Geochemical Characteristics and Water Content of Melt Inclusions in the Tuff of the Tiaojishan Formation, Liujiang Basin

ZHAO Huizhen; CHEN Yong; TU Cong; FENG Yanwei

doi:10.15898/j.ykcs.202404030074

Rock and Mineral Analysis > 2025 > 44(1): 88-101. > DOI: 10.15898/j.ykcs.202404030074

ZHAO Huizhen，CHEN Yong，TU Cong，et al. Geochemical Characteristics and Water Content of Melt Inclusions in the Tuff of the Tiaojishan Formation, Liujiang Basin[J]. Rock and Mineral Analysis，2025，44（1）：88−101. DOI: 10.15898/j.ykcs.202404030074

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Geochemical Characteristics and Water Content of Melt Inclusions in the Tuff of the Tiaojishan Formation, Liujiang Basin

ZHAO Huizhen^{1, 2,},
CHEN Yong^{1, 2, ,},
TU Cong³,
FENG Yanwei^{1, 2}

1.
National Key Laboratory of Deep Oil and Gas, China University of Petroleum (East China), Qingdao 266580, China
2.
School of Geosciences, China University of Petroleum (East China), Qingdao 266580, China
3.
School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China

More Information

Received Date: April 02, 2024
Revised Date: July 30, 2024
Accepted Date: August 06, 2024
Available Online: September 07, 2024
Published Date: September 04, 2024

Abstract

HIGHLIGHTS
(1) The establishment of a calibration curve is crucial for the quantitative determination of water content in melt inclusions using laser Raman spectroscopy.

(2) The water content of melt inclusions has a strong linear relationship with Raman spectroscopy parameters, allowing a calibration curve to be established with only a few standard samples.

(3) The average water content of melt inclusions in the tuffaceous rocks from the Tiaojishan Formation in the Liujiang Basin is 2.62%, indicating an acidic, water-enriched magmatic system.

ABSTRACT

Water, as the primary volatile component in magmatic systems, has a significant impact on the formation and evolution of magma. The Tiaojishan Formation igneous rocks in the Liujiang Basin are significant products of Yanshanian volcanic activity. Although previous studies have extensively explored their geochemical characteristics, the water content of the magma in the Liujiang Basin during Yanshanian volcanic activity remains unclear. Melt inclusions, which capture the original magmatic information, serve as the most direct samples for determining the water content of magma. Based on geochemical analysis, this study quantitatively determines the water content in melt inclusions using laser Raman spectroscopy with standard samples. The results show that the lower tuff samples of the Tiaojishan Formation are characterized by high Si and Al contents, enrichment in LILEs, depletion in HFSEs, enrichment in LREEs, and depletion in HREEs. The water content in melt inclusions reveals a range of 0.99% to 4.98%, with an average of 2.62%. These characteristics jointly indicate the water-enriched acidic magmatic activity during the early Tiaojishan period in this area. Combining the water content of melt inclusions with the large-scale volcanic eruptions in the stage, this study suggests that high water content in the magma enhanced the eruptive dynamics of the magmatic system, making it a contributing factor to the large-scale volcanic eruption. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202404030074.
- Liujiang Basin,
- Tiaojishan Formation,
- tuff,
- melt inclusions,
- water content,
- laser Raman spectroscopy
BRIEF REPORT
Significance: Water (H₂O) is the most significant volatile component in natural magmatic systems, playing a vital role in shaping the physical and chemical properties of magma. Its presence significantly affects magma viscosity, melting point, and crystallization. Therefore, water exerts a controlling influence over the overall trends of magmatic differentiation and evolution, guiding the chemical evolution of the magma as it cools and solidifies over time^[1-3]. Melt inclusions, as snapshots of magma during geological periods, can preserve the original characteristics of the magma, making them the most direct geological samples for assessing water content in magmas^[6-8]. Studying the water content in melt inclusions not only reveals the processes of magmatic differentiation and evolution, but also provides critical evidence for understanding the characteristics of magmatic activity.
　　Despite the importance of water in influencing magmatic processes, current studies on the water content in Mesozoic volcanic rocks, specifically within the Yanshanian Orogen, remain limited. The Tiaojishan Formation volcanics are among the most representative calc-alkaline volcanic rocks of the Mesozoic Yanshanian Orogen, marking the onset of large-scale volcanic eruptions during the Yanshan period^[20]. Although extensive research has focused on the geochemistry of these volcanic rocks, the water content within the Tiaojishan Formation’s volcanics is not well-understood^[21-25]. This knowledge gap limits our understanding of how water influences magma behavior during large-scale volcanic events of the Yanshan period.
　　This study addresses the gap by quantifying the water content in melt inclusions from tuff in the Lower Tiaojishan Formation (J₂t), an early volcanic product of the Yanshanian Orogen. Utilizing micro-laser Raman spectroscopy, which allows high-resolution, rapid, and non-destructive water content measurement, the study provides quantitative petrochemical data essential for understanding magmatic processes in this region. Our findings advance the understanding of water’s role in regional magmatic differentiation, contributing key insights into the volcanic activity of the Yanshanian Orogen.
Methods: The tuff samples used in this study were collected from the lower part of the Tiaojishan Formation outcrop in the Liujiang Basin, Qinhuangdao, Hebei Province. All experiments were conducted at the National Key Laboratory of Deep Oil and Gas of China University of Petroleum (East China). A Leica DM2700P microscope was used for microscopic observation, while IRIS Intrepid Ⅱ XSP ICP-OES and ELAN9000 ICP-MS were employed for the analysis of major and trace elements. For microscopic laser Raman spectroscopy testing, a LABRAM HR EVO Laser Raman Spectrometer manufactured by HORIBA FRANCE SAS was utilized.
　　The microscopic laser Raman spectroscopy experiments are conducted with a laser power of 30mW, an integration time of 30s, and each measurement was integrated three times. To enhance the accuracy of the experimental outcomes, the Raman spectra are subjected to a detailed processing procedure. This process involves several critical steps, beginning with intensity correction, which adjusts the spectral data to account for any fluctuations in laser power or detector sensitivity. Following this, baseline correction is applied to remove any background noise or interference, ensuring that the true signal is accurately isolated. Finally, bands integration is performed, where the area under specific peaks within the spectrum is calculated, allowing for a precise quantification of the target components. Acidic silicate glass exhibits a strong LF₄₇₀ Raman peak height/intensity (Fig.2), and A_WF/A_LF is preferentially selected as the optimal calibration parameter^[11,19]. Subsequently, a crucial calibration curve for water content is established with the glass standards synthesized by Professor Gao Xiaoying’s team from University of Science and Technology of China. Nine well-preserved primary melt inclusions were carefully selected under a microscope for analysis. These inclusions underwent rigorous testing and detailed data processing, during which their water content was meticulously calculated based on the data.
Data and Results: The experimental results obtained by petrographic observation, analysis of major and trace elements and microscopic laser Raman spectroscopy are shown in the following two parts.
　　(1) Petrological and geochemical characteristics
　　The tuff from the lower part of the Tiaojishan Formation is classified as Rhyolite lithic-crystalline tuff, characterized by a blocky texture. It predominantly comprises crystal fragments (35%), rock fragments (25%) and matrix (40%). The crystal fragments are mainly composed of quartz and feldspar, with particle sizes reaching up to 1.8mm; The rock fragments consist mainly of rhyolite debris, with particle sizes ranging from 0.5 to 2mm. The matrix is composed of fine dust and volcanic ash.
　　The major and trace element analysis results of the whole-rock tuff samples are presented in Table 2 and Table 3, respectively. The samples are marked by high concentrations of Si and Al, enrichment in large ion lithophile elements (LILEs), and depletion in high field strength elements (HFSEs) (Fig.4b). The samples also exhibit enrichment in light rare earth elements (LREEs) and depletion in heavy rare earth elements (HREEs) (Fig.4c), along with a negative Eu anomaly and low Sr content. The TAS diagram (Fig.4a) positions the tuff within the rhyolite field, suggesting its formation is closely associated with acidic magmatic activity. The Ta/Yb-Th/Yb diagram (Fig.4d) places the samples within the active continental margin, inferring that the study area was significantly influenced by oceanic subduction and magmatic activity during this period.
　　(2) Characteristics of melt inclusions and water content in the tuff
　　The melt inclusions are primarily isolated and randomly distributed within the lattice defects of quartz phenocrysts, indicative of their primary magmatic origin. These inclusions appear colorless or pale yellow, and exhibit a variety of morphologies, including polygonal (Fig.5a, b), ellipsoidal (Fig.5c, d), and oval shapes (Fig.5e), with diameters varying between 30μm and 165μm. Based on their phase characteristics, the melt inclusions can be categorized into three types: (1)glassy+crystalline melt inclusions (Fig.5a), (2)glassy+bubble-bearing melt inclusions (Fig.5b, d), and (3)glassy melt inclusions (Fig.5c, e). The melt inclusions contain either no or only a few small vapor bubbles, indicating their formation in a volcanic facie with a relatively rapid cooling rate^[6,43-44].
　　Water peaks were identified at 3100−3800cm⁻¹; in the nine melt inclusions, with no detection of CO₂ or other volatiles (Fig.5f). According to Bowen’s reaction series^[45], quartz forms in the late stage of magmatic fractional crystallization, and the composition of melt inclusions captured by quartz closely resembles the pre-eruption magma. In other words, the water content in these melt inclusions reflects the water content in the magma before the eruption^[2].
　　The calibration equation for water content is C_H2O=1.26×(A_WF/A_LF) with R²=0.998 (Fig.3). After processing the micro-laser Raman spectra of the nine melt inclusions, the results (A_WF, A_LF) are substituted into the water content calibration curve equation [Equation (2)]. Calculations were performed using Excel, and the water content results for the melt inclusions are presented in Table 4. The results indicate that the water content in the melt inclusions within quartz crystal fragments in the tuff from the Tiaojishan Formation in the Liujiang Basin ranges from 0.99% to 4.98%, with an average of 2.62% (Table 4). A comparison with statistical data provided by Li et al.^[1] shows that most ultrabasic to basic magmas have a water content ranging from 0 to 0.8%, while intermediate magmas typically range from 0.4% to 2.8%, with an average of 2.26%, and the water content in acidic magmas generally falls between 0.8% and 5.6%, with an average of 2.712%. The high-water content observed in the melt inclusions from the lower Tiaojishan Formation tuff in the Liujiang Basin suggests that the magma transited into an acidic state in the late stage of its evolution.

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