Valentin A. Nivin

The article presents a comprehensive analysis of long-term studies on hydrogen-hydrocarbon free gases (FGs) in the rocks of the Khibiny massif, systematically organized and generalized for the first time. Gasometric observations were predominantly conducted within underground mine workings, with occasional measurements taken during the drilling of exploration boreholes at the surface or in subsurface air within loose sediments. Methane is the primary component of these gases, followed in descending order by hydrogen, ethane, helium, other methane homologs, and alkenes. Nitrogen is also presumed to be present, although its proportions remain undefined. The carbon and hydrogen in FGs exhibit relatively heavy isotopic compositions, which progressively lighten from methane to ethane. The intensity of gas emissions is characterized by a gas flow rate from shot holes and boreholes, reaching up to 0.5 L/min but generally decreasing significantly within an hour of reservoir exposure. Gas-bearing areas, ranging in size from a few meters to tens of meters, are distributed irregularly and without discernible patterns. The FG content in rocks and ores varies from trace amounts to approximately 1 m³ of gas per cubic meter of undisturbed rock. These gases are primarily residual, preserved within microfractures and cavities following the isolation of fluid inclusions. Their distribution and composition may fluctuate due to the dynamic geomechanical conditions of the rock mass. The release of flammable and explosive FGs presents a significant hazard during ore deposit exploration and development, necessitating the implementation of rigorous safety measures for mining and drilling operations. Additionally, the environmental implications and potential applications of gas emissions warrant attention. Future comprehensive studies of the Khibiny gases using advanced methodologies and equipment are expected to address various scientific and practical challenges.

The origin of hydrogen–hydrocarbon gases present in the rocks of the Khibiny massif in unusually high concentrations has been the subject of many years of discussion. To assess the role of potential mechanisms and relative time of formation of gases occluded in inclusions in minerals, the molecular weight distribution of C₁–C₅ alkanes in the main rock types of the Khibiny massif was studied. For this purpose, the occluded gases were extracted from rocks by mechanical grinding and their composition was analyzed on a gas chromatograph. It is established that the molecular weight distribution of occluded hydrocarbon gases in the Khibiny massif corresponds to the classical Anderson–Schulz–Flory distribution. In addition, the slopes of the linear relationships are relatively steep. This indicates a predominantly abiogenic origin of the occluded gases of the Khibiny massif. At the same time, a small proportion of biogenic hydrocarbons is present and is associated with the influence of meteoric waters. It was also found that in the Khibiny massif, the proportion of relatively high-temperature gases decreases towards the Main foidolite Ring in the following sequence: foyaite and khibinite–trachytoid khibinite–rischorrite and lyavochorrite–foidolites and apatite–nepheline ores. In the same sequence, an increase in the proportion of heavy hydrocarbons and the increasing role of oxidation and condensation reactions in the transformation of hydrocarbons occurs.

The occurrence of hydrocarbon gases (HCG) in unusually high concentrations for magmatic complexes, in the Lovozero and some other alkaline massifs, is of both geochemical and practical interest. The nature of these gases, despite the long history of research, remains the subject of debate. As an approach to solving this problem, we studied the coupled distribution of occluded HCG and the recognized tracers of various geological processes, such as helium and argon isotopes. The extraction of the gas components trapped in fluid micro-inclusions was carried out by the mechanical crushing of rock and mineral samples. A positive correlation was found between the ³He/⁴He and CH₄/C₂H₆ ratios, whereas a negative correlation of the latter was found with the ³⁶Ar concentration, which in turn was directly related, in varying degrees, to the content of HCG and most strongly with pentanes. Conjugacy of the processes of the heavier gaseous hydrocarbons, a loss of the deep component of the fluid phase and dilution of it with the atmogenic component was established. In the absence of a correlation between CH₄ and ³He, the value of the CH₄/³He ratio in the Lovozero gas substantially exceeded the estimates of it in gases of a mantle origin, and mainly corresponded to the crustal values. However, in some samples, a small fraction of mantle methane was allowed. The peculiarities of the relationships between hydrocarbon gases and the isotopes of noble gases indicate a sequential process of abiogenic generation and transformation of HCG at the magmatic and post-magmatic stages during the formation of the Lovozero massif. The obtained results confirm the usefulness of this approach in solving the origin of reduced gases in alkaline igneous systems.

The Khibiny and Lovozero massifs—the world’s largest alkaline massifs—contain deposits with unique reserves of phosphorus and rare metals, respectively. The reduced gas content in the rocks and, especially, the ore deposits of these massifs is unusually high for igneous complexes, thus representing both geochemical and practical interests. There are three morphological types (or occurrence forms) of the gas phase in these deposits: occluded (predominantly in vacuoles of micro-inclusions in minerals), diffusely dispersed, and free. All three morphological types have the same qualitative chemical gas composition. Methane is the main component, and molecular hydrogen (which sometimes dominates) and ethane are the subordinate constituents. Heavier methane homologs (up to and including pentanes), alkenes, helium, and rarely carbon oxide and dioxide are present in minor or trace amounts. All three morphological types of gases are irregularly distributed in space to various degrees. Free gases also show a release intensity that varies in time. The majority of researchers recognize that the origin of these gases is abiogenic and mostly related to the formation of the massifs and deposits. However, the relative time and mechanism of their generation are still debated. Emissions of combustible and explosive hydrogen–hydrocarbon gases pose hazards during the underground mining of ore deposits. Therefore, the distinctive features of gas-bearing capacity are an essential part of the mining and geological characterization of such deposits because they provide a basis for establishing and implementing special measures of the gas regime during mining operations.

The paper presents the results of a long–term (52 months) monitoring of molecular hydrogen release from the rocks of the Lovozero Massif. Observations are performed in an underground mine with the...

The distribution of He and Ar isotopes has been studied in 41 rock samples and seven monomineralic fractions from ore-bearing layered units and poorly differentiated host gabbronorite of the Western Pana mafic–ultramafic pluton on the Kola Peninsula. The gases assigned for mass-spectrometric analysis were released by means of whole-rock sample melting and by comminution mainly from fluid microinclusions. The data show that the present-day isotopic composition of noble gases in rocks from the pluton is caused by many factors: the degree of melt degassing, various concentrations and retention of the trapped isotopes, the contents of radioactive elements, and the generation and loss of radiogenic gases. The hypabyssal conditions of pluton formation facilitate the loss of primary mantle-derived volatile components and the dilution of magmatic fluid with near-surface paleometeoric waters containing air dissolved therein. The correlation of noble gas isotopes and ore-forming chemical elements does not suggest derivation of the latter from crustal material and evidences their mantle origin. Variations in the geochemical indices of the gas corroborate previously established or proposed multistage formation of the pluton, mainly, the autometamorphic character of postmagmatic processes and the participation of fluids in ore formation.

Relationships between methane and its homologues mainly contained in fluid microinclusions have been studied in 332 monomineralic fractions from the Khibiny and Lovozero alkaline plutons. Hydrocarbon gases (HCG) were extracted for subsequent chromatographic analysis using the bulk method of sample comminution. The molecular weight distribution (MWD) of gaseous alkanes in the same and associated minerals is different depending on geological setting of the samples. The molecular mass of HCG increases (i) with decrease in temperature and capture of fluid inclusions in the course of transformation of primary magmatic minerals and the formation of late minerals as products of intensified postmagmatic processes; (ii) in the direction from khibinite at the margin and foyaite in the core of the Khibiny pluton to the central ring structure; and (iii) from the bottom to top of the differentiated complex in the Lovozero pluton. The results obtained coupled with other geochemical data suggest multistage generation and transformation of hydrocarbons from the magmatic to the final low-temperature hydrothermal stage. The MWD of hydrocarbon components in gases occluded by minerals can serve as an indicator of conditions characteristic of rock and ore formation, as well as of the consecutive formation and transformation of associated minerals revealing ambiguous and controversial relationships.

The distribution of volatiles in ore units of the Western Pana layered mafic pluton in the Kola province was studied with pyrolytic gas chromatography. In comparison with barren rocks, the rocks containing Pt-Pd mineralization are characterized by a much higher concentration of volatiles, especially H₂S, SO₃, and CH₄. With a drop in temperature, the redox potential of the fluid phase in the ore-magmatic system increased. PGE mineralization was largely formed at the postcumulus stage with participation of volatiles under variable redox conditions.

The composition and concentrations of gases disseminated in rocks (and moving through them mainly via diffusion) and characteristics of their release from these rocks were studied in the Khibina and Lovozero massifs in the Kola Peninsula. Similar to fluid inclusions occluded in vacuoles in minerals and unlike local “jet” gas exhalations, diffusively disseminated gases (DDG) ubiquitously occur in the massifs in variable concentrations. Along with predominant methane and hydrogen, subordinate amounts of methane homologues, and helium, DDG most commonly contain carbon dioxide (in higher concentrations than gases in other modes of their occurrence). One of the most important factors controlling the spontaneous release character of diffusively disseminated gases and their proportions of individual components is the geomechanical state of the rocks. It is proved that the distributions of all modes of gas occurrence in the rocks are generally not interrelated, and hence, it is senseless to utilize the contents of occluded and forcibly extracted gases to predict hazardous gas emissions in mines during the development of mineral deposits related to nepheline syenite complexes.