Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium
"> Figure 1
<p>Location of samples used in this study. See <a href="#app1-minerals-06-00088" class="html-app">Table S1</a> for coordinates.</p> "> Figure 2
<p>Photographs of seamount phosphorites: (<b>A</b>) cement-supported breccia; cement from carbonate fluorapatite (CFA)-replaced pelagic foraminifera matrix. (<b>B</b>) Massive, layered (<b>A</b>–<b>D</b>), recrystallized phosphorite; protolith cannot be distinguished, low porosity. (<b>C</b>) Massive bed of CFA-replaced foraminifera, with nearly pristine microfossil structure; minor rim cement on foraminifera indurates the rock; very high porosity. (<b>D</b>) CFA-replaced carbonate sand that filled fractures in basalt. Note Fe-Mn crust on at least one surface of each sample.</p> "> Figure 3
<p>Scatter plot of phosphorus versus calcium for seamount and continental margin phosphorite deposits analyzed here. Arrows show deviations from the carbonate fluorapatite end member (most pure phosphorite) with increasing calcite and detrital/authigenic (Si, Al, and Fe) contents.</p> "> Figure 4
<p>Bar diagram of mean contents of individual rare earth elements and yttrium for the sample groups studied here; note that the order for each element follows the order in the key.</p> "> Figure 5
<p>Post Archean Australian Shale-normalized rare earth element plot for mean data of sample groups compared with patterns for Prime Crust Zone (PCZ) crusts, Clarion-Clipperton Zone (CCZ) nodules, and seawater (× 10<sup>9</sup>) at ~2000 m water depth [<a href="#B19-minerals-06-00088" class="html-bibr">19</a>].</p> "> Figure 6
<p>Bar diagram of ratio of mean REY data for seamount phosphorites and Pacific Prime Crust Zone ferromanganese crusts.</p> "> Figure 7
<p>Comparison of mean total HREY contents of ferromanganese deposits with seamount and continental margin phosphorites.</p> "> Figure 8
<p>Bar diagram of mean total REY data for ferromanganese crusts and nodules compared to mean data for seamount and continental margin phosphorites.</p> ">
Abstract
:1. Introduction
2. Samples and Methods
2.1. Sample Collection
2.2. Sample Preparation and Analyses
3. Results
3.1. Mineralogy
3.2. Geochemistry
3.3. Rare Earth Elements (REY)
3.4. Correlations
4. Discussion
4.1. Comparison of CM and Seamount Mineralization, and REY Mass Balance
4.2. CFA Structure and Substitutions by REY
4.3. Controls on REY Composition
4.4. Comparisons with Terrestrial Carbonatite REY Deposits and Marine Fe-Mn Deposits
5. Conclusions
- (1)
- Continental margin (CM) marine phosphorites have low total REY contents (mean 161 ppm) and high HREY complements (mean 49%), while seamount phosphorites have 4–6-times higher individual REY contents (except for Ce, which is comparable; mean ΣREY 727 ppm), and very high HREY complement (mean 60%).
- (2)
- The predominant causes of higher concentrations and larger HREY complements in seamount phosphorites compared to CM phosphorites is the geological time of formation, changes in seawater REY concentrations over time, water depth of formation, differences in organic carbon content in the depositional environments and its role in the development of diagenetic zones in the sediment, and possibly the concurrent precipitation of Fe-Mn oxides with the seamount phosphorites.
- (3)
- Fe-Mn crusts and nodules are another potential resource for REY. Both Fe-Mn deposit types have significantly lower HREY complements than the phosphorites and crusts have three to ten times higher REY concentrations. These differences can be explained by the mechanisms of incorporation of the REY into the mineral deposits: Predominantly sorption by the Fe-Mn oxides with surface oxidation of the Ce, and predominantly by substitution for Ca in the CFA structure, and to lesser extents by inheritance from the host rock and by sorption.
- (4)
- Seamount phosphorites occur in the same places as Fe-Mn crusts on seamounts and the phosphorites are typically covered with Fe-Mn crusts, making exploration for phosphorites challenging. Consequently, it would require the development of new technology or detailed sampling to identify phosphorite substrate rock beneath the Fe-Mn crusts. Detailed sampling and geophysical measurements of a single guyot might provide geological or morphological criteria that would be useful for future exploration.
- (5)
- An ideal mine site might be one where the substrate rock is phosphorite, in which case it would be desirable to collect both phosphorite and Fe-Mn crusts at the same time. This approach would provide two potential multi-component ore deposits in one mining operation, one with P and REY co-products and one with focus metals (Co, Ni, and Mn) and byproducts (e.g., Mo, REY, and Te).
- (6)
- Potential ore deposits with high HREY complements, like the marine phosphorites analyzed in this paper, could help supply the HREY needed for high-tech and green-tech applications without creating an oversupply of the LREY. Consequently, a search for such deposits with the largest HREY/LREY ratios would help alleviate the supply/oversupply problem.
- (7)
- Land-based phosphorite deposits offer a similar potential REY resource as a byproduct or co-product of the focus phosphate mining (e.g., [6,7]). Recovery of these land-based REY would require the addition of costly infrastructure and changes in extractive processing to the existing mining operations. Production of REY as a co-product of phosphorite mining would be advantageous if considered in the early stages of planning a new mining operation, such as those currently proposed for CM offshore sites.
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Cruise ID | Sample ID | Major 2 | Moderate | Minor |
---|---|---|---|---|
AVON02 | 11-Massive | CFA | calcite | -- |
AVON02 | 11-Porous | CFA | -- | calcite |
AVON02 | 55-13 | CFA | -- | K-feldspar, chlorite |
F10-89-CP | D10-17 | CFA | -- | -- |
F7-86-HW | CD19-1A | CFA | -- | calcite, quartz, plagioclase |
F7-86-HW | CD30-8 | CFA | plagioclase | chlorite |
TN037 | D10-M-1 | CFA | -- | phillipsite, quartz |
TN037 | D12-2 | CFA | -- | quartz |
TUNES6 | D32-6 | CFA | plagioclase | chlorite, smectite, sepiolite |
TUNES6 | D32-9 | CFA | calcite | barite |
V2-91-CP | D4-12 | CFA | -- | K-feldspar, smectite, amphibole |
V2-91-CP | D7-8 | CFA | -- | quartz, ilmenite, palygorskite |
Leached Samples 3 | ||||
SO66 | 26 DSR 1 | CFA | -- | -- |
SO66 | 26 DSR 2 | CFA | -- | -- |
SO66 4 | 28 DSR 6 | CFA | -- | -- |
SO66 | 29 DSR 5 | CFA | -- | phillipsite |
SO66 | 50 DSR 3 | CFA | -- | -- |
SO66 | 61 DSR 1 | CFA | -- | -- |
SO66 4 | 69 DSO 2 | CFA | phillipsite | -- |
SO66 | 80 DSK 6 | CFA | -- | -- |
SO66 | 85 DSK 1 | CFA | -- | -- |
L5-83-HW 4 | D5-A3-2 | CFA | -- | -- |
L5-83-HW 4 | D29-A1-b | CFA | -- | -- |
F7-86-HW 4 | CD14-2D | CFA | -- | -- |
F2-88-HW 4 | D12-1A | CFA | -- | quartz |
F2-88-HW 4 | D12-5 | CFA | -- | quartz |
SO83 | 64 GTV 1 | CFA | -- | -- |
SO83 | 118 GTV 6 | CFA | -- | -- |
SO83 | 126 GTV 3 | CFA | -- | -- |
Cruise ID | Sample ID | Major 2 | Moderate | Minor |
---|---|---|---|---|
CA Borderland | ||||
L-1-74-SC | LCB-14-A | CFA | Px | analcime, quartz |
L-1-74-SC | LCB-14-B | CFA | Px, plagioclase | analcime |
L-1-74-SC | LCB-1-4B | CFA | -- | quartz, dolomite |
L-1-74-SC | LCB-1-4C | CFA | quartz, plagioclase | -- |
L-1-74-SC | LCB-20-6C | CFA | plagioclase | quartz |
L-1-74-SC | LCB-20-8B | CFA | -- | Quartz (?) |
L-2-76-SC | CD281-A | CFA | -- | quartz |
L-2-76-SC | CD281-B | CFA | -- | Plagioclase (?) |
L-2-76-SC | CD350-A | CFA | -- | glauconite or illite, quartz (?) |
L-2-76-SC | CD350-B | CFA | -- | quartz, glauconite or illite |
Peru Margin | ||||
JSL | 3350-1a | CFA | quartz, plagioclase | -- |
JSL | 3350-1b | CFA | quartz, plagioclase | Illite (?), amphibole (?) |
JSL | 3352-4 | CFA | plagioclase, quartz | -- |
JSL | 3355-2 | CFA | quartz, plagioclase | -- |
JSL | 3363-4 | CFA | quartz, plagioclase | -- |
JSL | 3365-2 | CFA | quartz | -- |
JSL | 3372-1 | CFA, quartz | plagioclase, pyrite | -- |
JSL | 3365 | CFA | plagioclase, quartz | -- |
JSL | 3352-6 | CFA | plagioclase | quartz |
RC-2306 | 1-2, GS-1 | CFA | plagioclase, Px, quartz | K-feldspar, glauconite |
Chatham Rise | ||||
NA | DD9+2-8 | CFA | ASi | glauconite, pyrite (?) |
NA | DD9+8 | CFA, calcite | -- | plagioclase, glauconite, quartz |
NA | DD16+2-8 | CFA | calcite | quartz, glauconite, pyrite |
NA | DD16+8 | CFA | calcite, goethite | quartz, glauconite |
NA | DD19+2-8 | CFA | calcite, ASi | glauconite, pyrite |
NA | DD19+8 | CFA | calcite, plagioclase | quartz, glauconite |
NA | DD21+2-8 | CFA | ASi | calcite, glauconite, pyrite (?) |
Chatham Rise | ||||
NA | DD21+8 | CFA | calcite | goethite, pyrite, plagioclase, glauconite (?) |
NA | DD22+2-8 | CFA | calcite | quartz, glauconite, pyrite (?) |
NA | DD22+8 | CFA, calcite | plagioclase | -- |
NA | DD23+2-8 | CFA | calcite, ASi | pyrite, glauconite, quartz (?) |
NA | DD23+8 | CFA, calcite | -- | glauconite or illite |
NA | DD24+2-8 | aragonite, calcite | CFA | plagioclase, glauconite, chlorite (?) |
NA | DD24+8 | CFA, calcite | -- | illite/smectite (mixed layer) (?) |
Blake Plateau | ||||
GOS 74 | 2397-A | CFA | quartz, calcite | glauconite |
GOS 74 | 2397-B | CFA | calcite | quartz, glauconite or illite |
GOS 74 | 2399-A | CFA | calcite, goethite | glauconite or illite |
GOS 74 | 2399-B | CFA | calcite | glauconite or illite |
GOS 74 | 2476-A | CFA, calcite | -- | quartz |
GOS 74 | 2476-B | CFA, calcite | -- | k-feldspar, birnessite |
GOS 74 | 2480 | CFA | calcite | glauconite or illite, quartz, birnessite |
GOS 74 | 2485 | CFA | calcite | glauconite or illite, quartz |
CHN46-1 | Station 15-2 | CFA | calcite, 10 Å manganate | -- |
AT266 | D42-4 | CFA | calcite, 10 Å manganate | analcime |
E. Atlantic 3 | ||||
SO83 | 23 GTV II A3 | CFA | -- | quartz |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 10 | 1.60 | 1.37 | 0.90 | 0.50 | 3.27 |
Si | 10 | 3.73 | 2.58 | 2.80 | 0.73 | 9.07 |
Al | 10 | 0.95 | 0.61 | 0.94 | 0.16 | 3.01 |
Si/Al | 10 | 3.94 | 5.12 | 1.36 | 2.68 | 6.24 |
Mg | 10 | 0.71 | 0.57 | 0.33 | 0.43 | 1.36 |
Ca | 10 | 30.6 | 32.1 | 3.83 | 22.8 | 34.5 |
Na | 10 | 1.27 | 1.18 | 0.27 | 1.02 | 1.85 |
K | 10 | 0.41 | 0.44 | 0.19 | 0.15 | 0.72 |
Ti | 10 | 0.19 | 0.03 | 0.33 | 0.01 | 0.89 |
P | 10 | 11.6 | 12.3 | 1.67 | 8.16 | 13.2 |
Ca/P | 10 | 2.64 | 2.63 | 0.07 | 2.57 | 2.79 |
P2O5 | 10 | 26.6 | 28.1 | 3.84 | 18.7 | 30.3 |
S | 10 | 1.10 | 1.13 | 0.28 | 0.62 | 1.58 |
SO3 | 10 | 2.74 | 2.81 | 0.69 | 1.55 | 3.93 |
CO2 | 10 | 6.31 | 6.60 | 0.93 | 4.34 | 7.06 |
LOI 2 | 10 | 11.1 | 11.0 | 0.69 | 10.2 | 12.2 |
H2O+ | 10 | 4.71 | 4.75 | 0.23 | 4.40 | 5.05 |
As (ppm) | 10 | 13 | 13 | 6.1 | 6.0 | 27 |
Ba | 10 | 684 | 647 | 487 | 145 | 1290 |
Cl | 10 | 1032 | 905 | 368 | 670 | 1790 |
Co | 10 | 5.8 | 4.3 | 3.5 | 2.8 | 13 |
Cr | 10 | 111 | 107 | 45 | 43 | 181 |
Cu | 10 | 23 | 20 | 5.0 | 18 | 31 |
F | 10 | 20,909 | 22,750 | 5205 | 8990 | 25,400 |
Li | 10 | 6.4 | 4.5 | 5.7 | 2.0 | 20 |
Mn | 10 | 79 | 33 | 91 | 17 | 256 |
Mo | 10 | 10 | 6.7 | 12 | 4.0 | 44 |
Ni | 10 | 44 | 43 | 6.0 | 35 | 55 |
Pb | 10 | 4.2 | 3.6 | 1.7 | 2.2 | 7.6 |
Sr | 10 | 2072 | 2100 | 257 | 1560 | 2340 |
U | 10 | 106 | 83 | 67 | 62 | 285 |
V | 10 | 101 | 115 | 41 | 49 | 165 |
Zn | 10 | 57 | 49 | 19 | 41 | 94 |
Zr | 10 | 37 | 16 | 46 | 8.0 | 141 |
La | 10 | 23.6 | 23.0 | 6.37 | 15.1 | 32.6 |
Ce | 10 | 18.7 | 14.7 | 11.5 | 7.00 | 42.6 |
Pr | 10 | 4.23 | 3.77 | 1.78 | 2.05 | 7.39 |
Nd | 10 | 16.8 | 15.0 | 7.08 | 7.90 | 29.4 |
Sm | 10 | 3.43 | 3.03 | 1.50 | 1.60 | 6.10 |
Eu | 10 | 0.97 | 0.82 | 0.48 | 0.43 | 1.85 |
Gd | 10 | 4.63 | 4.49 | 1.49 | 2.48 | 6.53 |
Tb | 10 | 0.71 | 0.70 | 0.22 | 0.38 | 1.00 |
Dy | 10 | 4.61 | 4.66 | 1.29 | 2.63 | 6.34 |
Y | 10 | 59.7 | 59.7 | 13.4 | 40.2 | 78.4 |
Ho | 10 | 1.07 | 1.10 | 0.26 | 0.67 | 1.44 |
Er | 10 | 3.51 | 3.54 | 0.82 | 2.25 | 4.55 |
Tm | 10 | 0.49 | 0.50 | 0.11 | 0.31 | 0.63 |
Yb | 10 | 2.79 | 2.85 | 0.56 | 1.90 | 3.60 |
Lu | 10 | 0.43 | 0.43 | 0.09 | 0.30 | 0.58 |
ΣREY 3 | 10 | 146 | 144 | 41 | 85 | 205 |
%HREY 4 | 10 | 54 | 57 | 6 | 42 | 61 |
Cecn 5 | 10 | 0.63 | 0.62 | 0.14 | 0.38 | 0.85 |
Cesn 5 | 10 | 0.47 | 0.47 | 0.10 | 0.29 | 0.64 |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 10 | 1.72 | 1.55 | 0.60 | 1.17 | 2.97 |
Si | 10 | 8.47 | 7.41 | 3.08 | 5.05 | 14.6 |
Al | 10 | 2.00 | 1.68 | 0.66 | 1.34 | 3.31 |
Si/Al | 10 | 4.23 | 4.10 | 0.50 | 3.51 | 4.87 |
Mg | 10 | 0.66 | 0.67 | 0.09 | 0.42 | 0.74 |
Ca | 10 | 25.2 | 26.3 | 3.09 | 19.1 | 28.7 |
Na | 10 | 1.31 | 1.26 | 0.17 | 1.05 | 1.60 |
K | 10 | 0.73 | 0.65 | 0.26 | 0.44 | 1.21 |
Ti | 10 | 0.09 | 0.08 | 0.02 | 0.07 | 0.13 |
P | 10 | 9.69 | 10.1 | 1.27 | 7.24 | 11.1 |
Ca/P | 10 | 2.60 | 2.60 | 0.04 | 2.53 | 2.70 |
P2O5 | 10 | 22.2 | 23.1 | 2.91 | 16.6 | 25.5 |
S | 10 | 1.40 | 1.37 | 0.54 | 0.73 | 2.63 |
SO3 | 10 | 3.50 | 3.42 | 1.35 | 1.82 | 6.55 |
CO2 | 10 | 5.90 | 6.22 | 1.01 | 4.03 | 7.02 |
LOI 2 | 10 | 10.6 | 10.8 | 1.50 | 8.07 | 13.3 |
H2O+ | 10 | 4.49 | 4.55 | 0.66 | 3.50 | 5.40 |
As (ppm) | 10 | 29 | 26 | 20 | 7.0 | 81 |
Ba | 10 | 136 | 106 | 64 | 84 | 281 |
Cl | 10 | 1829 | 1762 | 595 | 1007 | 3037 |
Co | 10 | 3.9 | 4.0 | 1.0 | 2.7 | 5.5 |
Cr | 10 | 76 | 70 | 23 | 49 | 116 |
Cu | 10 | 13 | 14 | 2.2 | 8.4 | 15 |
F | 10 | 22,157 | 20,588 | 3747 | 18173 | 29,394 |
Li | 10 | 10 | 11 | 2.0 | 7.0 | 14 |
Mn | 10 | 98 | 91 | 21 | 71 | 141 |
Mo | 10 | 17 | 12 | 17 | 2.9 | 63 |
Ni | 10 | 43 | 42 | 18 | 21 | 81 |
Pb | 10 | 6.4 | 6.0 | 1.8 | 4.2 | 9.8 |
Sr | 10 | 1756 | 1855 | 238 | 1330 | 1980 |
U | 10 | 115 | 123 | 35 | 48 | 177 |
V | 10 | 62 | 64 | 12 | 40 | 80 |
Zn | 10 | 40 | 40 | 8.3 | 30 | 56 |
Zr | 10 | 71 | 75 | 22 | 36 | 95 |
La | 10 | 10.4 | 10.5 | 1.25 | 8.50 | 12.6 |
Ce | 10 | 17.7 | 16.8 | 2.98 | 14.7 | 23.5 |
Pr | 10 | 2.30 | 2.22 | 0.32 | 1.96 | 2.93 |
Nd | 10 | 9.09 | 9.20 | 1.18 | 7.50 | 11.1 |
Sm | 10 | 1.84 | 1.85 | 0.26 | 1.50 | 2.20 |
Eu | 10 | 0.47 | 0.46 | 0.09 | 0.33 | 0.62 |
Gd | 10 | 2.00 | 2.09 | 0.31 | 1.41 | 2.46 |
Tb | 10 | 0.31 | 0.31 | 0.04 | 0.24 | 0.37 |
Dy | 10 | 1.96 | 1.98 | 0.35 | 1.27 | 2.39 |
Y | 10 | 18.8 | 18.4 | 4.39 | 9.60 | 24.2 |
Ho | 10 | 0.44 | 0.44 | 0.08 | 0.28 | 0.54 |
Er | 10 | 1.33 | 1.34 | 0.24 | 0.83 | 1.70 |
Tm | 10 | 0.21 | 0.21 | 0.04 | 0.12 | 0.25 |
Yb | 10 | 1.32 | 1.33 | 0.22 | 0.80 | 1.60 |
Lu | 10 | 0.22 | 0.22 | 0.04 | 0.12 | 0.27 |
ΣREY 3 | 10 | 68 | 70 | 9 | 52 | 80 |
%HREY 4 | 10 | 40 | 41 | 5 | 29 | 45 |
Cecn 5 | 10 | 1.13 | 1.12 | 0.04 | 1.07 | 1.19 |
Cesn 5 | 10 | 0.85 | 0.84 | 0.03 | 0.81 | 0.90 |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 15 | 3.24 | 3.08 | 1.23 | 1.26 | 5.00 |
Si | 15 | 4.28 | 4.62 | 1.91 | 1.33 | 6.55 |
Al | 15 | 0.58 | 0.60 | 0.31 | 0.17 | 1.39 |
Si/Al | 15 | 7.41 | 7.65 | 1.95 | 3.93 | 11.4 |
Mg | 15 | 0.62 | 0.59 | 0.22 | 0.34 | 0.93 |
Ca | 15 | 31.0 | 30.9 | 3.08 | 27.0 | 35.7 |
Na | 15 | 0.70 | 0.69 | 0.04 | 0.63 | 0.78 |
K | 15 | 1.05 | 1.01 | 0.59 | 0.33 | 1.92 |
Ti | 15 | <0.04 | <0.01 | 0.09 | <0.01 | 0.31 |
P | 15 | 8.36 | 8.77 | 1.50 | 5.45 | 9.86 |
Ca/P | 15 | 3.72 | 3.65 | 0.99 | 2.75 | 5.73 |
P2O5 | 15 | 19.2 | 20.1 | 3.43 | 12.5 | 22.6 |
S | 15 | 0.64 | 0.64 | 0.12 | 0.47 | 0.90 |
SO3 | 15 | 1.59 | 1.60 | 0.29 | 1.17 | 2.25 |
CO2 | 2 | 5.82 | 5.82 | 0.43 | 5.51 | 6.12 |
LOI 2 | 15 | 16.9 | 16.8 | 5.22 | 9.97 | 24.2 |
H2O+ | 2 | 4.05 | 4.05 | 0.07 | 4.00 | 4.10 |
As (ppm) | 15 | 22 | 23 | 7.9 | 11 | 39 |
Ba | 15 | 94 | 50 | 91 | 34 | 335 |
Cl | 15 | 850 | 810 | 346 | 340 | 1630 |
Co | 15 | 6.7 | 7.7 | 2.1 | 3.0 | 9.7 |
Cr | 15 | 40 | 44 | 20 | 15 | 76 |
Cu | 15 | 8.0 | 7.0 | 4.5 | 1.0 | 17 |
F | 15 | 17,860 | 17,400 | 4085 | 11,000 | 24,800 |
Li | 15 | 7.7 | 8.0 | 3.6 | 3.0 | 13 |
Mn | 15 | 93 | 78 | 65 | 57 | 324 |
Mo | 15 | 2.9 | 2.8 | 1.5 | 0.94 | 7.3 |
Ni | 15 | 30 | 30 | 10 | 15 | 53 |
Pb | 15 | 12 | 12 | 4.7 | 5.2 | 20 |
Sr | 15 | 1447 | 1330 | 493 | 1110 | 2660 |
U | 15 | 155 | 130 | 77 | 64 | 334 |
V | 15 | 71 | 73 | 16 | 47 | 94 |
Zn | 15 | 27 | 27 | 5.4 | 17 | 38 |
Zr | 15 | 24 | 22 | 9.7 | 10 | 52 |
La | 15 | 22.7 | 20.4 | 13.6 | 7.60 | 48.9 |
Ce | 15 | 15.6 | 15.8 | 8.05 | 4.10 | 29.8 |
Pr | 15 | 2.84 | 2.75 | 1.35 | 1.02 | 5.38 |
Nd | 15 | 11.5 | 11.2 | 5.41 | 4.30 | 21.7 |
Sm | 15 | 1.97 | 1.90 | 0.86 | 0.80 | 3.60 |
Eu | 15 | 0.49 | 0.47 | 0.22 | 0.18 | 0.90 |
Gd | 15 | 2.71 | 2.52 | 1.27 | 1.09 | 5.11 |
Tb | 15 | 0.39 | 0.36 | 0.18 | 0.16 | 0.73 |
Dy | 15 | 2.54 | 2.32 | 1.21 | 0.98 | 4.88 |
Y | 15 | 37.6 | 33.8 | 21.0 | 13.6 | 78.1 |
Ho | 15 | 0.67 | 0.61 | 0.34 | 0.25 | 1.35 |
Er | 15 | 2.04 | 1.84 | 1.01 | 0.82 | 4.09 |
Tm | 15 | 0.29 | 0.26 | 0.14 | 0.12 | 0.57 |
Yb | 15 | 1.75 | 1.60 | 0.84 | 0.70 | 3.40 |
Lu | 15 | 0.26 | 0.22 | 0.13 | 0.10 | 0.53 |
ΣREY 3 | 15 | 103 | 95 | 55 | 36 | 209 |
%HREY 4 | 15 | 47 | 48 | 3 | 38 | 50 |
Cecn 5 | 15 | 0.78 | 0.81 | 0.08 | 0.59 | 0.87 |
Cesn 5 | 15 | 0.59 | 0.61 | 0.06 | 0.45 | 0.66 |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 10 | 2.35 | 2.34 | 1.12 | 0.80 | 3.88 |
Si | 10 | 2.86 | 2.42 | 1.51 | 1.17 | 6.45 |
Al | 10 | 0.71 | 0.75 | 0.28 | 0.31 | 1.28 |
Si/Al | 10 | 4.04 | 4.35 | 2.15 | 1.60 | 7.91 |
Mg | 10 | 0.65 | 0.64 | 0.16 | 0.43 | 0.92 |
Ca | 10 | 31.8 | 32.2 | 2.07 | 27.1 | 34.9 |
Na | 10 | 0.71 | 0.70 | 0.12 | 0.53 | 0.91 |
K | 10 | 0.51 | 0.50 | 0.33 | 0.19 | 1.27 |
Ti | 10 | 0.05 | 0.04 | 0.03 | 0.02 | 0.11 |
P | 10 | 8.80 | 8.84 | 1.25 | 6.76 | 10.9 |
Ca/P | 10 | 3.61 | 3.53 | 0.72 | 2.93 | 5.17 |
P2O5 | 10 | 20.2 | 20.3 | 2.86 | 15.5 | 25.0 |
S | 10 | 0.68 | 0.66 | 0.14 | 0.51 | 0.96 |
SO3 | 10 | 1.70 | 1.64 | 0.35 | 1.27 | 2.40 |
CO2 | 10 | 13.0 | 12.9 | 4.01 | 6.62 | 20.0 |
LOI 2 | 10 | 16.7 | 16.4 | 3.84 | 11.3 | 23.8 |
H2O+ | 10 | 3.70 | 3.90 | 0.70 | 2.45 | 4.50 |
As (ppm) | 10 | 35 | 34 | 15 | 12 | 59 |
Ba | 10 | 323 | 217 | 394 | 22 | 1301 |
Cl | 10 | 506 | 457 | 202 | 199 | 895 |
Co | 10 | 126 | 56 | 137 | 5.6 | 338 |
Cr | 10 | 99 | 82 | 92 | 12 | 269 |
Cu | 10 | 72 | 17 | 95 | 5.4 | 290 |
F | 10 | 27,216 | 27,516 | 3248 | 21,912 | 32,171 |
Li | 10 | 14 | 12 | 7.7 | 7.0 | 31 |
Mn | 10 | 9108 | 4647 | 11,565 | 232 | 30,051 |
Mo | 10 | 22 | 13 | 22 | 3.5 | 72 |
Ni | 10 | 467 | 107 | 583 | 26 | 1738 |
Pb | 10 | 19 | 13 | 14 | 4.9 | 40 |
Sr | 10 | 1376 | 1354 | 300 | 1001 | 1990 |
U | 10 | 62 | 36 | 84 | 5.3 | 285 |
V | 10 | 113 | 122 | 39 | 37 | 174 |
Zn | 10 | 87 | 93 | 41 | 39 | 160 |
Zr | 10 | 73 | 79 | 43 | 22 | 151 |
La | 10 | 71.1 | 57.9 | 42.5 | 23.4 | 133 |
Ce | 10 | 36.2 | 34.4 | 20.7 | 7.60 | 77.8 |
Pr | 10 | 10.8 | 8.48 | 6.73 | 3.83 | 22.6 |
Nd | 10 | 48.0 | 37.1 | 30.6 | 17.0 | 102 |
Sm | 10 | 9.09 | 7.10 | 5.93 | 3.10 | 20.1 |
Eu | 10 | 2.45 | 1.93 | 1.57 | 0.88 | 5.23 |
Gd | 10 | 12.9 | 10.1 | 8.43 | 4.48 | 27.1 |
Tb | 10 | 1.71 | 1.32 | 1.10 | 0.61 | 3.53 |
Dy | 10 | 11.8 | 8.92 | 7.60 | 4.17 | 23.1 |
Y | 10 | 130 | 101 | 83.7 | 38.4 | 257 |
Ho | 10 | 2.58 | 1.97 | 1.66 | 0.87 | 4.76 |
Er | 10 | 7.75 | 5.80 | 4.97 | 2.55 | 14.8 |
Tm | 10 | 1.17 | 0.88 | 0.75 | 0.38 | 2.32 |
Yb | 10 | 6.65 | 4.90 | 4.36 | 2.20 | 13.9 |
Lu | 10 | 1.19 | 0.87 | 0.79 | 0.38 | 2.52 |
ΣREY 3 | 10 | 353 | 286 | 211 | 124 | 663 |
%HREY 4 | 10 | 50 | 51 | 7 | 33 | 59 |
Cecn 5 | 10 | 0.55 | 0.50 | 0.29 | 0.27 | 1.24 |
Cesn 5 | 10 | 0.41 | 0.38 | 0.22 | 0.20 | 0.94 |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 12 | 0.66 | 0.42 | 0.75 | 0.06 | 2.89 |
Si | 12 | 2.33 | 1.86 | 2.11 | 0.03 | 7.15 |
Al | 12 | 0.78 | 0.64 | 0.65 | 0.02 | 2.12 |
Si/Al | 12 | 2.99 | 2.87 | 0.52 | 1.55 | 3.37 |
Mg | 12 | 0.27 | 0.24 | 0.14 | 0.11 | 0.62 |
Ca | 12 | 34.7 | 35.4 | 3.25 | 26.2 | 37.8 |
Na | 12 | 0.80 | 0.83 | 0.15 | 0.56 | 1.09 |
K | 12 | 0.36 | 0.27 | 0.31 | 0.02 | 0.86 |
Ti | 12 | <0.08 | <0.05 | 0.08 | <0.01 | 0.28 |
P | 12 | 12.7 | 12.9 | 1.27 | 9.95 | 14.0 |
Ca/P | 12 | 2.73 | 2.66 | 0.26 | 2.58 | 3.51 |
P2O5 | 12 | 29.1 | 29.7 | 2.90 | 22.8 | 32.2 |
S | 12 | 0.68 | 0.71 | 0.09 | 0.54 | 0.80 |
SO3 | 12 | 1.71 | 1.76 | 0.22 | 1.35 | 2.00 |
CO2 | 9 | 5.12 | 5.13 | 1.22 | 3.75 | 6.96 |
LOI 2 | 12 | 9.14 | 8.08 | 2.90 | 6.67 | 17.5 |
H2O+ | 9 | 2.22 | 2.10 | 0.32 | 1.90 | 2.80 |
As (ppm) | 12 | 5.2 | 5.0 | 1.7 | 3.0 | 9.0 |
Ba | 12 | 483 | 81 | 725 | 20 | 1900 |
Cl | 12 | 1208 | 755 | 958 | 310 | 3410 |
Co | 12 | 21 | 12 | 22 | 1.7 | 67.8 |
Cr | 12 | 21 | 14 | 15 | 7.0 | 51.0 |
Cu | 12 | 77 | 64 | 56 | 15 | 205 |
F | 12 | 25,767 | 28,250 | 5461 | 12,300 | 30,300 |
Li | 12 | <6.6 | <6.0 | 5.9 | <1.0 | 20 |
Mn | 12 | 1210 | 775 | 1343 | 46 | 3873 |
Mo | 12 | 3.1 | 2.8 | 2.3 | 0.75 | 7.3 |
Ni | 12 | 116 | 61 | 115 | 21 | 366 |
Pb | 12 | 7.0 | 6.3 | 5.1 | 1.1 | 15 |
Sr | 12 | 1223 | 1175 | 338 | 724 | 1920 |
U | 12 | 6.7 | 6.3 | 1.9 | 4.7 | 11 |
V | 12 | 33 | 33 | 10 | 22 | 59 |
Zn | 12 | 51 | 49 | 20 | 26 | 100 |
Zr | 12 | 91 | 79 | 52 | 9.5 | 211 |
La | 12 | 102 | 79.7 | 61.8 | 16.6 | 214 |
Ce | 12 | 15.0 | 13.1 | 7.56 | 3.10 | 30.2 |
Pr | 12 | 14.4 | 9.21 | 10.3 | 2.85 | 36.8 |
Nd | 12 | 60.6 | 38.8 | 43.6 | 11.9 | 153 |
Sm | 12 | 11.5 | 7.05 | 8.82 | 2.40 | 31.1 |
Eu | 12 | 3.26 | 2.16 | 2.43 | 0.73 | 8.31 |
Gd | 12 | 18.2 | 13.2 | 12.8 | 3.47 | 42.5 |
Tb | 12 | 2.44 | 1.87 | 1.65 | 0.46 | 5.67 |
Dy | 12 | 17.4 | 14.5 | 11.3 | 3.03 | 38.7 |
Y | 12 | 224 | 205 | 132 | 38.9 | 437 |
Ho | 12 | 4.19 | 3.75 | 2.54 | 0.71 | 8.69 |
Er | 12 | 13.4 | 12.3 | 7.88 | 2.29 | 26.9 |
Tm | 12 | 1.88 | 1.77 | 1.10 | 0.34 | 3.88 |
Yb | 12 | 12.9 | 12.3 | 7.62 | 2.40 | 27.2 |
Lu | 12 | 1.98 | 1.92 | 1.19 | 0.35 | 4.19 |
ΣREY 3 | 12 | 503 | 434 | 292 | 112 | 1022 |
%HREY 4 | 12 | 60 | 58 | 8 | 47 | 74 |
Cecn 5 | 12 | 0.25 | 0.17 | 0.34 | 0.06 | 1.29 |
Cesn 5 | 12 | 0.19 | 0.13 | 0.25 | 0.05 | 0.98 |
Element | N | Mean 1 | Median | StDev | Min | Max |
---|---|---|---|---|---|---|
Fe (wt %) | 18 | 0.46 | 0.39 | 0.39 | 0.01 | 1.38 |
Si | 18 | 1.67 | 1.26 | 1.44 | 0.32 | 5.28 |
Al | 18 | 0.58 | 0.43 | 0.54 | 0.05 | 1.88 |
Si/Al | 18 | 2.88 | 3.13 | 1.10 | 2.19 | 6.01 |
Mg | 18 | 0.21 | 0.20 | 0.11 | 0.04 | 0.45 |
Ca | 18 | 35.4 | 36.3 | 2.08 | 30.4 | 37.9 |
Na | 18 | 0.66 | 0.66 | 0.11 | 0.50 | 0.85 |
K | 18 | <0.17 | <0.06 | 0.19 | <0.01 | 0.69 |
Ti | 18 | <0.05 | <0.04 | 0.05 | 0.004 | 0.22 |
P | 18 | 13.5 | 13.8 | 0.84 | 11.8 | 14.6 |
Ca/P | 18 | 2.62 | 2.63 | 0.04 | 2.58 | 2.77 |
P2O5 | 18 | 31.0 | 31.6 | 1.93 | 27.0 | 33.5 |
S | 18 | 0.71 | 0.72 | 0.15 | 0.49 | 0.94 |
SO3 | 18 | 1.77 | 1.79 | 0.37 | 1.22 | 2.35 |
CO2 | 18 | 6.35 | 6.40 | 1.35 | 3.84 | 7.99 |
LOI 2 | 18 | 8.73 | 8.58 | 1.44 | 5.88 | 11.7 |
H2O+ | 5 | 2.14 | 2.34 | 0.33 | 1.76 | 2.45 |
As (ppm) b | 0 | -- | -- | -- | -- | -- |
Ba | 13 | 4401 | 267 | 521 | 195 | 2140 |
Cl | 18 | 497 | 400 | 646 | 50 | 2980 |
Co | 13 | 11 | 10 | 5.3 | 4.0 | 23 |
Cr | 13 | 18 | 18 | 7.1 | 9.0 | 33 |
Cu | 15 | 38 | 34 | 20 | 15 | 89 |
F | 18 | 39,011 | 39,250 | 4078 | 31,800 | 46,000 |
Li | 13 | 5.5 | 5.0 | 2.7 | 2.0 | 10 |
Mn | 18 | 709 | 300 | 1550 | 75 | 6816 |
Mo | 12 | 5.5 | 5.5 | 2.2 | 1.0 | 9.0 |
Ni | 13 | 23 | 21 | 15 | 9.0 | 71 |
Pb | 13 | 151 | 146 | 41 | 91 | 218 |
Sr | 15 | 1563 | 1410 | 453 | 1000 | 2580 |
U | 16 | 12 | 8.5 | 7.3 | 6.3 | 30 |
V | 13 | 35 | 35 | 10 | 21 | 50 |
Zn | 13 | 80 | 63 | 49 | 38 | 205 |
Zr | 13 | 44 | 38 | 18 | 20 | 77 |
La | 18 | 180 | 189 | 89.2 | 7.20 | 372 |
Ce | 18 | 28.5 | 29.4 | 17.9 | 2.00 | 74.0 |
Pr | 18 | 23.1 | 20.0 | 13.7 | 1.00 | 49.3 |
Nd | 18 | 102 | 88.9 | 60.2 | 4.40 | 222 |
Sm | 18 | 20.3 | 17.3 | 12.9 | 0.97 | 46.8 |
Eu | 18 | 5.33 | 4.77 | 3.21 | 0.22 | 11.8 |
Gd | 18 | 32.2 | 29.9 | 19.1 | 1.40 | 73.9 |
Tb | 18 | 4.69 | 4.45 | 2.80 | 0.18 | 10.7 |
Dy | 18 | 30.8 | 29.6 | 17.8 | 1.40 | 69.7 |
Y | 13 | 441 | 415 | 233 | 145 | 976 |
Ho | 18 | 8.16 | 8.38 | 4.64 | 0.41 | 19.2 |
Er | 18 | 24.6 | 25.3 | 13.8 | 1.20 | 57.3 |
Tm | 18 | 3.51 | 3.50 | 1.99 | 0.20 | 8.30 |
Yb | 18 | 21.7 | 20.8 | 12.4 | 1.30 | 52.2 |
Lu | 13 | 3.74 | 3.41 | 2.00 | 1.03 | 8.01 |
ΣREY 3 | 13 | 935 | 824 | 490 | 250 | 1992 |
%HREY 4 | 13 | 62 | 62 | 5 | 56 | 70 |
Cecn 5 | 18 | 0.20 | 0.19 | 0.08 | 0.05 | 0.35 |
Cesn 5 | 18 | 0.15 | 0.14 | 0.06 | 0.04 | 0.27 |
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
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Hein, J.R.; Koschinsky, A.; Mikesell, M.; Mizell, K.; Glenn, C.R.; Wood, R. Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium. Minerals 2016, 6, 88. https://doi.org/10.3390/min6030088
Hein JR, Koschinsky A, Mikesell M, Mizell K, Glenn CR, Wood R. Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium. Minerals. 2016; 6(3):88. https://doi.org/10.3390/min6030088
Chicago/Turabian StyleHein, James R., Andrea Koschinsky, Mariah Mikesell, Kira Mizell, Craig R. Glenn, and Ray Wood. 2016. "Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium" Minerals 6, no. 3: 88. https://doi.org/10.3390/min6030088