The applicability of traditional chemical geothermometers

doi:10.13745/j.esf.sf.2024.7.15

Abstract

Abstract:

Geothermometers are used to estimate the reservoir temperatures in hydrothermal systems. To clarify the limitations and validity of traditional chemical geothermometers we conduct a comprehensive review in this study. We found that certain chemical geothermometer types (Na-Li, Li-Mg, Ca-Mg, SO₄-F) were not widely usable, as hydrochemical equilibrium systems in some areas were influenced by the regional geological conditions. Meanwhile, the use of Na-K-Ca type(β=1/3) was constrained by a variety of hydrochemical factors, thus it should be used with caution in low-medium-temperature geothermal systems. The types more suitable for estimating the reservoir temperatures were Na-K, K-Mg, and SiO₂. The Na-K type gave relatively accurate estimates for the high-temperature reservoirs (>200 ℃) where extensive water-rock reactions occurred; while the K-Mg and SiO₂ types were more suitable for the low-medium-temperature reservoirs. In sedimentary geothermal systems, chemical geothermometers were not recommended for estimating the equilibrium temperature of geothermal waters directly. Besides, determining the occurrence state and the hydrothermal equilibrium status of a geothermal reservoir was prerequisite for selecting chemical geothermometers; yet, even within a suitable application range, the measurement results should be compared and validated against the calculation results. In high-temperature geothermal systems the accuracy of chemical geothermometers could be verified by the mixing processes; in low-medium-temperature systems the measurement uncertainty increased due to lack of extensive water-rock reactions, thus validation by various methods became even more important. Results from this study can be used to guide the selection of chemical geothermometers.

Key words: hydrothermal geothermal systems, hydrochemistry, geothermometers, water-rock reaction, equilibrium

CLC Number:

P641.3

LI Jiexiang, XU Yadong, LIN Wenjing. The applicability of traditional chemical geothermometers[J]. Earth Science Frontiers, 2024, 31(6): 145-157.

Figures/Tables 9

Fig.1 Plots of CNa/CK vs. t(°C) for Na-K geothermometers. Modified after [15].

Table 1 Equations for Na-K geothermometers

Na/K地热温度计表达式	参考文献
t(℃)=856/[lg(C_Na/C_K)+0.857]-273.15	[18]
t(℃)=883/[lg(C_Na/C_K)+0.780]-273.15	[19]
t(℃)=933/[lg(C_Na/C_K)+0.993]-273.15 (25~250 ℃)	[20]
t(℃)=1 319/[lg(C_Na/C_K)+1.699]-273.15 (250~350 ℃)	[20]
t(℃)=1 217/[lg(C_Na/C_K)+1.483]-273.15	[21]
t(℃)=1 178/[lg(C_Na/C_K)+1.470]-273.15	[22]
t(℃)=1 390/[lg(C_Na/C_K)+1.750]-273.15	[14]
t(℃)=(1 289±76)/[(lg(C_Na/C_K)+1.615(±0.179)]-273.15	[23]
t(℃)=733.6-770.511lg(C_Na/C_K)+378.189lg(C_Na/C_K)²-95.753lg(C_Na/C_K)³+9.544lg(C_Na/C_K)⁴	[17]
t(℃)=1 052/{1+exp[1.714lg(C_Na/C_K)]+0.252}+76	[24]
t(℃)=1 273.2tanh{[-0.414 4lg(C_Na/C_K)]-0.564 2}+1 156.9	[16]
t(℃)=(883±15)/[lg(C_Na/C_K)+0.894(±0.032)]-273.15	[16]

Fig.2 Geothermal water Na-K-Ca ternary diagram. Modified after [34].

Table 2 Equations for Li geothermometers

锂地热温度计	适用地质条件	来源
T(K)=1 000/[lg(M_Na/M_Li)+0.38]	火山型和花岗岩地热区(M_Cl < 0.3 mol/L)	[36]
T(K)=1 195/[lg(M_Na/M_Li)-0.13]	火山型和花岗岩地热区(M_Cl > 0.3 mol/L)	[36]
T(K)=1 040/[lg(M_Na/M_Li)+0.43]	花岗岩地热区	[40]
T(K)=1 049/[lg(M_Na/M_Li)+0.44]	火山型和花岗岩地热区(M_Cl< 0.3 mol/L)	[23]
T(K)=1 267/[lg(M_Na/M_Li)+0.07]	火山型和花岗岩地热区(M_Cl > 0.3 mol/L)	[23]
T(K)=1 590/[lg(M_Na/M_Li)+1.299]	沉积盆地	[41]
T(K)=855/[lg(M_Na/M_Li)-1.275]	裂谷地热区	[37]
T(K)=1 967/[lg(M_Na/M_Li)+1.267]	玄武岩地热区 (200~325 ℃)	[37]
T(K)=920/[lg(M_Na/M_Li)-1.105]	裂谷地热区	[39]
T(K)=2 002/[lg(M_Na/M_Li)+1.322]	玄武岩地热区 (200~325 ℃)	[39]
T(K)=2 200/[(lgC_Li/ $C M g 0.5$ )-1.322]	沉积盆地	[38]

Table 2 Equations for Li geothermometers

锂地热温度计	适用地质条件	来源
T(K)=1 000/[lg(M_Na/M_Li)+0.38]	火山型和花岗岩地热区(M_Cl < 0.3 mol/L)	[36]
T(K)=1 195/[lg(M_Na/M_Li)-0.13]	火山型和花岗岩地热区(M_Cl > 0.3 mol/L)	[36]
T(K)=1 040/[lg(M_Na/M_Li)+0.43]	花岗岩地热区	[40]
T(K)=1 049/[lg(M_Na/M_Li)+0.44]	火山型和花岗岩地热区(M_Cl< 0.3 mol/L)	[23]
T(K)=1 267/[lg(M_Na/M_Li)+0.07]	火山型和花岗岩地热区(M_Cl > 0.3 mol/L)	[23]
T(K)=1 590/[lg(M_Na/M_Li)+1.299]	沉积盆地	[41]
T(K)=855/[lg(M_Na/M_Li)-1.275]	裂谷地热区	[37]
T(K)=1 967/[lg(M_Na/M_Li)+1.267]	玄武岩地热区 (200~325 ℃)	[37]
T(K)=920/[lg(M_Na/M_Li)-1.105]	裂谷地热区	[39]
T(K)=2 002/[lg(M_Na/M_Li)+1.322]	玄武岩地热区 (200~325 ℃)	[39]
T(K)=2 200/[(lgC_Li/ $C M g 0.5$ )-1.322]	沉积盆地	[38]

Fig.3 Plots of CNa/CK vs. t(°C) for Na-Li geothermometers

Table 3 Equations of SiO2 geothermometers

SiO₂地热温度计表达式		参考文献
石英	t(℃)=1 309/(5.19-lg $C S i O 2$ )-273.15 (无蒸汽损失)	[47]
	t(℃)=1 522/(5.75-lg $C S i O 2$ )-273.15 (100 ℃最大蒸汽损失)	[47]
	t(℃)= -42.198+0.288 31 $C S i O 2$ -0.000 366 86( $C S i O 2$ )²+0.000 000 316 65( $C S i O 2$ )³+77.034lg $C S i O 2$ (无蒸汽损失)	[48]
	t(℃)= -53.5+0.112 36 $C S i O 2$ -0.000 055 59( $C S i O 2$ )²+0.000 000 017 72( $C S i O 2$ )³+88.39 lg $C S i O 2$ (100 ℃最大蒸汽损失)	[48]
	t(℃)= -55.3+0.365 9 $C S i O 2$ -0.000 539 54( $C S i O 2$ )²+0.000 000 551 32( $C S i O 2$ )³+74.36lg $C S i O 2$	[17]
	t(℃)= -44.119+0.244 69 $C S i O 2$ -0.000 174 14( $C S i O 2$ )²+79.305lg $C S i O 2$ (20~210 ℃)	[23]
	t(℃)= 140.82+0.235 17 $C S i O 2$ (210~330 ℃)	[23]
	t(℃)= 1 175.7/(4.88- lg $C S i O 2$ )-273.15	[49]
玉髓	t(℃)= 1 032/(4.69- lg $C S i O 2$ )-273.15 (无蒸汽损失)	[47]
	t(℃)= 1 112/(4.91- lg $C S i O 2$ )-273.15 (无蒸汽损失,25~180 ℃)	[20]
	t(℃)= 1 264/(5.31- lg $C S i O 2$ )-273.15 (100 ℃最大蒸汽损失,100~180 ℃)	[20]

Table 3 Equations of SiO2 geothermometers

SiO₂地热温度计表达式		参考文献
石英	t(℃)=1 309/(5.19-lg $C S i O 2$ )-273.15 (无蒸汽损失)	[47]
	t(℃)=1 522/(5.75-lg $C S i O 2$ )-273.15 (100 ℃最大蒸汽损失)	[47]
	t(℃)= -42.198+0.288 31 $C S i O 2$ -0.000 366 86( $C S i O 2$ )²+0.000 000 316 65( $C S i O 2$ )³+77.034lg $C S i O 2$ (无蒸汽损失)	[48]
	t(℃)= -53.5+0.112 36 $C S i O 2$ -0.000 055 59( $C S i O 2$ )²+0.000 000 017 72( $C S i O 2$ )³+88.39 lg $C S i O 2$ (100 ℃最大蒸汽损失)	[48]
	t(℃)= -55.3+0.365 9 $C S i O 2$ -0.000 539 54( $C S i O 2$ )²+0.000 000 551 32( $C S i O 2$ )³+74.36lg $C S i O 2$	[17]
	t(℃)= -44.119+0.244 69 $C S i O 2$ -0.000 174 14( $C S i O 2$ )²+79.305lg $C S i O 2$ (20~210 ℃)	[23]
	t(℃)= 140.82+0.235 17 $C S i O 2$ (210~330 ℃)	[23]
	t(℃)= 1 175.7/(4.88- lg $C S i O 2$ )-273.15	[49]
玉髓	t(℃)= 1 032/(4.69- lg $C S i O 2$ )-273.15 (无蒸汽损失)	[47]
	t(℃)= 1 112/(4.91- lg $C S i O 2$ )-273.15 (无蒸汽损失,25~180 ℃)	[20]
	t(℃)= 1 264/(5.31- lg $C S i O 2$ )-273.15 (100 ℃最大蒸汽损失,100~180 ℃)	[20]

Fig.4 Relationship between SiO2 concentration and temperature for SiO2

Fig.5 Relationship between Ca2+-Mg2+ activity ratio and temperature under rock-water equilibria

Fig.6 Relationship between F-- SO 4 2 - activity ratio and temperature under rock-water equilibrium

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