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Article

Sr and Nd Isotopes in Mineral Fractions of Ferromanganese Crusts from the Northernmost Pacific

by
Pavel Mikhailik
1,*,
Irina Vishnevskaya
1,2,
Liang Yi
3,
Natalia Soloshenko
4 and
Vadim Pellinen
5
1
Far East Geological Institute, FEB RAS, Vladivostok 690022, Russia
2
Vernadsky Institute of Geochemistry and Analytical Chemistry, RAS, Moscow 119334, Russia
3
State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092, China
4
Zavaritsky Institute of Geology and Geochemistry, UB RAS, Ekaterinburg 620010, Russia
5
Institute of the Earth’s Crust, SB RAS, Irkutsk 644033, Russia
*
Author to whom correspondence should be addressed.
J. Mar. Sci. Eng. 2023, 11(10), 1920; https://doi.org/10.3390/jmse11101920
Submission received: 23 August 2023 / Revised: 24 September 2023 / Accepted: 25 September 2023 / Published: 5 October 2023
(This article belongs to the Section Geological Oceanography)
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Abstract

:
A study of the isotopic compositions of neodymium and strontium in four mineral fractions of the hydrogenous ferromanganese crusts of the northernmost Pacific has been carried out for the first time. The relationship of the 87Sr/86Sr ratio and εNd value of the residual fraction in heterochronous layers of the ferromanganese crusts have shown that the sources of detrital matter are from rock weathering by the Yukon River, the Kuskokwim River, the Anadyr River and the rivers of Kamchatka. The amount of aluminosilicate impurity does not affect the isotopic compositions of the chemogenic (loosely bound, Mn oxides or manganese, hydrous Fe oxides or ferrous) fractions. The decreased εNd value in the ferrous fraction seems to be related to the presence of rare earth element (REE) phosphate complexes in seawater. The increase in those complexes is a consequence of melt waters entering the ocean during warming periods. Our data indicate that the carbonate REE complexes are not the dominant form of the REEs in the northernmost Pacific, which leads to the fact that the neodymium isotopic compositions of the manganese and ferrous fractions of hydrogenous ferromanganese crusts are different. A decrease in εNd value in the ferrous fraction may be a marker of a local increase in the surface water bioproductivity. Our data also show that the increase of the REE in the ferrous fraction relative to the manganese fraction does not reflect the participation of hydrothermal matter in the formation of mixed hydrogenous–hydrothermal crusts but is a consequence of an increase in the REE phosphate complexes.

1. Introduction

Ferromanganese deposits (crusts, nodules, etc.) developed on sea floors are marine sources for strategic metals, such as Mn, Co, and rare earth element (REE), and informative proxies recording oceanic paleoenvironment changes, e.g., [1,2,3]. These ferromanganese crusts usually grow on slopes and/or sediment-free seamounts/guyots, with a water depth range of 400 to 7000 m [1,4,5]. There are two types of ferromanganese crusts widespread on the seafloor, i.e., hydrogenous and hydrothermal [6]. For hydrogenous ones, metals are mainly from ambient seawater, while for hydrothermal ones, hydrothermal fluids are the main source [7]. For different geneses, mineralogical, geochemical and isotopic properties of ferromanganese crust are distinct, e.g., [8,9].
During the period of growth that spans millions of years, e.g., [10], hydrogenous crusts absorb dissolved metals from the seawater, and studying REEs and metal isotopes makes it possible to reconstruct water masses [11,12,13,14,15]. In addition, volcanic activities, aeolian input, and cosmogenic matter also have fingerprints in the growth processes of these crusts [16,17], and metal/mineral changes can be correlated with the glacial–interglacial alternations [18,19,20,21,22]. For example, most REEs in hydrothermal crusts are associated with hydrous Fe oxides [23,24], while in hydrogenous crusts, REEs may be influenced by the competition between manganese and ferrous fractions [23,25].
Studying Sr and Nd isotopic composition of ferromanganese deposits helps to identify metal sources, reconstruct formation processes, and establish age models, e.g., [17,26,27]. Although the behavior of Sr and Nd isotopes in bulk ferromanganese crusts has been broadly studied [8,9,12,13,28,29], the balance of εNd values and the 87Sr/86Sr ratios in different mineral fractions of ferromanganese deposits are not well known. To address this question, we have examined a collection of ferromanganese crust samples from the northernmost Pacific Ocean.

2. Materials and Methods

2.1. Study Area

The study area is not far from the continent, from aeolian source regions, and from active volcanic fields (Figure 1), allowing us to trace how profound the terrigenous influence is in the neodymium and strontium isotopic compositions in mineral fractions of ferromanganese crusts.
The Hanzei and Detroit Guyots are parts of the northern segment of the Emperor Ridge, which extends southward for 2300 km to the Hawaiian hotspot [30]. These guyots are flat-topped seamounts that represent an earlier stage of the Hawaiian hotspot (~80–60 Ma). The age of the Detroit Guyot is about 82–76 Ma [31,32,33], while the Hanzei Guyot is thought to be older than 73 Ma [34]. The Rat Fracture Zone (FZ) extends in a S-N direction and intersects the Aleutian Trench at nearly a right angle. The Stalemate FZ has a strike that is oriented north-west. Around 169°45′ E, the Stalemate FZ bends in a north-north-west direction and gradually into the trench [35].

2.2. Studied Crusts

The studied ferromanganese crusts (Figure 2) were collected from the slopes of the Hanzei and Detroit Guyots in the Emperor Ridge (Figure 1a) and from the Rat and Stalemate FZs (Figure 1b), during the scientific expedition of the R/V Sonne (249th cruise, 2016). All of the studied crusts (Figure 2) are hydrogenous, based on mineral composition and metal ratios [36], and analysis of bulk samples indicates the following elemental contents (Table 1): Si (13.0 ± 5.1%), Al (2.7 ± 1.3%), Ca (1.9 ± 0.2%), Fe (19.1 ± 3.8%), Mn (13.3 ± 5.7%), Co (1300 ± 591 ppm), Cu (850 ± 816 ppm), and Ni (1644 ± 1298 ppm).
In the ternary diagram based on Mn-Fe-(Co+Cu+Ni) × 10 [6], part of the samples are located in the hydrothermal area or on the border between two genetic types (Figure 3). As is known, hydrothermal ferromanganese deposits composed of bernessite, todorokite or pyrolusite [7] and hydrogenic crusts contain vernadite [4]. Vernadite in hydrothermal deposits likely indicates a high growth rate and, as a consequence, low concentrations of Co, Cu and Ni are observed (Table 2), relative to typical hydrogenetic Co-rich crusts [37].
For this study, seven samples (Figure 2) from each of four crusts were collected (Table 1). For each sample, the bulk sample and four subsamples in different mineral fractions, namely loosely bound (I or carbonate), Mn oxide (II), hydrous Fe oxide (III), and residual (IV or silicate), were prepared for later measurements.
The maximum ∑REE (3147 ppm) is found in sample DR70-9/2, in which Cerium is 1841 ppm (Table 2). For the remaining crusts, this value varies between 804–2193 ppm (Table 2). All samples are characterized by a positive Ce anomaly (Ce/Ce* = Cesn/(Lasn × 0.5 + Prsn × 0.5); the index “sn” is normalized by the Post-Archean Australian shale (PAAS) [38], which varies from 1.36 to 3.10 (Figure 4, Table 2). Its maximum value is found in the FZ Rat sample (DR23-5), where Cerium is 958 ppm. The Eu anomaly (Eu/Eu* = Eusn/(Smsn × 0.5 + Gdsn × 0.5)) values are also positive, with a narrower range of 1.08–1.16 (Table 2). The REE patterns (Figure 4a) are similar to those of hydrogenetic deposits [39]. Moreover, in the discrimination diagrams, the samples are located in a hydrogenetic area (Figure 4b,c).

2.3. Measurements

The bulk chemical analysis was made in the Collective Use Center (CUC) of the Far East Geological Institute, Far East Branch of the Russian Academy of Science. In the course of the elemental analysis by plasma spectrometry (ICP-AES and ICP-MS), the samples were dried to a constant weight at 105 Co. A weighed portion of the dried test sample (0.03 g) was placed in a platinum dish; a mixture of concentrated acids (HF, HNO3, HClO4) was added in a ratio of 3:5:1 and evaporated to wet salts; the treatment was repeated with HNO3 and HClO4 acid in a ratio of 1:0.5 and evaporated to wet salts again. Then, the samples were sequentially treated with deionized water and concentrated HNO3, each time evaporating to wet salts. During the sample preparation, a Mn (IV) oxide precipitate was released from the samples. To restore it and convert it into a soluble form, treatment with 1–2 mL of 30% H2O2 and 10 mL of 26% HNO3 was performed with heating. Then, the sample solution was transferred into 50 mL polypropylene volumetric flasks and filled up to the mark with deionized water. Aliquots of 10 mL for ICP-AES and 2 mL for ICP-MS were taken from the resulting solutions. Before performing ICP-MS measurements, the solutions were diluted 5 times.
The concentrations of Mn, Fe, Ca, and Al were determined using the multielement method of inductively coupled plasma atomic emission spectrometry (ICP-AES) on an iCAP 7600 Duo spectrometer (Thermo Scientific, Waltham, MA, USA). In this case, the Si content in the sample was determined by the classical gravimetric method from a weighed portion of 0.1 g after fusing the powder sample with anhydrous sodium carbonate.
The trace element composition of the samples (Co, Ni, Cu, Sr, REE) was studied by inductively coupled plasma mass spectrometry (ICP-MS) using an Agilent 7700 spectrometer (Agilent Tech., Tokyo, Japan).
The pretreatment and measuring of Sr and Nd contents in mineral fractions are adapted from the procedures proposed by [40] and the details are listed in [9].
Our scheme of phase analysis comprises four fractions of successive sample treatment.
Fraction I. Treatment of 1 g sample with acetate buffer (1N CH3COOH + 1N CH3COONa·3H2O, pH = 5) for 5 h at room temperature, with the sample: reagent proportion of 1:50 (w/w). This procedure leads to the extraction of calcium carbonate and associated elements and the release of absorbed ions. The obtained solution was filtered off. The filtrate was mineralized with concentrated HNO3 in a microwave oven and was analyzed by ICP AES and ICP MS. The residue was washed with deionized type I water, dried, and subjected to the following treatment.
Fraction II. Extraction of Mn and associated elements by treatment of the residue with 0.5 M NH2OH (pH = 2) for 3 min at room temperature, with the residue:reagent proportion of 1:100 (w/w). The obtained solutions were filtered off, hydroxylamine in the filtrate was decomposed by concentrated HNO3 on heating, the solution was evaporated, and the precipitate was dissolved in 5% HNO3. The solutions were analyzed by ICP AES and ICP MS.
Fraction III. The weighed portion of the dried residue was treated with a mixture of 0.2 M oxalic acid and ammonium oxalate (pH = 3.5, residue:solution proportion of 1:175 (w/w)) for 12 h at room temperature. The filtrate was evaporated to a wet salt and treated with concentrated HNO3 to destroy the organic matrix. After evaporation, the residue was dissolved in 5% HNO3. The resulting solutions were analyzed by ICP AES and ICP MS. These extracts contained Fe hydroxides.
Fraction IV. The solid residue obtained in the previous chemical treatment (an aluminosilicate fraction) was ashed together with the filter at 600 °C in a muffle furnace. Then, it was dissolved in a mixture of HF, HNO3, and HClO4 in a Teflon weighing bottle on heating. The obtained solutions were analyzed by ICP AES and ICP MS.
The isotopic composition of Sr and Nd (35 measurements in total) was conducted in the CUC “Geoanalitik” of the Institute of Geology and Geochemistry, the Ural Branch of the Russian Academy of Sciences (UB RAS) (Ekaterinburg). The portion of the dry substance of each fraction was dissolved in 0.5 mL of 7 M HNO3 and centrifuged for 15 min at 6000 rpm (EBA 21 centrifuge, Hettich, Germany). The resulting solution was applied to the Sr resin column (100–200 mesh, Triskem). Sr was extracted by the stepwise elution technique in 7 M and 0.05 M HNO3. The eluate was evaporated to wet salts and dissolved in 5 mL of 0.5% HNO3. This solution was used to measure the 87Sr/86Sr ratio. The Sr isotopic composition was analyzed using a multi-collector inductively coupled mass spectrometer (Neptune Plus, Thermo Scientific). The correctness of the measurement technique was assessed using the international standard Sr SRM-987 (87Sr/86Sr ratio during the period of operation was 0.710256 ± 0.000017, 2σ, n = 21). The mass fractionation was corrected by normalizing exponentially with an 88Sr/86Sr ratio of 8.3752.
For Nd isotopic composition, the procedure was carried out following [8]. The correctness of the measurement technique was assessed using the international standard JNdi-1 (143Nd/144Nd ratio in the standard during the operation was 0.512107 ± 0.000010, 2σ, n = 15). The measurement error of the Nd isotopic composition was 0.005%.
For young samples (<10 Ma), the following equation for calculating εNd used in this study is as follows:
ε N d ( 0 ) = N d 143 N d 144 N d 143 N d 144 C H U R − 1 · 10,000
where 143Nd/144Nd is the Nd isotopic composition in the natural sample, and (143Nd/144Nd)CHUR is from the “homogeneous chondrite reservoir” with a value of 0.512638 [41].

3. Results

3.1. Sr and Nd in Bulk Samples

The Sr content varies substantially, from 659 ppm to 1707 ppm, and the obtained 87Sr/86Sr ratio of bulk samples ranges from 0.707973 to 0.709141 (Table 2). We also observe a significant correlation between Sr content and 87Sr/86Sr ratio (r = 0.84, p < 0.01, n = 7). In addition, the 87Sr/86Sr ratio of sample DR59-11/1 (0.707973 ± 0.000005) shifts to the values of typical volcanic rocks, implying a large number of quartz-plagioclase inputs during the crustal growth (Table 1).
The Nd isotopic composition, in terms of εNd, ranges from −2.3 to −4.4 (Table 2), corresponding to isotopic compositions of North Pacific deep water [42]. The εNd value of −2.3 is found in the sample with the maximum amount of allothigenous contamination, which is similar to previous estimates in the Detroit Guyot (−2.2 ± 0.1) [28]. The minimum value of εNd (−4.4) is found in the ferromanganese crust of the Hanzei Guyot, where Al and Si inputs are limited. This value of εNd (−4.4) can be correlated to values of the Miocene deep water in the northernmost Pacific [43].

3.2. Sr and Nd in Mineral Fractions

Sr and Nd isotopic compositions in mineral fractions are shown in Figure 5, and the difference between various fractions is evident. For sample DR65-6/1, the 87Sr/86Sr ratio in loosely bound (I), Mn oxide (II), and hydrous Fe oxide (III) are similar, i.e., 0.709182, 0.709188, and 0.709083, respectively, while the 87Sr/86Sr ratio in residual (IV) is different to others, that is, 0.706693. The difference between the four fractions is consistent with previous studies [44], confirming an exchange and equilibration of strontium isotopic composition in the marine ferromanganese deposits [45]. In contrast, εNd changes have a large variance among various fractions. The change pattern of the 87Sr/86Sr ratio and εNd values in samples DR65-6/2, DR70-90/1, DR70-90/2, and DR59-11/2 is similar to that of sample DR65-6/1 (Table 3). However, the 87Sr/86Sr ratio in samples DR59-11/1 and DR23-5 displays a large variance among various mineral fractions: 87Sr/86Sr ratios in loosely bound (I) and Mn oxide (II) are similar, while the 87Sr/86Sr ratios of hydrous Fe oxide (III) and silicate (IV) are significantly low (Figure 5e,g).

4. Discussion

Strontium isotopic composition is a valuable tool for age determination of deep-sea deposits, named as the Sr isotope stratigraphy, e.g., [45,46]. Our study has found that 87Sr/86Sr ratios of chemogenic fractions (I–III) are similar in different samples, against with that 87Sr/86Sr ratio in the samples with different ages should be distinct [44]. Thus, our 87Sr/86Sr results confirm a previous suggestion that the exchange and equilibration of strontium isotopic composition in the marine ferromanganese deposits may result in a failure in the Sr isotope stratigraphy [45].
Moreover, mineral fractions are known to exhibit different patterns of chemical elements in ferromanganese deposits [36,40], including REEs [23,25,47,48,49], which suggests that all chemogenic fractions record isotopic equilibrium [26,50]. In our study, similar εNd values in samples DR23-5 and DR70-9/1 support this inference in surficial layers. A similar result is also observed in sample DR70-9/2, implying a unifying mechanism for the precipitation of the neodymium isotopic compositions over the depositing period.
However, it is found that for the samples taken from the surface layers (0–2 mm) of the Detroit Guyot (DR65-6/1) and the Stalemate FZ (DR59-11/1), the εNd values in the Fe oxide fraction are persistently lower by 1.2–1.7 epsilon units, compared to the Mn oxide fraction. This discrepancy suggests that the isotopic equilibrium may have been disrupted in these samples.
During warm periods, the melting of glaciers could significantly increase detrital inputs, such as eolian dust, river sand, and glacial rubble, resulting in a more negative εNd [20]. In addition, chemical weathering was induced during warm periods, leading to an increase in dissolved elements [51], which also contributes to a local negative in εNd values. Thawing waters are found to be enriched with carbon and phosphate ions (PO4)3− due to excessive productivity [52]. The increased supply of nutrient-rich freshwater from ice melt waters may induce the development of highly productive zones, reorganizing the distribution and species of microfauna, primarily diatoms and radiolarians [53,54,55]. The effect was evident during the Bølling–Allerød warming period (14,690–12,890 ka) in the Underwater Shirshov Ridge (the Bering Sea) and the Kamchatka Peninsula [55], and thus might be similar during the depositional period of the studied crusts.
It has been demonstrated that Nd tends to change with phosphate ions [56,57], and with phosphorus-associating Fe oxides [36,40,58]. Moreover, REEs in a water column gradually increase from the surface to the bottom, which is similar to the characteristics of nutrients such as phosphate. REEs can be enriched by coprecipitation with Fe-Mn oxide and phosphate, which is higher in the latter [27].
Phosphate ion acts as a complex-forming medium which increases in river, lake, and subsurface waters [59,60]. Melt waters lead to a decrease in dissolved REEs [59], indicating their complexation with phosphate ions. Thawing waters carrying REE phosphates with low εNd values may thus contribute to crust formation. Consequently, the positively charged Fe oxide fraction (III) not only sorbs carbonate complex (Nd(CO3)2−), which is the main form of Nd in seawater [61], but also phosphate complexes of Nd in the form of NdPO40. Moreover, Fourier transform infrared spectroscopy studies have shown that phosphorus in non-phosphated layers of ferromanganese crusts is mainly found in the form of phosphate ions (PO43−) [62]. Manganese oxides have a negative surface charge (fraction II) and preferentially sequester the monocarbonate form of neodymium (NdCO3+). The revealed influence of meltwater with a more negative εNd value on the formation of the isotopic composition of seawater in the northern Pacific confirms that the isotopic composition of seawater is mainly determined by terrigenous inputs [27,63].
Additionally, the percentage of neodymium bound to hydrous Fe oxides in samples with decreased εNd values is high (Figure 6). This REEs distribution between Mn and Fe oxides is attributed to the influence of hydrothermal matter and has been observed in the crusts in a mixed hydrogenous–hydrothermal genesis. In hydrogenetic deposits, similar REEs between these two fractions were observed [25]. In our case, the high REE content in the Fe oxide fraction relative to the Mn fraction suggests additional sorption of REE phosphate complexes in ferrous oxyhydroxides.
Furthermore, we observed a linear relationship between εNd values and 87Sr/86Sr ratios (Figure 7). This indicates a single source of detrital materials with similar initial isotope-geochemical characteristics during the depositional period.
Terrigenous matters in these crusts in our study are primarily delivered through the Strait of Kamchatka. Over the past 40 Myr, the Meiji Drift has formed in the southern tip of this strait, situated between the Emperor Ridge and the Aleutian Island Arc [31]. The main sediment sources in this area are from the Yukon, Kuskokwim, and Anadyr Rivers, as well as rivers from Kamchatka flowing into the Bering Sea [64]. The 87Sr/86Sr ratio and εNd values of these rocks vary considerably, ranging from 0.703 to 0.709 and from −10.1 to +9, respectively [20,65]. The 87Sr/86Sr ratio in the residual fraction of the studied samples varies from 0.705 to 0.706 (Table 3), generally agreeing with the average value of weathered rocks in the Bering Sea pool. Aeolian material is not a significant proportion [28], because the rates of dust deposition are low [66], only about an order lower than the one near the Meiji Drift [31].
Fine sediments in the Meiji Drift (ODP Hole 884) reveals that the rocks are dated to 40–60 Ma, with εNd values of −1 to +2 during glacial periods, while during interglacial periods, younger rocks (2–15 Ma) have much higher εNd values, from +5 to +9 [64]. Therefore, an increase in εNd values in the silicate fraction of the studied crusts in the northernmost Pacific may indicate a higher concentration of eroded materials from young island arc rocks during warming periods. An increase in the supply of drop stones during the warming period was detected in the upper part of the DR65-6 sample during elemental scanning, expressed in a high content of Si and Al (Figure 8, [67]).

5. Conclusions

We studied the isotopic composition of neodymium and strontium in four mineral fractions of the hydrogenous ferromanganese crusts of the northernmost Pacific in this work.
The 87Sr/86Sr ratios of chemogenic fractions (I, II, III) are similar (0.70913 ± 0.00010), close to the ratio in contemporary ocean water (0.70917). This supports the assumption that the exchange and mixing of the strontium isotopic composition takes place between seawater and the crust. Therefore, the data obtained from the ferromanganese crusts cannot be used for the Sr isotopic stratigraphy.
The decreased εNd value in the ferrous (III) fraction seems to be related to the presence of REE phosphate complexes in seawater. The increase in those complexes is a consequence of melt waters during warming periods, which have a more negative εNd value.
Our studies show that the carbonate REE complexes are not the dominant form, which leads to εNd differences in the manganese and ferrous fractions of hydrogenous ferromanganese crusts. A decrease in the εNd value in the ferrous fraction relative to the manganese fraction may indicate a local increase in surface water bioproductivity. Moreover, our data show that the increased REE in the ferrous fraction does not reflect the influence of hydrothermal materials, as shown for the ferromanganese deposits in the mid-ocean ridges in the Indian Ocean [25].
Based on isotopic (Sr, Nd) characteristics, the detrital matters in ferromanganese crusts has a common source with the Meiji Drift sediments.

Author Contributions

Conceptualization, P.M., I.V. and L.Y.; methodology, I.V. and N.S.; software, P.M., N.S. and V.P.; formal analysis, I.V. and N.S.; investigation, P.M.; resources, P.M. and V.P.; data curation, I.V.; writing—original draft preparation, P.M., I.V. and L.Y.; writing—review and editing, P.M. and L.Y.; visualization, P.M. and I.V.; supervision, P.M.; project administration, P.M.; funding acquisition, P.M. and V.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research was undertaken thanks to Grant No. 22-27-00079 from the Russian Science Foundation, https://rscf.ru/en/project/22-27-00079/ (accessed on 21 June 2022).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

All data have been provided in the paper.

Acknowledgments

The authors are grateful to M.V. Portnyagin and D.P. Saveliev for donating ferromanganese crusts for the study, which were dredged during the scientific expedition of the marine research ship “Sonne” (249th cruise, 2016) of the BERING project, the expedition having been sponsored by the German Ministry of Education and Research.

Conflicts of Interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as potential conflicts of interest. Any use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by the authors or their affiliated institutions.

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Figure 1. Location of the study area and crust sites. (a) The Hanzei and Detroit Guyots in the Emperor Ridge; (b) The Rat and Stalemate Fracture Zones.
Figure 1. Location of the study area and crust sites. (a) The Hanzei and Detroit Guyots in the Emperor Ridge; (b) The Rat and Stalemate Fracture Zones.
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Figure 2. The studied sections of ferromanganese crust in this work. (a) Fe-Mn crust from the Detrioit Guyot; (b) Fe-Mn crust from the Hanzei Guyot; (c) Fe-Mn crust from the Stalemate FZ; (d) Fe-Mn crust from the Rat FZ.
Figure 2. The studied sections of ferromanganese crust in this work. (a) Fe-Mn crust from the Detrioit Guyot; (b) Fe-Mn crust from the Hanzei Guyot; (c) Fe-Mn crust from the Stalemate FZ; (d) Fe-Mn crust from the Rat FZ.
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Figure 3. Ternary diagram of Fe, Mn, and (Co+Cu+Ni) × 10, following [6]. The yellow-shaded area indicates the main influence of hydrothermal (Ht) processes; Hg, hydrogenetic; Ed, early diagenetic.
Figure 3. Ternary diagram of Fe, Mn, and (Co+Cu+Ni) × 10, following [6]. The yellow-shaded area indicates the main influence of hydrothermal (Ht) processes; Hg, hydrogenetic; Ed, early diagenetic.
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Figure 4. Shale-normalized REE distribution patterns of ferromanganese crusts (a) and sample location in graphs of (b) Ce/Ce* ratio vs. Nd concentration and (c) Ce/Ce* ratio vs. Ysn/Hosn ratio.
Figure 4. Shale-normalized REE distribution patterns of ferromanganese crusts (a) and sample location in graphs of (b) Ce/Ce* ratio vs. Nd concentration and (c) Ce/Ce* ratio vs. Ysn/Hosn ratio.
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Figure 5. Sr and Nd isotopic compositions in mineral fractions of the studied crusts. (a,b) Fe-Mn crust from the Detrioit Guyot; (c,d) Fe-Mn crust from the Hanzei Guyot; (e,f) Fe-Mn crust from the Stalemate FZ; (g) Fe-Mn crust from the Rat FZ.
Figure 5. Sr and Nd isotopic compositions in mineral fractions of the studied crusts. (a,b) Fe-Mn crust from the Detrioit Guyot; (c,d) Fe-Mn crust from the Hanzei Guyot; (e,f) Fe-Mn crust from the Stalemate FZ; (g) Fe-Mn crust from the Rat FZ.
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Figure 6. Histograms of εNd value in different mineral fractions. 1—loosely bound; 2—Mn oxides; 3—hydrous Fe oxides; 4—residual.
Figure 6. Histograms of εNd value in different mineral fractions. 1—loosely bound; 2—Mn oxides; 3—hydrous Fe oxides; 4—residual.
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Figure 7. Scatter plot of εNd value vs. 87Sr/86Sr ratio in residual fraction of ferromanganese crusts.
Figure 7. Scatter plot of εNd value vs. 87Sr/86Sr ratio in residual fraction of ferromanganese crusts.
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Figure 8. Element distribution of the studied part of the DR65-6 sample. Red frame is studied area.
Figure 8. Element distribution of the studied part of the DR65-6 sample. Red frame is studied area.
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Table 1. The information on the studied crusts.
Table 1. The information on the studied crusts.
No.Sampling PositionLatitude, NLongitude, WWater Depth, mStructureMinerals (a)
Fracture Zones
DR23-50–2 mm48°44′17″177°30′14″5088–4510RatVernadite,
10 Å Manganate
DR59-11/10–2 mm51°1′26″172°1′19″4274–3814StalemateQuartz, Plagioclase, Vernadite (?)
DR59-11/231–36 mmVernadite
Emperor Guyots
DR65-6/10–2 mm50°31′59″167°28′59″3313–2897DetroitVernadite
DR65-6/220–25 mmVernadite
DR70-9/10–2 mm50°1′1″167°30′32″3685–3278HanzeiVernadite
DR70-9/260–65 mmVernadite
Note: (a) Mineral data were from [36] (?)—probably.
Table 2. Chemical composition of bulk samples of the studied crusts.
Table 2. Chemical composition of bulk samples of the studied crusts.
ElementDR65-6/1DR65-6/2DR70-9/1DR70-9/2DR23-5DR59-11/1DR59-11/2
Mn (%)10.215.010.321.815.84.0616.2
Fe (%)20.222.521.221.511.816.220.0
Ca (%)1.701.851.772.152.232.071.84
Si (%)14.39.8113.65.3215.521.510.8
Al (%)2.951.872.820.873.824.632.02
Co (ppm)119812911278249011725001176
Ni (ppm)7441582799325436072261297
Cu (ppm)35147249811092596284637
Sr (ppm)10751334108417078336591200
Y (ppm)15221315422590.167.2196
La (ppm)237347249408132125317
Ce (ppm)78011318901841958397930
Pr (ppm)55.077.059.911138.031.978.4
Nd (ppm)224315240400149129315
Sm (ppm)52.371.055.093.939.129.974.7
Eu (ppm)13.218.012.620.99.587.3418.5
Gd (ppm)58.278.054.388.738.130.179.3
Tb (ppm)8.1211.58.3314.05.834.3411.6
Dy (ppm)44.362.844.873.130.822.662.3
Ho (ppm)8.1411.88.2513.55.353.9511.5
Er (ppm)22.332.522.236.914.710.531.0
Tm (ppm)3.074.473.065.272.111.424.28
Yb (ppm)19.428.619.432.713.09.2527.1
Lu (ppm)2.824.092.814.791.871.323.90
∑REE (ppm)152921931670314714398041965
Ce/Ce*1.571.591.681.983.101.441.36
Eu/Eu*1.111.131.081.081.161.151.13
εNd−3.3 ± 0.1−3.2 ± 0.1−3.3 ± 0.1−4.4 ± 0.1−3.2 ± 0.2−2.3 ± 0.2−3.3 ± 0.1
87Sr/86Sr0.708780 ± 0.0000060.709110 ± 0.0000040.709047 ± 0.0000070.709141 ± 0.0000080.708563 ± 0.0000100.707973 ± 0.0000050.709021 ± 0.000010
Note: Element concentration, εNd value and 87Sr/86Sr ratio data were from [9,36].
Table 3. εNd and 87Sr/86Sr ratio in mineral fractions.
Table 3. εNd and 87Sr/86Sr ratio in mineral fractions.
DR65-6/1DR65-6/2
(a)IIIIIIIVIIIIIIIV
εNd−3.0−3.7−4.8−3.6−3.2−3.2−3.3−2.2
±σ0.20.30.40.10.10.10.10.2
87Sr/86Sr0.7091820.7091880.7090830.7066930.7092040.7091730.7088910.705495
±σ0.0000060.0000070.0000090.0000120.0000110.0000060.0000080.000007
DR70-9/1DR70-9/2
(a)IIIIIIIVIIIIIIIV
εNd−3.6−3.8−3.0−3.7−4.2−4.2−4.5−4.1
±σ0.10.20.30.10.10.10.30.1
87Sr/86Sr0.7091960.7091860.7091670.7061060.7091830.7091880.7089610.706727
±σ0.0000090.0000070.0000080.0000060.0000060.0000100.0000120.000017
DR59-11/1DR59-11/2
(a)IIIIIIIVIIIIIIIV
εNd−4.4−3.0−4.7−1.8−3.0−3.4−1.9−2.9
±σ0.30.20.50.10.20.21.50.3
87Sr/86Sr0.7091840.7091970.7089080.7048980.7092100.7091610.7091150.705741
±σ0.0000070.0000080.0000180.0000080.0000120.0000190.0000030.000009
DR23-5
(a)IIIIIIIV
εNd−3.6−3.4−3.4−3.0
±σ0.40.20.30.3
87Sr/86Sr0.7091950.7091780.7089780.706433
±σ0.0000060.0000080.0000130.000005
Note: (a) loosely bound (I), Mn oxide (II), Fe oxide (III), and residual (IV).
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Mikhailik, P.; Vishnevskaya, I.; Yi, L.; Soloshenko, N.; Pellinen, V. Sr and Nd Isotopes in Mineral Fractions of Ferromanganese Crusts from the Northernmost Pacific. J. Mar. Sci. Eng. 2023, 11, 1920. https://doi.org/10.3390/jmse11101920

AMA Style

Mikhailik P, Vishnevskaya I, Yi L, Soloshenko N, Pellinen V. Sr and Nd Isotopes in Mineral Fractions of Ferromanganese Crusts from the Northernmost Pacific. Journal of Marine Science and Engineering. 2023; 11(10):1920. https://doi.org/10.3390/jmse11101920

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Mikhailik, Pavel, Irina Vishnevskaya, Liang Yi, Natalia Soloshenko, and Vadim Pellinen. 2023. "Sr and Nd Isotopes in Mineral Fractions of Ferromanganese Crusts from the Northernmost Pacific" Journal of Marine Science and Engineering 11, no. 10: 1920. https://doi.org/10.3390/jmse11101920

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