Indication of biomarkers for coal origin traceability
-
摘要:
为了保障进口煤炭质量和安全, 急需建立起一套行之有效的产地溯源方法对进口煤炭进行产地溯源和掺假识别。利用气相色谱-质谱联用仪(GC-MS)对来自5个进口国家的煤炭样品进行了分析, 并对有机质中代表性生物标志化合物进行了定性和定量分析, 以期对煤炭产地溯源新方法新技术提供启示。结果表明: 根据样品饱和烃Ph/nC18和Pr/nC17关系结果认为这5个国家的煤炭样品基本都处于低成熟-成熟阶段, 澳大利亚、俄罗斯、马来西亚和菲律宾的煤炭主要为陆源氧化环境下的Ⅲ型有机质; 除来自印度尼西亚的c56号样品外, 印尼其他煤炭样品和菲律宾全部煤炭样品的正构烷烃分布以中高相对分子质量为主, 暗示母质来源可能为陆源高等植物。研究结果证明不同的样品来自于不同的沉积环境, 有着不同的有机质输入类型等, 采用特定的指标可在一定程度上对溯源可起到指示作用。
Abstract:As the second-largest economy in the world, China has extremely rich coal resources, but the coal resources available for direct mining and utilization are relatively limited and need to rely heavily on imports. To ensure the quality and safety of imported coal, it is urgent to establish a set of effective origin traceability methods to trace the origin and identify the adulteration of imported coal. In this study, coal samples from five importing countries were analysed by gas chromatography-mass spectrometry (GC-MS), and representative biological fingerprint compounds in the organic matter were analysed qualitatively and quantitatively to provide enlightenment for new methods and technologies of coal origin traceability. According to the relationship between Ph/nC18 and Pr/nC17, the coal samples of these five countries are considered to be in the low maturity stage. The coal of Australia, Russia, Malaysia and the Philippines is mainly type Ⅲ organic matter in a terrestrial oxidation environment. Except for the C56 sample from Indonesia, the distribution of n-alkanes in other coal samples from Indonesia and all coal samples from the Philippines mainly have medium and high molecular weight, suggesting that the source of parent material may be terrestrial higher plants. Different samples from different sedimentary environments have different types of organic matter input, and the application of specific indicators of organic matters is an effective method for geographical origin traceability of imported coal to a certain extent.
-
Key words:
- coal origin traceability /
- coal import /
- biological fingerprint characteristics /
- GC-MS
-
图 1 样品饱和烃Pr/nC17和Ph/nC18关系图
Figure 1. Relationship between Pr/nC17 and Ph/nC18 of saturated hydrocarbons
图 3 C27、C28、C29 3种ααα型规则甾烷相对含量三角图
Ⅰ.藻类；Ⅱ.陆生植物；Ⅲ.浮游植物；Ⅳ.混合来源；Ⅴ.藻类为主；Ⅵ.浮游植物为主；Ⅶ.陆生植物为主
Figure 3. Triangle of C27, C28 and C29 ααα-regular steranes
图 4 (孕甾烷+升孕甾烷)/C29ααα20R与规则甾烷/17α(H)-藿烷关系图
Figure 4. (pregnane+pregnane)/C29ααα20R vs.regular sterane/17α(H)-hopane
图 5 Ts/Tm和C30藿烷/C30莫烷的变化趋势图
Figure 5. Variation trend of Ts/Tm and C30 hopane/C30 morane
图 7 规则甾烷/17α(H)-藿烷与升藿烷指数关系图
Figure 7. Relationship between regular sterane/17α(H)-hopane and l-hopane index
表 1 各国煤炭样品信息
Table 1. Coal sample information of each country
样品号 国别 产地 c1 俄罗斯 俄罗斯Vanino c4 印尼 印尼Adangbay c5 印尼 印尼Asam Asam c7 印尼 印尼Bunati c9 印尼 印尼Kaltorang c10 印尼 印尼Muara Berau c16 俄罗斯 俄罗斯新西伯利亚新库兹涅茨克欧亚斯煤矿 c39 澳大利亚 澳大利亚Adelaide c40 澳大利亚 澳大利亚Balmain c42 澳大利亚 澳大利亚Bell Bay c44 俄罗斯 俄罗斯Kuzbass c46 印尼 印尼PT adaro Indonesia c47 印尼 印尼PT bara tabang c49 印尼 印尼PT bukit asaml(perserd)tbk c51 印尼 印尼PT mandiri intiperkasa c54 印尼 印尼PT tunas inti abadi c56 印尼 印尼PT baba anugrah sejahtera c57 印尼 印尼PT Berau coal c59 菲律宾 菲律宾Semirara Mining and Power Corporation c60 马来西亚 马来西亚Sibuti c61 俄罗斯 俄罗斯South Kuzbass c62 菲律宾 菲律宾Subac Nipa c64 澳大利亚 澳大利亚Yancoal Australia Sales Pty Itd 
下载: 导出CSV
表 2 5个国家生物标志化合物参数数据
Table 2. Parameter data of five national biological standards
样品 国家 正构烷烃 无环异戊二烯类烷烃 甾烷 萜烷 OEP CPI 主峰碳 Pr/ nC17 Ph/ nC18 Pr/ Ph C29ααα20S/ (S+R) C29αββ/ (ααα+αββ) Ts/Tm C30(H)/ C30(M) 2γ/C31(H) c39 澳大利亚 1.25 1.04 22.00 1.33 0.37 2.66 0.40 0.40 0.41 2.41 0.72 c40 3.65 4.35 31.00 2.41 0.46 5.76 0.32 0.46 0.55 3.14 6.74 c64 3.71 3.53 31.00 3.42 0.39 5.87 0.31 0.46 0.52 2.91 8.52 c1 俄罗斯 1.28 1.11 23.00 0.86 0.29 2.36 0.41 0.32 9.28 2.15 0.72 c16 2.28 1.85 23.00 2.06 0.32 4.17 0.51 0.55 0.99 1.65 5.64 c44 1.47 1.32 23.00 2.06 0.48 2.49 0.52 0.61 1.10 1.67 0.92 c61 1.41 1.17 23.00 0.88 0.19 3.34 0.34 0.29 5.35 2.83 0.74 c59 菲律宾 3.81 5.02 31.00 0.96 0.32 3.76 0.23 0.43 0.82 4.47 1.66 c62 3.73 4.64 31.00 1.22 0.36 3.89 0.27 0.44 0.67 4.35 1.56 c20 马亚西亚 2.58 3.44 31.00 3.68 0.73 4.74 0.29 0.42 0.78 1.76 3.80 c4 印度尼西亚 4.97 6.40 31.00 0.73 0.43 1.40 0.41 0.77 0.58 1.95 2.95 c5 2.97 3.87 31.00 0.91 0.32 2.30 0.25 0.49 0.46 3.80 2.61 c7 3.82 4.61 31.00 0.99 0.32 2.94 0.23 0.30 0.50 2.31 6.14 c9 4.00 5.05 31.00 0.61 0.30 1.61 0.27 0.65 0.27 1.80 3.37 c10 3.25 3.77 31.00 0.65 0.41 1.78 0.32 0.52 0.32 2.54 4.45 c42 2.08 2.05 27.00 1.24 0.22 5.04 0.21 0.43 1.51 2.68 1.15 c46 3.64 4.50 31.00 0.83 0.21 2.65 0.43 0.26 0.29 4.01 4.16 c47 3.10 3.91 31.00 0.94 0.32 2.02 0.37 0.54 0.38 1.80 0.32 c49 2.38 2.69 27.00 4.24 0.46 6.58 0.35 0.48 0.82 1.17 3.47 c51 3.51 4.19 31.00 0.56 0.42 1.51 0.31 0.59 0.32 2.96 1.94 c54 3.79 4.07 31.00 0.50 0.33 1.76 0.23 0.30 0.32 1.34 3.29 c56 2.17 1.90 25.00 2.00 0.25 4.70 0.27 0.54 1.78 2.15 0.89 c57 3.63 4.58 31.00 0.34 0.27 1.00 0.43 0.64 0.12 0.57 5.59 注：OEP.奇偶优势指数；CPI.碳优势指数
下载: 导出CSV
-
[1] 王英杰, 潘守举, 孙艳红. 中国进口澳大利亚煤现状及对国内市场的影响[J]. 煤炭与化工, 2016, 39(4): 33-35. https://www.cnki.com.cn/Article/CJFDTOTAL-HHGZ201604011.htmWang Y J, Pan S J, Sun Y H. Current situation of China's import of Australian coal and its impact on the domestic market[J]. Coal and Chemical Industry, 2016, 39(4): 33-35(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-HHGZ201604011.htm [2] Jacob T. When good intentions turn bad: The unintended consequences of the 2016 Tanzanian coal import ban[J]. The Extractive Industries and Society, 2020, 7(2): 337-340. doi: 10.1016/j.exis.2019.02.009 [3] Wu J Z, Zhang J. Analysis of capacity adaptability of global coal terminals[J]. Academic Journal of Engineering and Technology Science, 2019, 2(2): 51-58. [4] 王向利, 张良晓, 梁逸曾, 等. GC-MS结合化学计量学方法用于女贞子乙醚提取物的定性定量分析[J]. 中国中药杂志, 2010, 35(17): 2303-2307. https://www.cnki.com.cn/Article/CJFDTOTAL-ZGZY201017019.htmWang X L, Zhang L X, Liang Y Z, et al. Qualitative and quantitative analysis of ethyl ether extract from Fructus Ligustri Lucidi by GC-MS combined with chemometrics[J]. Chinese Journal of Traditional Chinese Medicine, 2010, 35 (17): 2303-2307(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-ZGZY201017019.htm [5] 程顶胜. 中国泥盆纪煤有机地球化学特征[J]. 中国煤田地质, 2006, 18(5): 7-10, 24. doi: 10.3969/j.issn.1674-1803.2006.05.003Cheng D S. Organic geochemical characteristics of Devonian coal in China[J]. Coal Geology of China, 2006, 18(5): 7-10, 24(in Chinese with English abstract). doi: 10.3969/j.issn.1674-1803.2006.05.003 [6] Escobar M, Márquez G, Inciarte S, et al. The organic geochemistry of oil seeps from the Sierra de Perijá eastern foothills, Lake Maracaibo Basin, Venezuela[J]. Organic Geochemistry, 2011, 42(7): 727-738. doi: 10.1016/j.orggeochem.2011.06.005 [7] 毛婉慧. 川东北华蓥山地区龙潭组烃源岩有机地球化学特征和有机相划分[D]. 武汉: 中国地质大学(武汉), 2011.Mao W H. Organic geochemical characteristics and organic facies division of Longtan Formation source rocks in Huayingshan area, Northeast Sichuan[D]. Wuhan: China University of Geosciences(Wuhan), 2011(in Chinese with English abstract). [8] 于海成. 邢台矿区葛泉矿9号煤煤质、煤岩及煤相特征分析[J]. 煤炭与化工, 2019, 42(4): 107-111. https://www.cnki.com.cn/Article/CJFDTOTAL-HHGZ201904032.htmYu H C. Analysis of coal quality, coal petrography and coal facies characteristics of No. 9 coal in Gequan mine of Xingtai mining area[J]. Coal and Chemical Industry, 2019, 42 (4): 107-111(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-HHGZ201904032.htm [9] 吴士豪, 薄朋慧, 徐飞, 等. 贵州松河煤矿晚二叠世煤的有机地球化学特征[J]. 地质科技通报, 2020, 39(4): 141-149. doi: 10.19509/j.cnki.dzkq.2020.0418Wu S H, Bo P H, Xu F, et al. Organic geochemical characteristics of Late Permian coal in Songhe coal mine, Guizhou[J]. Geological Science and Technology Bulletin, 2020, 39(4): 141-149(in Chinese with English abstract). doi: 10.19509/j.cnki.dzkq.2020.0418 [10] 唐跃刚, 王绍清, 郭鑫, 等. 煤有机地球化学研究进展与展望[J]. 矿物岩石地球化学通报, 2021, 40(3): 574-596, 777. https://www.cnki.com.cn/Article/CJFDTOTAL-KYDH202103004.htmTang Y G, Wang S Q, Guo X, et al. Research progress and prospect of coal organic geochemistry[J]. Mineral and Rock Geochemistry Bulletin, 2021, 40(3): 574-596, 777(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-KYDH202103004.htm [11] 刘洪星, 王登, 纪中云, 等. 库车坳陷东部依南2井烃源岩地球化学特征[J]. 资源环境与工程, 2018, 32(2): 233-236. https://www.cnki.com.cn/Article/CJFDTOTAL-HBDK201802015.htmLiu H X, Wang D, Ji Z Y, et al. Geochemical characteristics of source rocks from well Yinan 2 in Eastern Kuqa Depression[J]. Resources, Environment and Engineering, 2018, 32(2): 233-236(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-HBDK201802015.htm [12] 吴小红, 吕新华. 东濮凹陷胡庆油田烃源岩地球化学特征分析[J]. 海洋石油, 2005, 25(3): 29-35. doi: 10.3969/j.issn.1008-2336.2005.03.006Wu X H, Lü X H. Geochemical characteristics of source rocks in Huqing oilfield, Dongpu depression[J]. Offshore Oil, 2005, 25(3): 29-35(in Chinese with English abstract). doi: 10.3969/j.issn.1008-2336.2005.03.006 [13] Jiang W M, Li Y, Yang C, et al. Organic geochemistry of source rocks in the Baiyun Sag of the Pearl River Mouth Basin, South China Sea[J]. Marine and Petroleum Geology, 2021, 124: 104836. doi: 10.1016/j.marpetgeo.2020.104836 [14] 窦廷焕, 高菊芬. Pr/Ph值与煤化程度的关系及成煤环境意义[J]. 煤田地质与勘探, 1996, 24(1): 19-21. https://www.cnki.com.cn/Article/CJFDTOTAL-MDKT601.005.htmDou T H, Gao J F. The relationship between Pr/Ph value and degree of coalification and the significance of coal forming environment[J]. Coalfield Geology and Exploration, 1996, 24(1): 19-21(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-MDKT601.005.htm [15] 龚迎莉, 孙玮琳, 汪双清, 等. 生油岩中有机质加速溶剂萃取和索氏萃取方法对比[J]. 岩矿测试, 2009, 28(5): 416-422. doi: 10.3969/j.issn.0254-5357.2009.05.004Gong Y L, Sun W L, Wang S Q, et al. Comparison of accelerated solvent extraction and Soxhlet extraction methods for organic matter in source rocks[J]. Rock and Mineral Testing, 2009, 28 (5): 416-422(in Chinese with English abstract). doi: 10.3969/j.issn.0254-5357.2009.05.004 [16] 陈中红, Moldowan J M, 刘昭茜. 东营凹陷生物降解稠油甾烷分子的选择蚀变[J]. 地球科学进展, 2012, 27(10): 1108-1114. https://www.cnki.com.cn/Article/CJFDTOTAL-DXJZ201210011.htmChen Z H, Moldowan J M, Liu Z X. Selective alteration of sterane molecules in biodegradable heavy oil in Dongying Depression[J]. Progress in Geosciences, 2012, 27(10): 1108-1114(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-DXJZ201210011.htm [17] 刘春艳. 新疆三塘湖盆地石炭系烃源岩地球化学特征研究[D]. 兰州: 兰州大学, 2009.Liu C Y. Geochemical characteristics of Carboniferous source rocks in Santanghu Basin, Xinjiang[D]. Lanzhou: Lanzhou University, 2009(in Chinese with English abstract). [18] 柯友亮, 王华, 甘华军, 等. 准噶尔盆地南缘芦草沟组上段油页岩有机地球化学特征及其沉积意义[J]. 地质科技情报, 2019, 38(3): 199-207. https://www.cnki.com.cn/Article/CJFDTOTAL-DZKQ201903021.htmKe Y L, Wang H, Gan H J, et al. Organic geochemical characteristics and sedimentary significance of the Upper Lucaogou Formation in the southern margin of Junggar Basin[J]. Geological and Technological Information, 2019, 38 (3): 199-207(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-DZKQ201903021.htm [19] 丁飞. 东营凹陷深层烃源岩可溶有机质特征与沉积有机相划分[D]. 青岛: 中国海洋大学, 2008.Ding F. Characteristics of soluble organic matter and division of sedimentary organic facies of deep source rocks in Dongying Sag[D]. Qingdao Shandong: Ocean University of China, 2008(in Chinese with English abstract). [20] 童成英, 何守阳, 丁虎. 茶叶产地与品质的元素、同位素鉴别技术研究进展[J]. 生态学杂志, 2018, 37(5): 1574-1583. https://www.cnki.com.cn/Article/CJFDTOTAL-STXZ201805036.htmTong C Y, He S Y, Ding H. Research progress on identification technology of elements and isotopes for origin and quality of tea[J]. Journal of Ecology, 2018, 37 (5): 1574-1583(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-STXZ201805036.htm [21] 覃建华, 高儇博, 彭寿昌, 等. 准噶尔盆地吉木萨尔凹陷页岩油地球化学特征及油—源对比[J]. 东北石油大学学报, 2021, 45(1): 1-10, 123. https://www.cnki.com.cn/Article/CJFDTOTAL-DQSY202101001.htmQin J H, Gao L B, Peng S C, et al. Geochemical characteristics and oil source correlation of shale oil in Jimusaer Sag, Junggar Basin[J]. Journal of Northeast Petroleum University, 2021, 45(1): 1-10, 123(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-DQSY202101001.htm [22] 周勇水, 彭君, 李红磊, 等. 成熟度对甾萜类化合物组成特征的影响: 以银额盆地查干凹陷为例[J]. 东北石油大学学报, 2020, 44(6): 103-113, 11. https://www.cnki.com.cn/Article/CJFDTOTAL-DQSY202006011.htmZhou Y S, Peng J, Li H L, et al. Effect of maturity on the composition of steroids and terpenes: A case study of Chagan Sag in Yine Basin[J]. Journal of Northeast Petroleum University, 2020, 44(6): 103-113, 11(in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-DQSY202006011.htm [23] 陈文彬, 廖忠礼, 张予杰, 等. 北羌塘盆地侏罗系布曲组烃源岩地球化学特征及意义[J]. 中国地质, 2007, 34(5): 927-934. https://www.cnki.com.cn/Article/CJFDTOTAL-DIZI200705020.htmChen W B, Liao Z L, Zhang Y J, et al. Geochemical characteristics and significance of source rocks of Jurassic Buqu Formation in North Qiangtang Basin[J]. Geology of China, 2007, 34(5): 927-934 (in Chinese with English abstract). https://www.cnki.com.cn/Article/CJFDTOTAL-DIZI200705020.htm -
下载:
点击查看大图
计量
- 文章访问数: 479
- PDF下载量: 35
- 被引次数: 0
