Assessment of the Effect of Organic Matter on Rare Earth Elements and Yttrium Using the Zhijin Early Cambrian Phosphorite as an Example
Abstract
:1. Introduction
2. Regional Geology
2.1. Paleogeography
2.2. Deposit Geology
3. Materials and Methods
3.1. Sampling
3.2. Compositions of Major Elements, Trace Elements, and REY
3.3. Scanning Electron Microscopy (SEM)
3.4. Analyses of Isotopes and Total Organic Carbon
3.5. In Situ REY Analysis Using LA-ICP-MS
3.6. In Situ Major Element Analysis
4. Results
5. Discussion
5.1. Diagenetic Evaluation
5.2. Decoupling of Carbonate and Organic Carbon Isotopes
5.2.1. Controls on δ13Ccarb
5.2.2. Controls on δ13Corg
5.3. Effect of Organic Matter on REY Enrichment
6. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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No. | Depth (m) | Lithology | δ13Ccarb | δ18O | δ13Corg | ∆13C | TOC |
---|---|---|---|---|---|---|---|
MTC-1 | 49.65 | Phosphorite | −1.13 | −7.41 | −33.62 | 32 | 0.60 |
MTC-2 | 49.65 | Phosphorus dolomite | −1.31 | −7.12 | −29.96 | 29 | 0.19 |
MTC-3 | 50.74 | Phosphorite | −0.77 | −7.31 | −32.30 | 32 | 0.54 |
MTC-4 | 50.74 | P-bearing dolomite | −0.85 | −7.87 | −30.91 | 30 | 0.18 |
MTC-5 | 51.83 | Phosphorus dolomite | −0.57 | −7.17 | −33.85 | 33 | 0.97 |
MTC-6 | 51.83 | P-bearing dolomite | −0.84 | −2.63 | −29.35 | 29 | 0.14 |
MTC-7 | 52.92 | Phosphorite | −0.20 | −8.22 | −30.48 | 30 | 1.09 |
MTC-8 | 52.92 | P-bearing dolomite | −0.60 | −4.32 | −33.61 | 33 | 0.90 |
MTC-9 | 54.01 | Phosphorus dolomite | −0.65 | −4.99 | −33.23 | 33 | 0.84 |
MTC-10 | 54.01 | P-bearing dolomite | −0.55 | −2.65 | −30.21 | 30 | 0.16 |
MTC-11 | 55.10 | Phosphorite | 0.12 | −8.81 | −30.29 | 30 | 0.83 |
MTC-12 | 56.19 | Phosphorite | 0.44 | −7.47 | −30.82 | 31 | 0.95 |
MTC-13 | 56.19 | P-bearing dolomite | −0.26 | −3.72 | −30.57 | 30 | 0.14 |
MTC-14 | 57.28 | Phosphorite | −0.11 | −7.44 | −31.03 | 31 | 0.98 |
MTC-15 | 57.28 | P-bearing dolomite | 0.39 | −1.83 | −30.04 | 30 | 0.15 |
MTC-16 | 58.37 | Phosphorite | 0.41 | −8.84 | −32.07 | 32 | 1.04 |
MTC-17 | 58.37 | P-bearing dolomite | 0.35 | −8.14 | −31.21 | 32 | 0.19 |
MTC-18 | 59.46 | Phosphorus dolomite | −0.02 | −9.15 | −33.26 | 33 | 0.78 |
MTC-19 | 59.46 | P-bearing dolomite | 0.19 | −8.68 | −33.53 | 34 | 0.53 |
MTC-20 | 60.55 | Phosphorite | −0.41 | −10.18 | −33.42 | 33 | 1.27 |
MTC-21 | 60.55 | P-bearing dolomite | −0.34 | −9.84 | −32.78 | 32 | 0.33 |
MTC-22 | 61.64 | Phosphorite | −0.61 | −9.93 | −33.61 | 33 | 0.84 |
MTC-23 | 61.64 | P-bearing dolomite | 0.05 | −11.28 | −33.38 | 33 | 0.36 |
MTC-24 | 61.99 | Phosphorite | −0.62 | −10.86 | −31.72 | 31 | 0.24 |
MTC-25 | 61.99 | P-bearing dolomite | 0.40 | −12.57 | −30.53 | 31 | 0.08 |
MTC-26 | 62.16 | Phosphorite | −1.21 | −12.87 | −30.56 | 29 | 0.21 |
MTC-27 | 62.16 | Phosphorus dolomite | 0.16 | −11.84 | −30.53 | 31 | 0.11 |
MTC-28 | 63.19 | Phosphorite | −1.29 | −12.63 | −30.47 | 29 | 0.20 |
MTC-29 | 63.19 | Phosphorus dolomite | 0.10 | −11.58 | −31.39 | 31 | 0.14 |
MTC-30 | 64.22 | Phosphorite | −1.37 | −12.99 | −30.91 | 30 | 0.26 |
MTC-31 | 64.22 | P-bearing dolomite | 0.62 | −11.20 | −32.76 | 33 | 0.17 |
MTC-32 | 65.25 | Phosphorite | −0.05 | −11.60 | −33.52 | 33 | 0.78 |
MTC-33 | 65.25 | P-bearing dolomite | 0.69 | −11.18 | −31.84 | 33 | 0.39 |
MTC-34 | 66.28 | Phosphorite | −1.16 | −13.17 | −32.94 | 32 | 0.56 |
MTC-35 | 66.28 | Phosphorus dolomite | 0.68 | −11.13 | −33.56 | 34 | 0.44 |
MTC-36 | 67.31 | Phosphorite | −1.27 | −13.35 | −33.02 | 32 | 0.80 |
MTC-37 | 67.31 | Phosphorus dolomite | 0.66 | −10.98 | −33.20 | 34 | 0.61 |
MTC-38 | 68.34 | Phosphorite | −0.14 | −11.26 | −30.25 | 30 | 0.17 |
MTC-39 | 68.34 | Phosphorus dolomite | 0.54 | −11.02 | −26.34 | 27 | 0.12 |
MTC-40 | 69.37 | Phosphorite | −0.29 | −11.59 | −30.26 | 30 | 0.17 |
MTC-41 | 69.37 | Phosphorus dolomite | 0.20 | −10.76 | −28.86 | 29 | 0.11 |
MTC-42 | 70.40 | Phosphorite | −0.53 | −11.89 | −30.39 | 30 | 0.17 |
MTC-43 | 70.40 | P-bearing dolomite | 0.50 | −10.85 | −32.99 | 33 | 0.17 |
MTC-44 | 71.43 | Phosphorite | −1.51 | −13.52 | −31.52 | 30 | 0.25 |
MTC-45 | 71.43 | P-bearing dolomite | 0.38 | −10.27 | −29.67 | 30 | 0.11 |
MTC-46 | 72.46 | Phosphorite | −1.13 | −11.73 | −31.89 | 31 | 0.26 |
MTC-47 | 72.46 | P-bearing dolomite | −0.01 | −9.76 | −29.06 | 29 | 0.11 |
MTC-48 | 73.49 | Phosphorite | −0.79 | −10.91 | −32.38 | 32 | 0.45 |
MTC-49 | 73.49 | Phosphorus dolomite | 0.06 | −9.90 | −30.75 | 31 | 0.12 |
MTC-50 | 74.52 | Phosphorite | −0.86 | −10.56 | −30.96 | 30 | 0.20 |
MTC-51 | 74.52 | Phosphorus dolomite | −0.60 | −9.52 | −30.64 | 30 | 0.07 |
MTC-52 | 75.55 | Phosphorus dolomite | −3.54 | −12.99 | −31.56 | 28 | 0.21 |
MSC-1 | 34.0 | Phosphorite | −1.23 | −6.88 | −30.01 | 29 | 0.02 |
MSC-2 | 33.5 | Phosphorite | −1.64 | −6.28 | −30.30 | 29 | 0.03 |
MSC-3 | 33.0 | Phosphorite | −1.13 | −5.22 | −30.48 | 29 | 0.04 |
MSC-4 | 32.5 | Phosphorite | −1.54 | −6.27 | −31.84 | 30 | 0.02 |
MSC-5 | 31.9 | Phosphorite | −2.08 | −6.67 | −31.69 | 30 | 0.01 |
MSC-6 | 31.5 | Phosphorite | −2.54 | −7.35 | −31.38 | 29 | 0.02 |
MSC-7 | 31.0 | Phosphorite | −3.68 | −7.84 | −32.02 | 28 | 0.03 |
MSC-8 | 30.5 | Phosphorite | −3.67 | −7.38 | −32.64 | 29 | 0.03 |
MSC-9 | 30.0 | Phosphorite | −5.23 | −10.17 | −31.78 | 27 | 0.03 |
MSC-10 | 29.5 | Phosphorite | −4.17 | −9.00 | −32.38 | 28 | 0.02 |
MSC-11 | 29.0 | Phosphorite | −3.67 | −6.47 | −31.74 | 28 | 0.02 |
MSC-12 | 28.0 | Phosphorite | −3.94 | −10.21 | −30.85 | 27 | 0.02 |
MSC-14 | 27.0 | Phosphorite | −2.10 | −6.63 | −28.45 | 26 | 0.04 |
MSC-15 | 26.0 | Phosphorite | −2.30 | −7.27 | −28.77 | 26 | 0.03 |
MSC-18 | 24.7 | Phosphorite | −3.83 | −10.37 | −32.33 | 28 | 0.02 |
MSC-19 | 24.2 | Phosphorite | −3.74 | −10.17 | −32.95 | 29 | 0.02 |
MSC-20 | 23.7 | Phosphorite | −3.84 | −10.49 | −28.08 | 24 | 0.03 |
MSC-21 | 23.3 | Phosphorite | −4.00 | −10.73 | −25.50 | 22 | 0.03 |
MSC-22 | 22.9 | Phosphorite | −2.70 | −9.17 | −29.02 | 26 | 0.03 |
MSC-23 | 22.6 | Phosphorite | −3.00 | −10.06 | −30.15 | 27 | 0.03 |
MSC-24 | 22.3 | Phosphorite | −3.30 | −10.57 | −29.46 | 26 | 0.01 |
MSC-25 | 22.0 | Phosphorite | −2.22 | −9.27 | −28.21 | 26 | 0.03 |
MSC-26 | 21.6 | Phosphorite | −2.43 | −9.82 | −31.17 | 29 | 0.01 |
MSC-27 | 21.3 | Phosphorite | −2.35 | −9.85 | −31.53 | 29 | 0.05 |
MSC-28 | 21.1 | Phosphorite | −1.84 | −10.21 | −30.06 | 28 | 0.03 |
MSC-29 | 20.9 | Phosphorite | −1.86 | −9.75 | −30.79 | 29 | 0.02 |
Lithology | Phosphorus-Bearing Dolomites | n = 16 | Phosphorus Dolomites | n = 13 | Phosphorites | n = 23 | |||
---|---|---|---|---|---|---|---|---|---|
Min. | Max | Average | Min. | Max | Average | Min. | Max. | Average | |
P2O5 | 1.88 | 9.66 | 5.72 | 10.3 | 18.1 | 14.0 | 19.1 | 37.0 | 29.8 |
La | 28.0 | 115 | 68.1 | 80.2 | 200 | 138 | 124 | 437 | 316 |
Ce | 19.5 | 82.2 | 44.9 | 59.2 | 154 | 90.9 | 83.1 | 269 | 199 |
Pr | 4.74 | 19.5 | 11.7 | 15.8 | 39.2 | 24.2 | 21.7 | 71.8 | 54.2 |
Nd | 19.4 | 84.1 | 50.5 | 72.2 | 169 | 105 | 96.7 | 313 | 233 |
Sm | 3.78 | 16.5 | 9.32 | 13.3 | 31.3 | 19.4 | 17.2 | 56.5 | 42.2 |
Eu | 0.76 | 3.36 | 2.04 | 2.90 | 6.28 | 4.28 | 3.89 | 12.4 | 9.26 |
Gd | 4.63 | 18.3 | 11.1 | 15.5 | 36.4 | 23.2 | 20.8 | 67.5 | 50.6 |
Tb | 0.63 | 2.61 | 1.54 | 2.19 | 4.99 | 3.18 | 2.97 | 9.22 | 6.86 |
Dy | 4.02 | 16.4 | 9.50 | 14.0 | 29.4 | 19.6 | 19.1 | 55.4 | 41.9 |
Y | 45.4 | 199 | 109 | 163 | 320 | 225 | 241 | 637 | 475 |
Ho | 0.91 | 3.64 | 2.09 | 2.95 | 6.49 | 4.23 | 4.21 | 11.8 | 8.99 |
Er | 2.70 | 10.1 | 5.72 | 8.17 | 16.3 | 11.0 | 11.3 | 30.5 | 23.3 |
Tm | 0.38 | 1.22 | 0.70 | 0.92 | 1.85 | 1.30 | 1.32 | 3.55 | 2.71 |
Yb | 2.16 | 6.41 | 3.72 | 4.55 | 8.81 | 6.31 | 5.97 | 16.8 | 12.7 |
Lu | 0.30 | 0.88 | 0.50 | 0.59 | 1.04 | 0.82 | 0.75 | 2.25 | 1.65 |
∑REY | 137 | 558 | 330 | 481 | 990 | 676 | 654 | 1969 | 1477 |
Elements | Dolomite-1 | Dolomite-2 | Dolomite-3 | Dolomite-4 | Dolomite-5 | Dolomite-6 | Dolomite-7 | Dolomite-8 | Average | Dolomite Cement-1 | Dolomite Cement-2 | Dolomite Cement-3 | Dolomite Cement-4 | Dolomite Cement-5 | Average |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Na2O | 0.020 | 0.028 | 0.022 | 0.022 | 0.005 | 0.020 | 0.023 | 0.021 | 0.020 | 0.030 | 0.053 | 0.046 | 0.035 | 0.043 | 0.041 |
MgO | 27.3 | 26.8 | 27.2 | 27.2 | 27.4 | 26.6 | 26.7 | 28.6 | 27.2 | 26.5 | 28.1 | 28.5 | 27.7 | 28.2 | 27.8 |
Al2O3 | 0.029 | 0.080 | 0.445 | 0.053 | 0.149 | 0.030 | 0.083 | 0.458 | 0.166 | 0.030 | 0.047 | 0.045 | 0.053 | 0.036 | 0.042 |
SiO2 | 0.178 | 0.668 | 1.22 | 0.589 | 4.00 | 0.244 | 7.35 | 16.6 | 3.86 | 0.056 | 0.195 | 0.344 | 0.224 | 0.037 | 0.171 |
P2O5 | 0.014 | 0.029 | 0.030 | 0.025 | 0.108 | 0.010 | 0.130 | 0.056 | 0.050 | 0.042 | 0.027 | 0.042 | 0.021 | 0.019 | 0.030 |
K2O | 0.002 | 0.015 | 0.141 | 0.008 | 0.051 | 0.001 | 0.019 | 0.135 | 0.047 | 0.007 | 0.013 | 0.013 | 0.016 | 0.011 | 0.012 |
CaO | 41.5 | 41.8 | 42.1 | 41.8 | 42.4 | 41.8 | 41.8 | 41.8 | 41.9 | 42.4 | 44.0 | 44.0 | 44.0 | 44.0 | 43.7 |
TiO2 | 0.000 | 0.006 | 0.060 | 0.000 | 0.007 | 0.000 | 0.002 | 0.004 | 0.010 | 0.000 | 0.001 | 0.001 | 0.003 | 0.000 | 0.001 |
MnO | 0.434 | 0.419 | 0.468 | 0.389 | 0.391 | 0.403 | 0.441 | 0.383 | 0.416 | 0.161 | 0.190 | 0.182 | 0.171 | 0.172 | 0.175 |
FeO | 1.66 | 1.41 | 2.05 | 1.15 | 1.11 | 1.45 | 1.92 | 0.782 | 1.44 | 0.391 | 0.389 | 0.410 | 0.380 | 0.412 | 0.396 |
La | 7.45 | 9.56 | 5.76 | 11.3 | 4.65 | 6.89 | 8.01 | 7.60 | 7.66 | 8.79 | 16.4 | 20.1 | 10.7 | 12.0 | 13.6 |
Ce | 3.96 | 4.82 | 3.25 | 5.84 | 2.69 | 3.63 | 4.61 | 4.22 | 4.13 | 4.74 | 8.75 | 11.0 | 5.68 | 6.04 | 7.25 |
Pr | 0.714 | 0.957 | 0.614 | 1.11 | 0.522 | 0.726 | 0.979 | 0.800 | 0.802 | 1.23 | 2.30 | 2.96 | 1.50 | 1.68 | 1.93 |
Nd | 2.89 | 3.42 | 2.24 | 4.11 | 2.10 | 2.59 | 4.04 | 3.47 | 3.11 | 5.48 | 9.80 | 12.5 | 5.97 | 6.93 | 8.13 |
Sm | 0.443 | 0.635 | 0.392 | 0.665 | 0.294 | 0.443 | 0.649 | 0.509 | 0.504 | 1.00 | 1.80 | 2.30 | 1.20 | 1.09 | 1.48 |
Eu | 0.160 | 0.198 | 0.152 | 0.192 | 0.091 | 0.119 | 0.213 | 0.173 | 0.162 | 0.236 | 0.272 | 0.359 | 0.222 | 0.195 | 0.257 |
Gd | 0.581 | 0.833 | 0.570 | 0.846 | 0.434 | 0.827 | 0.834 | 0.710 | 0.704 | 1.43 | 2.28 | 2.91 | 1.52 | 1.68 | 1.97 |
Tb | 0.122 | 0.144 | 0.103 | 0.149 | 0.084 | 0.155 | 0.149 | 0.135 | 0.130 | 0.271 | 0.373 | 0.456 | 0.248 | 0.293 | 0.328 |
Dy | 0.953 | 1.17 | 0.968 | 1.28 | 0.632 | 1.04 | 1.30 | 1.16 | 1.06 | 2.03 | 2.88 | 3.58 | 1.89 | 2.42 | 2.56 |
Y | 15.7 | 18.8 | 13.2 | 20.0 | 9.19 | 15.3 | 17.4 | 16.2 | 15.7 | 28.0 | 38.0 | 41.1 | 26.0 | 29.3 | 32.5 |
Ho | 0.325 | 0.323 | 0.271 | 0.366 | 0.188 | 0.328 | 0.335 | 0.294 | 0.304 | 0.526 | 0.73 | 0.822 | 0.520 | 0.560 | 0.631 |
Er | 1.13 | 1.27 | 1.04 | 1.23 | 0.632 | 1.15 | 1.34 | 1.06 | 1.11 | 1.90 | 2.46 | 2.81 | 1.70 | 1.80 | 2.13 |
Tm | 0.215 | 0.221 | 0.201 | 0.194 | 0.114 | 0.258 | 0.244 | 0.172 | 0.202 | 0.275 | 0.386 | 0.395 | 0.237 | 0.249 | 0.308 |
Yb | 1.90 | 1.70 | 1.61 | 1.45 | 0.910 | 2.04 | 2.10 | 1.49 | 1.65 | 1.96 | 2.61 | 2.63 | 1.65 | 1.86 | 2.14 |
Lu | 0.271 | 0.229 | 0.258 | 0.242 | 0.164 | 0.342 | 0.316 | 0.214 | 0.255 | 0.276 | 0.391 | 0.367 | 0.241 | 0.282 | 0.311 |
REY | 36.8 | 44.2 | 30.6 | 49.0 | 22.7 | 35.9 | 42.6 | 38.2 | 37.5 | 58.1 | 89.4 | 104 | 59.3 | 66.4 | 75.5 |
ErN/LuN | 0.634 | 0.843 | 0.611 | 0.771 | 0.586 | 0.512 | 0.642 | 0.753 | 1.05 | 0.957 | 1.16 | 1.07 | 0.968 | ||
Gd/Gd* | 0.816 | 0.967 | 0.893 | 0.981 | 0.970 | 1.19 | 0.917 | 0.910 | 1.11 | 1.41 | 1.41 | 1.27 | 1.38 |
Samples | Mg | Ca | Mn | Fe | Total |
---|---|---|---|---|---|
Dolomite | 21.3 | 29.6 | 0.279 | 0.757 | 51.9 |
Dolomite | 21.0 | 29.9 | 0.268 | 0.733 | 51.9 |
Dolomite | 21.0 | 29.7 | 0.264 | 0.803 | 51.8 |
Dolomite | 22.0 | 30.3 | 0.153 | 0 | 52.4 |
Dolomite | 20.9 | 29.8 | 0.391 | 1.37 | 52.4 |
Dolomite | 21.3 | 29.6 | 0.279 | 0.757 | 51.9 |
Dolomite | 21.0 | 29.9 | 0.268 | 0.733 | 51.9 |
Dolomite | 21.0 | 29.7 | 0.264 | 0.803 | 51.8 |
Dolomite | 22.0 | 30.3 | 0.153 | 0 | 52.4 |
Dolomite | 21.0 | 29.9 | 0.354 | 0.922 | 51.9 |
Dolomite | 21.0 | 29.9 | 0.284 | 1.25 | 52.5 |
Dolomite | 21.1 | 30.0 | 0.307 | 0.983 | 52.4 |
Dolomite | 20.4 | 31.4 | 0.163 | 0.218 | 52.1 |
Dolomite | 21.8 | 30.5 | 0.128 | 0.259 | 52.7 |
Dolomite | 21.6 | 30.9 | 0.204 | 0.188 | 52.9 |
Dolomite | 19.5 | 33.2 | 0.131 | 0.067 | 52.8 |
Dolomite | 19.6 | 32.7 | 0.132 | 0.051 | 52.6 |
Dolomite | 21.5 | 30.8 | 0.120 | 0.175 | 52.6 |
Dolomite | 21.5 | 30.8 | 0.116 | 0.253 | 52.6 |
Average | 21.1 | 30.5 | 0.224 | 0.543 | 52.3 |
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Wu, S.; Yang, H.; Fan, H.; Xia, Y.; Meng, Q.; He, S.; Gong, X. Assessment of the Effect of Organic Matter on Rare Earth Elements and Yttrium Using the Zhijin Early Cambrian Phosphorite as an Example. Minerals 2022, 12, 876. https://doi.org/10.3390/min12070876
Wu S, Yang H, Fan H, Xia Y, Meng Q, He S, Gong X. Assessment of the Effect of Organic Matter on Rare Earth Elements and Yttrium Using the Zhijin Early Cambrian Phosphorite as an Example. Minerals. 2022; 12(7):876. https://doi.org/10.3390/min12070876
Chicago/Turabian StyleWu, Shengwei, Haiying Yang, Haifeng Fan, Yong Xia, Qingtian Meng, Shan He, and Xingxiang Gong. 2022. "Assessment of the Effect of Organic Matter on Rare Earth Elements and Yttrium Using the Zhijin Early Cambrian Phosphorite as an Example" Minerals 12, no. 7: 876. https://doi.org/10.3390/min12070876