Nitrogen isotopic compositions in NH4+-mineral-bearing coal: Origin and isotope fractionation

Panpan Xie, Shifeng Dai, James C. Hower, Victor P. Nechaev, David French, Ian T. Graham, Xibo Wang, Lei Zhao, Jianping Zuo

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24 Scopus citations

Abstract

Coals containing ammonium-bearing aluminosilicates usually have highly-elevated concentrations of critical elements, including Ga, Al, U, V, Re, Se, and rare earth elements. Coals from the Moxinpo and Yishan coalfields of southern China and the Daqingshan Coalfield of northern China are unusual in containing abundant ammonium-bearing minerals (buddingtonite and ammonian illite). Understanding the source of N in the ammonium-bearing minerals could provide useful information, not only for the enrichment of the critical elements, but also for the formation of these unusual minerals. A geochemical and nitrogen isotope study was undertaken in order to investigate the origin and behavior of nitrogen in the minerals and associated coals. The N contents decrease as rank increases from low volatile bituminous to semi-anthracite, indicating that substantial N was thermally lost during coalification. The isotopic composition of organic nitrogen (δ15Norg) ranges from 3.7 to 7.7‰ and increases with coal rank in the studied samples. However, this does not indicate that the isotope fractionation of organic N was due to the coal rank advance; rather, it is largely caused by the depositional environments of peat accumulation and coal-precursor plant assemblages. δ15N values of inorganic N (δ15Nino) in NH4+-minerals generally have a wider range (5.1 to 12.4‰) than those of organic matter (3.7 to 7.5‰) in coal and are commonly higher than those of δ15Norg in the same coal sample. The N in the ammonium-bearing aluminosilicates was derived from the decomposition of the organic matter of the coals that were subjected to increased geothermal gradient (and fluid flow) as a consequence of igneous intrusion or infiltration of high-temperature hydrothermal fluids. The N released from organic matter was transported by high-T fluids, from which 14N was preferentially converted into volatile matter and 15N readily remained in the fluids. Subsequently NH4+ in the high-T fluids substituted for K+ in pre-existing minerals or NH4+ − bearing high-T fluids reacted with pre-existing kaolinite in the coals, leading to more positive δ15N values for the NH4+-bearing minerals than those of the organic matter in these coals. Therefore, the δ15Nino values in coal, in a wider context, could be potentially used to estimate the degree of high-T heating on coal metamorphism, to trace the pathway of hydrothermal fluids circulating within the coal basin, and to provide useful information on the sources of critical elements that are enriched in coals.

Original languageEnglish
Article number119946
JournalChemical Geology
Volume559
DOIs
StatePublished - Jan 5 2021

Bibliographical note

Publisher Copyright:
© 2020 The Authors

Keywords

  • Ammonian illite
  • Buddingtonite
  • Isotope fractionation
  • Nitrogen in coal
  • Nitrogen isotopes

ASJC Scopus subject areas

  • Geology
  • Geochemistry and Petrology

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