proxies, and provide an effective indicator for interpreting the response of terrestrial ecosystems to global climate change.
METHODS (1) Analytical method: An optimized analytical method of Py-GC/MS was established and applied to evaluate lignin-derived phenolic compounds in typical arid lake sediment. Samples were heated to 650℃ for 20s (heating rate 20℃/ms) and pyrolysis products were injected into the gas chromatography (GC) system in split mode, then separated in a nonpolar, low-bleed fused silica column (DB-1MS, 60m, 0.25mm i.d., 0.25μm film thickness, J&W). The GC oven program was set to increase from 40 to 320℃ at a rate of 4℃/min, and left at 320℃ for 18min. With internal electron ionization and ion trapping, the compounds were fragmented and identified in full scan mode (40-450amu). Blank and duplicate samples were analysed for quality control.
(2) Establishment of climatic proxy: Yiheshariwusu was selected as a typical arid lake and pyrolytical phenolic compounds of sediment cores were analysed. Historical variation of phenolic compound combing with radiocarbon dating results were revealed. According to "demethyl/demethoxy" oxidation reaction pathway of microorganisms to lignin, indicator related to degradation degree of lignin was established, and by comparing the indicators with conventional climate proxies previously published in the region, correlations between the indicators and climate features such as effective precipitation can be explored.
RESULTS (1) Py-GC/MS analysis method for phenolic compounds was optimized. Phenolic compounds in the total pyrolytic products of sediments were categorized into 2 groups according to the type of functional group: alkyl-phenols (phenol compounds, PHs) and methoxy-phenols (lignin monomer compounds, LGs), which are further divided into o-, m- and p-compounds according to the position of the substituent on the benzene ring structure. Based on fine characterization of organic matter composition in the sediments of Yiheshariwusu Lake in Inner Mongolia, 21 phenolic compounds were identified and analyzed, including 9 PHs and 12 LGs (Table 1). Pyrolysis temperature is the main factor affecting the results of Py-GC/MS analysis of sediment organic matter fingerprinting. By discussing the effect of different pyrolysis temperatures on the distribution characteristics of the total pyrolytic products at 450℃, 550℃ and 650℃, it was determined that the relative concentration of lignin phenolic compounds increased significantly with increasing pyrolysis temperature. The ether bond (C—O—C) connecting the lignin skeleton structure benzene propane structural unit was further broken as the temperature was increased from 450℃ to 650℃. The relative concentration of phenolic compounds in the pyrolysis compounds reached the highest proportion (16.46%), while the proportion of aromatic hydrocarbons and aliphatic hydrocarbons increased by 3.98% and 10.26%, respectively. The natural macromolecules, which are not easily vaporized, are gradually cleaved into smaller ionic fragments of phenolic compounds under high pyrolysis temperature. As the cleavage temperature increases to 650℃, the flux of phenolic compounds into the chromatographic system increases and the gas chromatographic response is gradually enhanced, with the phenolic compounds reaching the highest ionic intensity response. At the same time, the unit peak area, shape and signal-to-noise ratio were all improved, which improved the accuracy of phenolic compound identification and analysis.
(2) Distribution characteristics of phenolic compounds in Yiheshariwusu Lake were discussed. According to AMS 14C age data, historical variation of total phenolic compounds, PHs and LGs in lake sediment are generally consistent since 6.7ka, showing the characteristics of high relative concentration of 6.7-4.0ka and low concentration since 4.0ka. The variation characteristics of o-PHs, m-PHs, and p-PHs are consistent with total PHs, yet the change characteristics of p-LGs and LGs are different, the relative concentration of p-LGs decreased significantly near 5.4ka and remained at a low level since 3.8ka (average relative concentration of 0.29%). Combined with the lithological characteristics of sediment cores, relative concentration of total phenolic compounds and PHs decreased significantly around 4.0ka, probably due to the change of sedimentary lithology from sand to clay with smaller grain sizes during 4.0-3.8ka, where compounds with smaller molecular weights were preserved in the sediments, and the relative concentration of aliphatic hydrocarbons (e.g., n-alkanes, n-alkenes) and aromatic hydrocarbons significantly increased.
(3) Environmental indication significance of phenolic compounds was studied. According to previous studies of free n-alkanes distribution proxies (e.g., ACL23-33), higher relative concentration in lake sediments of p-PHs indicated major herbaceous source of lignin, however, significant differences in the mean relative concentration of p-PHs and LGs indicated significant microbial degradation of organic matter. The mean value of p-PHs/p-LGs for Yiheshariwusu Lake sediments was 16.41 (n=31, range of 4.36-37.31), showing an overall increasing trend since 6.7ka, reflecting a gradual increase in microbial activities. p-PHs/p-LGs showed a consistent trend and negative correlation with δ13C27-33 (n=31, R=-0.77, p < 0.01), meanwhile, variation of p-PHs/p-LGs positively correlated with the trend of increasing pollen of Chenopodiaceae and Poaceae in Hulun Lake sediment (n=31, R=0.54, p < 0.01), and on a larger scale, p-PHs/p-LGs are consistent and positively correlated with the gradual increase in the standardized precipitation index since 6.7ka in the northern hemisphere mid-latitudes (n=31, R=0.62, p < 0.01) (Fig.E.1C).
CONCLUSIONS The suitable pyrolysis temperature for Py-GC/MS analysis of phenolic compounds in the sediments of Yiheshariwusu Lake is 650℃. The value of degradation index p-PHs/p-LGs corresponds to the degree of lignin degradation, and the larger the value, the stronger the microbial degradation. Applying the p-PHs/p-LGs index to the sediment samples of Yiheshariwusu Lake, the result show that degradation index (p-PHs/p-LGs) and the carbon isotope of free n-alkanes δ13C27-33 has solid correlation since 6.7ka, indirectly indicating the change of effective precipitation, as the climate turned wet generally since 6.7ka, with terrestrial higher plants dominant, humid climate and sufficient organic matter provided a suitable living environment and relatively stable nutrient source for microorganisms, and the degradation generally increased. Since effective precipitation decreased during 6.3-5.5ka and 4.1-3.6ka, the degradation of lignin by microorganisms was relatively weakened. The p-PHs/p-LGs index corresponds to the characteristics of effective precipitation in the Hulun Buir region, revealing the correlation between microbial degradation and humidity change in arid and semi-arid regions. These findings provide a scientific basis for exploring the response of terrestrial ecosystems to climate change in the northern marginal region of the East Asian monsoon.
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表 1 伊和沙日乌苏湖沉积物裂解产物中酚类化合物
Table 1. Pyrolytic phenolic compounds in sediment of Yiheshariwusu Lake
代号 化合物名称 保留时间(min) 化学式 分子量 特征离子(m/z) PH1 苯酚
Phenol20.14 C6H6O 94 94 PH2 2-甲基苯酚
2-Methylphenol23.02 C7H8O 108 107, 108 PH3 苯乙酮
Acetophenone23.22 C8H8O 120 105, 77 PH4 4-甲基苯
4-Methylphenol23.87 C7H8O 108 107, 108 PH5 2-乙基苯酚
2-Ethylphenol26.26 C8H10O 122 107, 122 PH6 3-乙基苯酚
3-Ethylphenol26.67 C8H10O 122 107, 122 PH7 4-乙基苯酚
4-Ethylphenol27.36 C8H10O 122 107, 122 PH8 2-乙基-6-甲基苯酚
2-Ethyl-6-methylphenol29.59 C9H12O 136 121, 136 PH9 2-乙基-5-甲基苯酚
2-Ethyl-5-methylphenol29.97 C9H12O 136 121, 136 LG1 2-甲氧基苯酚
2-Methoxyphenol (Guaiacol)23.22 C7H8O2 124 109, 124 LG2 4-甲氧基苯酚
Methoxyphenol24.24 C7H8O2 124 109, 124 LG3 5-甲基-2-甲氧基苯酚
Methoxy-5-methylphenol
(5-Methylguaiacol)28.07 C8H10O2 138 123, 138 LG4 4-乙基-2-甲氧基苯酚
4-Ethyl-2-methoxyphenol
(4-Ethylguaiacol)31.42 C9H12O2 152 137, 152 LG5 4-乙烯基-2-甲氧基苯酚
4-Vinyl-2-methoxyphenol
(4-Vinylguaiacol)32.54 C9H10O2 150 135, 150 LG6 2, 6-二甲氧基苯酚
2, 6-dimethoxyphenol (Syringol)33.46 C8H10O3 154 154, 139 LG7 4-(2-丙烯基)-2-甲氧基苯酚
4-(2-Propenyl)-2-methoxyphenol (Eugenol)37.06 C10H12O2 164 164, 149 LG8 4-乙酰基-2-甲氧基苯酚
4-Acetyl-2-methoxyphenol (4-Acetylguaiacol)37.85 C9H10O3 166 151, 166 LG9 4-乙基-2, 6-二甲氧基苯酚
4-Ethyl-2, 6-dimethoxyphenol (4-Ethylsyringol)39.19 C10H14O3 182 167, 182 LG10 4-乙烯基-2, 6-二甲氧基苯酚
4-Vinyl-2, 6-dimethoxyphenol (4-Vinylsyringol)40.28 C10H12O3 180 165, 180 LG11 4-羟基-3, 5-二甲氧基苯甲醛
4-Hydroxy-3, 5-dimethoxybenzaldehyde (syringaldehyde)43.06 C9H10O4 182 182, 181 LG12 4-(1-丙烯基)-2, 6-二甲氧基苯酚
4-(1-Propenyl)-2, 6-dimethoxyphenol
(4-Propenylsyringol)44.21 C11H14O3 194 194, 91 
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