The Effects of Hydrochloric Acid Pretreatment on Different Types of Clay Minerals
<p>X-ray diffraction (XRD) patterns of the individual clay mineral samples after different pretreatments with HCl. Black curves are the original standard samples; dark blue curves indicate 21 °C and red curves indicate 70 °C. (<b>A</b>) Ca-smectite (Ca-sme), (<b>B</b>) Na-smectite (Na-sme), (<b>C</b>) chlorite (Chl), (<b>D</b>) illite (Ill), and (<b>E</b>) kaolinite (Kao).</p> "> Figure 2
<p>Ratios of the XRD pattern parameters (i.e., intensity and full width at half maximum (FWHM)) after different pretreatments for Ca-smectite, Na-smectite, chlorite, illite, and kaolinite for each reflection. The y-axis (Y/Y<sub>0</sub>) is the ratio of the reflection after pretreatment to that with no pretreatment, which is intensity/intensity<sub>0</sub> and FWHM/FWHM<sub>0</sub>. The x-axis is the concentration of HCl. (<b>A</b>) Ca-smectite and Na-smectite, (<b>B</b>) chlorite, (<b>C</b>) illite, and (<b>D</b>) kaolinite.</p> "> Figure 3
<p>TEM images of the clay minerals (<b>A</b>,<b>C</b>,<b>E</b>,<b>G</b>,<b>I</b>,<b>K</b>) without pretreatment and (<b>B</b>,<b>D</b>,<b>F</b>,<b>H</b>,<b>J</b>,<b>L</b>) after pretreatment with 12 N HCl at 70 °C. Ca-smectite (Ca-Sm) (<b>A</b>) before and (<b>B</b>) after HCl pretreatment; Na-smectite (Na-Sm) (<b>C</b>) before and (<b>D</b>) after HCl pretreatment; chlorite (Chl) (<b>E</b>) before and (<b>F</b>) after HCl pretreatment; talc (<b>G</b>) before and (<b>H</b>) after HCl pretreatment; illite (<b>I</b>) before and (<b>J</b>) after HCl pretreatment; kaolinite (Kao) (<b>K</b>) before and (<b>L</b>) after HCl pretreatment. The red stars mark the sites where EDS data were obtained.</p> "> Figure 3 Cont.
<p>TEM images of the clay minerals (<b>A</b>,<b>C</b>,<b>E</b>,<b>G</b>,<b>I</b>,<b>K</b>) without pretreatment and (<b>B</b>,<b>D</b>,<b>F</b>,<b>H</b>,<b>J</b>,<b>L</b>) after pretreatment with 12 N HCl at 70 °C. Ca-smectite (Ca-Sm) (<b>A</b>) before and (<b>B</b>) after HCl pretreatment; Na-smectite (Na-Sm) (<b>C</b>) before and (<b>D</b>) after HCl pretreatment; chlorite (Chl) (<b>E</b>) before and (<b>F</b>) after HCl pretreatment; talc (<b>G</b>) before and (<b>H</b>) after HCl pretreatment; illite (<b>I</b>) before and (<b>J</b>) after HCl pretreatment; kaolinite (Kao) (<b>K</b>) before and (<b>L</b>) after HCl pretreatment. The red stars mark the sites where EDS data were obtained.</p> "> Figure 4
<p>Quantification of the mixed clay samples after different pretreatments.</p> "> Figure 5
<p>Results of clay mineral analysis obtained with the two methods and the actual clay contents of the 24 mixed standard samples. The orange dashed lines are the linear correlations between the height of the main XRD reflection after HCl pretreatment and the actual clay contents. The blue dashed lines are the linear correlations between the results obtained from the routine method and the actual clay contents. (<b>A</b>) Illite, (<b>B</b>) chlorite and kaolinite, (<b>C</b>) kaolinite, and (<b>D</b>) smectite.</p> "> Figure 6
<p>Comparison of the XRD patterns and data obtained for the natural red clay samples versus depth using the HCl pretreatment and routine methods. The orange curves are the ratios of the main XRD reflection height with pretreatment of 1 N HCl at 70 °C (smectite at 14.33 Å, illite at 10.00 Å, chlorite and kaolinite at 7.10 Å before HCl pretreatment; kaolinite at 7.10 Å after HCl pretreatment) to the height of the quartz peak at 3.33 Å. The blue curves are the relative contents of each clay mineral obtained with the routine method. (<b>A</b>) XRD pattern of a representative natural red clay sample. Sme = smectite, Chl = chlorite, Ill = illite, Kao = kaolinite, Qua = quartz, and Alb = albite. (<b>B</b>) Depth changes of the main XRD peak height ratio of Ill (001)/Qua (011) and relative content of Ill. (<b>C</b>) Depth change of the main XRD peak height ratio of Chl (002) + Kao (001)/Qua (011) and relative content of Chl. (<b>D</b>) Depth change of the main XRD peak height ratio of Kao (001)/Qua (011) and relative content of Kao. (<b>E</b>) Depth change of the main XRD peak height ratio of Sme (001)/Qua (011) and relative content of Sme. (<b>F</b>) Depth change of the paleoclimate proxy Sme (001)/(Ill (001) + Chl (002) + Kao (001) and Sme/(Ill + Chl + Kao) ratio.</p> ">
Abstract
:1. Introduction
2. Materials and Methods
2.1. Samples Description
2.2. Comparison between the HCl Pretreatment and Routine Methods
3. Results
3.1. Individual Clay Mineral Samples with Different HCl Pretreatments
3.2. Mixed Samples Subjected to Different HCl Pretreatments
3.3. Comparison of the HCl Pretreatment and Routine Methods in Analysing Mixed and Natural Samples
4. Discussion
4.1. Effects of HCl Pretreatment on the Structure of Individual Clay Minerals
4.2. Effects of HCl Pretreatment on the Identification and Quantification of Clay Minerals in Mixed Samples
4.3. Estimation of the Clay Mineral Index in Natural Samples with the HCl Pretreatment Method
4.4. Effect of HCl Pretreatment in Other Experiments
5. Conclusions
- Chlorite is the most soluble clay mineral in HCl and can be effectively dissolved in HCl with a concentration of >1 N. The different crystal structures of smectite exhibit differences in HCl dissolution. Ca-smectite with more substituted octahedral Al can be dissolved with HCl. Na-smectite is barely dissolved at any HCl concentration or temperature. Illite is partly dissolved in HCl, at ≥5 N HCl at 70 °C. Kaolinite is not effectively dissolved in HCl.
- The XRD peak of residual illite at 11–12° (7.0–7.5 Å) after HCl pretreatment is the main source of error in the identification and quantification of clay minerals by this method. 1 N HCl at 70 °C can dissolve most chlorite with limited effects on the other clay minerals. 3 N HCl at 70 °C can distinguish between the different types of smectite.
- The quantification of clay mineral contents from the peak heights of bulk sample XRD data after HCl pretreatment is less accurate than the routine method. Therefore, it is not suitable for the analysis of clay minerals for paleoclimate studies.
- The effects of HCl pretreatment on clay minerals in other types of research (e.g., grain size analysis and chemical pretreatment of mineral separates) needs to be considered. Ideally, the HCl concentration should be <1 N to avoid digestion of clay minerals.
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Details | |
---|---|
Clay Minerals | Ca-Smectite, Na-Smectite, Chlorite, Illite, and Kaolinite |
Weight | 0.05 g |
Temperature | 21 and 70 °C |
Concentration of HCl | 1, 3, 5, 7, 9, and 12 N |
Time | 24 h (21 °C) and 2 h (70 °C) |
Details | |||||||
---|---|---|---|---|---|---|---|
Sample Number | Std. 1 | Std. 2 | Std. 3 | Std. 4 | Std. 5 | Std. 6 | Std. 7 |
Contents (wt.%) | Ill 70, Chl 30 | Chl 20, Sme 80 | Sme 30, Kao 70 | Ill 70, Chl 10, Sme 20 | Ill 40, Chl 20, Sme 40 | Ill 30, Chl 10, Sme 40, Kao 20 | Ill 10, Chl 20, Sme 35, Kao 35 |
Concentration of HCl | 1, 5, and 12 N | ||||||
Temperature and reaction time with HCl | 21 °C (24 h) and 70 °C (2 h) | ||||||
Concentration of HAC | 1 N | ||||||
Temperature and reaction time with HAC | 21 °C (24 h) |
Elements | Al | Ca | Fe | K | Mg | Na | Ti | Zn | Ba | Sr |
---|---|---|---|---|---|---|---|---|---|---|
HCl–Ca-Sme | 17.26 | 2.07 | 3.09 | 1.15 | 3.80 | 2.52 | 0.20 | 0.17 | 0.06 | 0.06 |
Ca-Sme | 49.2 | 11.8 | 8.43 | 2.40 | 17.2 | 2.86 | 0.50 | 0.20 | 0.30 | 0.14 |
HCl–Na-Sme | 47.3 | 2.14 | 5.44 | 2.67 | 9.66 | 3.93 | 0.40 | 0.18 | 0.06 | 0.08 |
Na-Sme | 60.4 | 9.66 | 7.23 | 3.26 | 13.4 | 20.9 | 0.46 | 0.21 | 0.17 | 0.23 |
HCl–Chl | 1.96 | 2.02 | 2.85 | 0.40 | 81.4 | 2.70 | 1.24 | 0.15 | 0.04 | 0.07 |
Chl | 24.6 | 4.43 | 7.16 | 0.41 | 109 | 2.50 | 0.67 | 0.16 | 0.05 | 0.10 |
HCl–Ill | 59.4 | 2.62 | 2.95 | 15.7 | 2.00 | 3.82 | 3.47 | 0.18 | 0.32 | 0.15 |
Ill | 75.7 | 2.48 | 3.76 | 18.7 | 2.44 | 3.84 | 3.70 | 0.16 | 0.36 | 0.20 |
HCl–Kao | 135 | 2.24 | 2.82 | 2.22 | 0.42 | 2.61 | 1.52 | 0.18 | 0.07 | 0.09 |
Kao | 122 | 3.01 | 4.84 | 1.98 | 0.43 | 3.68 | 1.32 | 0.25 | 0.08 | 0.11 |
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Hu, B.; Zhang, C.; Zhang, X. The Effects of Hydrochloric Acid Pretreatment on Different Types of Clay Minerals. Minerals 2022, 12, 1167. https://doi.org/10.3390/min12091167
Hu B, Zhang C, Zhang X. The Effects of Hydrochloric Acid Pretreatment on Different Types of Clay Minerals. Minerals. 2022; 12(9):1167. https://doi.org/10.3390/min12091167
Chicago/Turabian StyleHu, Bin, Chunxia Zhang, and Xiaoyan Zhang. 2022. "The Effects of Hydrochloric Acid Pretreatment on Different Types of Clay Minerals" Minerals 12, no. 9: 1167. https://doi.org/10.3390/min12091167