ISSN 0016-7029, Geochemistry International, 2017, Vol. 55, No. 2, pp. 218–224. © Pleiades Publishing, Ltd., 2017. Original Russian Text © E.D. Berezhnaya, A.V. Dubinin, 2017, published in Geokhimiya, 2017, No. 2, pp. 186–193.
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Determination of the Platinum-Group Elements and Gold in Ferromanganese Nodule Reference Material NOD-A-1 E. D. Berezhnaya* and A. V. Dubinin Shirshov Institute of Oceanology, Russian Academy of Sciences, Nakhimovskii prosp. 36, Moscow, 117997 Russia *e-mail:
[email protected] Received December 28, 2015; accepted February 08, 2016
Abstract—The concentrations of Ru, Pd, Ir, Pt, and Au were determined in a ferromanganese nodule reference sample NOD-A-1 by inductively coupled plasma mass-spectrometry. Sample preparation procedures include acid digestion and anion exchange preconcentration. Standard addition method was used to eliminate losses of the analyte during the chromatographic separation. The results are in agreement with previously published data. The low level of intermediate precision for Au between different subsamples of the same sample probably originates from the heterogeneous distribution of Au in ferromanganese nodules. The accumulation of PGE in ferromanganese nodules was studied using international reference samples. Keywords: PGE, gold, ferromanganese nodule reference samples, ICP-MS DOI: 10.1134/S0016702917010037
INTRODUCTION The distribution of the platinum-group element (PGE) and gold (Au) is important for understanding the genesis and economic potential of marine ferromanganese sediments (crusts and nodules). Determination of precious metals in ferromanganese deposits creates considerable difficulties because of the low concentrations of PGE and Au in oceanic sediments and generally involves preconcentration of elements to minimize matrix interference effects. As a result, ferromanganese nodules and crusts reference samples are not currently available with certified values for all the PGE and Au. For national reference samples SDO 4-7 (or OOPE 601-604), certified values for Pt and Au (and Pd for SDO-6) and recommended values for Pd and Rh were published by Berkovits et al. (1991). Determinations of some PGE and Au were reported for JMn-1 (GSJ, Japan) and GSPN-2, 3 (CAGS, China) reference samples (Terashima et al., 1995; Plessen and Erzinger, 1998; Imai et al., 1999; Li et al., 1996; Balaram et al., 2006). More recently, cobalt-rich ferromanganese crust reference samples MCPt-1 and 2 were prepared by NRCG (China) and VNIIOkeangeologiya (Russia) and certified for Pt by Wang et al. (2011); however, Au data were not reported. The most complete set of data is available for ferromanganese nodule reference samples USGS NOD-A-1 and NOD-P-1 (U.S. Geological Survey, USA). The determinations performed using different analytical methods showed an overall lack of agreement. A study of PGE and Au geochemistry of oceanic ferromanganese crusts requires use of reference materials having a
definite recognized composition for assessing the accuracy of the results obtained. The goal of this study was to determine the concentrations of PGE (Ru, Pd, Ir, and Pt) and Au in a reference sample NOD-A-1. Chemical procedure for analysis of PGE and Au is generally a two-step process: digestion of a sample and preconcentration of the analyzed elements. The sample is dissolved using a number of techniques, including fire-assay (Kolesov and Sapozhnikov; 2003, Balaram et al., 2006; Banakar et al., 2007), high temperature/pressure Carius tube digestion (Pearson and Woodland, 2000; Muller and Heuman, 2000; Meisel et al., 2001), sodium peroxide fusion (Enzweiller et al., 1995; Totland et al., 1995), and acid microwave digestion (Totland et al., 1995, Kubrakova et al., 1996, Palesskii et al., 2009). Because of the absence of lowsolubility mineral phases (zircons or Cr-spinels) in ferromanganese nodules and crusts, the acid digestion technique can be expected to ensure complete digestion of the sample and recovery of elements to solution. Preconcentration of precious metals is performed using extraction, sorption, precipitation, coprecipitation, and fire-assay techniques (Zolotov et al., 2003; Mokhodoeva et al., 2007). Anion exchange chromatography was utilized in this study for preconcentration of PGE and Au and removal of matrix elements to avoid interference effects and to prepare the elements for further ICP—MS analysis. Another advantage of this technique is that it requires only a small amount of resin and mineral acids as eluents. Since this procedure rarely attains 100% PGE yield,
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many researchers use combined chromatographic separation and isotope dilution techniques for PGE analysis (Colodner et al., 1993; Pearson and Woodland, 2000; Jensen et al., 2003; Baker and Krogh-Jensen, 2004). The determination of PGE and Au in ferromanganese nodule reference samples was performed by adopting the methodology of Colodner et al. (1993) and Pearson and Woodland (2000), which was added with the procedures that allow the simultaneous determination of Au and PGE. MATERIALS AND METHODS Nodule sample NOD-A-1 was collected from the Atlantic Ocean (31°02′ N, 78°22′ W, water depth 788 m) (Flanagan and Gottfried, 1980). The sample was digested using sub-boiling distilled, high-purity concentrated nitric and hydrochloric acids and ultra-pure hydrofluoric acid (TraceSelect, Fluka). All eluents and solutions were prepared by dilution of these acids with deionized water (18.2 MOhm/cm, Millipore). Standard solutions in the concentration range of 10 μg/mL for Au, Ir, Pd, and Ru, and 50 μg/mL for Pt manufactured by High-Purity Standards, USA were used. Preconcentration of the precious metals was conducted by sorption onto anion-exchange resin (Dowex-1 × 8, Sigma Aldrich). A reference sample was dried at 105–110°С. About 0.4–0.8 g of the sample was placed in the Savillex PFA vial (USA), treated with a 3 : 2 : 1 mixture of HNO3 : HCl : HF (6–12 mL), heated at 95–100°С for 8 h and then evaporated and treated sequentially with 6–12 mL of aqua regia and 3–6 mL of hydrochloric acid. Some sample aliquots were digested by microwave (MCS-2, Berghof, Germany) to check for the completeness of the dissolution. The aliquot was treated repeatedly with a 3 : 1 mixture of aqua regia and hydrofluoric acid (15 mL) in closed Teflon breakers at 150°С for 20 min, 180°С for 25 min, and 200°С for 30 min. The solution was evaporated at 80°С to incipient dryness, then treated with concentrated hydrochloric acid and evaporated again. The resulting residue was dissolved in 5 mL of 0.5 N HCl and divided into four aliquots. Three aliquots were spiked with PGE and Au standard solutions (1; 2; 3 ng of Ru, Pd, Ir, and Au, and 5; 10; 15 ng of Pt, respectively, calculated to absolute weights). The spike solution was prepared so that spiking could be optimized for samples of different weight and required concentration. Blank determination was prepared using the same procedure as in the unspiked sample. Thus, one blank, one unspiked sample and three spiked samples were included in each batch. Preconcentration was performed simultaneously using five separate columns. A quartz column (d = 4.5 mm) was loaded with quartz wool and 0.5 mL of ion exchange resin. PGE and Au were absorbed from chlorinated hydrochloric acid solutions (0.4 N HCl + Cl2) because the presence of chlorine ensures Ir retention on anion resin (Pearson and Woodland, 2000). Once loaded, the resin was GEOCHEMISTRY INTERNATIONAL
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Table 1. Spike isotopes used for the determination of PGE and Au and major interferences Isotope 101
Ru
105
Pd
Interfering ions 64 88
ZnCl, 66ZnCl
SrOH, 89YO, 65CuAr
193Ir
177HfO
194
Pt
178
195
Pt
179
197Au
181TaO
HfO HfO
cleaned additionally with 0.4 N HCl + Cl2 to ensure efficient removal of matrix elements and metals that can cause interference (Hf, Zr, Cu, and Ni). After this step, the anion resin was washed with 1 N HNO3 + Cl2 to remove Zn and Pb. The platinum-group elements and gold were eluted with 20 mL of hot 14N HNO3, additional heating was used to maintain the eluent temperature in the column. The effluent was evaporated at 80°С on an infrared plate and diluted before the analysis with 3 mL of 0.5 N HCl with the addition of an In-Re internal standard (C(In) ≈ C(Re) ≈ 10 ng/g in the final solution). PGE and Au concentrations were determined with an Agilent 7500 quadrupole mass spectrometer using standard addition and external calibration. Blank concentrations of PGE and Au were determined using standard solutions. Indium and rhenium were used as internal standards for the light PGE and heavy PGE and Au, respectively. Spike isotopes and potential interfering ions are shown in Table 1. The values of the interferences was assessed from the intensity of signals from standards for the respective elements (Zn, Cu, Hf, and Ta). The influence of argide and chloride interferences was not significant. The contribution of oxide interferences was below the analytical error and did not require mathematical correction. The concentrations of PGE and Au in NOD-A-1 samples were quantified by the standard addition method. The calibration curve was obtained by plotting the analytical signal on the y-axis and the concentration of the added element on the x-axis. The coefficients (a, b) were calculated by the least squares method. The element concentration in a sample was calculated by extrapolating it to the point on the x-axis at which y = 0. Figure 1 shows the calibration curves for Ru, Pd, Ir, Pt, and Au. In most samples, calibration curves were characterized by a high correlation coefficient (R2 > 0.99). If R2 < 0.97, the element concentration in this sample was not calculated. 2017
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I, cps 6000
I, cps 8000
Ru
I, cps 30000
Pd
Ir
6000
5000
20000 4000
4000 3000
Y = 5451X + 10971 R2 = 0.99
2000 0
0.4
I, cps 150000
0.8
10000
2000
Y = 14341X + 2407 R2 = 0.98
0
1.2 C, ng/g
0
0.4
I, cps 9000
Pt
120000
0.8
1.2 C, ng/g
Y = 53699X + 19350 R2 = 1
0 0
0.4
0.8
1.2 C, ng/g
Au
6000
90000
3000 Y = 7288X + 66846 R2 = 1
60000 0
2
4
Y = 35563X + 249 R2 = 0.98
0
6 8 C, ng/g
0
0.4
0.8
1.2 C, ng/g
Fig. 1. Calibration curves for determining the concentrations of Ru, Pd, Ir, Pt, and Au by standard addition. The analyte concentration (ng/g) is plotted on the x-axis, the instrument response is plotted on the y-axis (I, cps).
RESULTS AND DISCUSSION Table 2 shows the mean (n = 8) concentrations of PGE and Au obtained in procedural blanks. The detection limits were reported as an average concentration of procedure blank plus its three standard deviations on a dry-weight basis for 200 mg aliquot of each sample. The detection limits obtained were sufficiently low to permit a reliable determination of PGE and Au in ferromanganese deposits. The variation in PGE concentrations in samples digested using different digestion techniques was within overall uncertainty. This allowed us to combine the results and suggest an almost complete digestion of samples for both methods. PGE yields through anion exchange columns were 90–95% yield for Ir, 95–100% for Pt and Au and only ~34% for Ru. The concentrations of Ru, Pd, Ir, Pt, and Au in reference sample NOD-A-1 together with earlier reported values are shown in Table 3. Sample that have Table 2. Average blank values (n = 8) and detection limits achieved (Cmin) Content Blank value, ng Cmin, ng/g
Ru 0.15 1.0
Pd
Ir
Pt
Au
0.011 0.006 0.010 0.018 0.08 0.10 0.14 0.17
lower correlation coefficients obtained by the standard addition method were excluded from the calculation of mean values. In particular, it took some time to optimize the spike composition for analysis of Pt. It is possible that the considerable scatter in the published data originates from low levels of some PGE or the use of different sample preparation and detection methods. For example, the simultaneous determination of PGE and Au was performed utilizing a combined NiS fire-assay—mass spectrometry (Balaram et al., 2006), while the methodology used by Axelsson et al. (2002) did not involve preconcentration step. Chowdhury and Paul (1983) used fire-assay spectrographic method for the determination of Pt. Aruscavage et al. (1984) used flameless atomic absorption to analyze Pt and Pd. The Pt values obtained in this study for NOD-A-1 coincide well with previously reported data. The Ru and Ir concentrations agree within error with those obtained by Balaram et al. (2006). The Pd concentrations show good agreement with the data of Aruscavage et al. (1984). Gold concentrations in NOD-A-1 obtained in this study vary from below detection limits in six out of eight samples (less than 0.2 ng/g) to 8 and 11 ng/g dry weight in the remaining two samples. These variations probably originate from the heterogeneous distribution of Au in ferromanganese nodules and much larger
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Table 3. Average concentrations of PGE and Au (ng/g) determined by standard addition method compared to previously published data. The number of determinations is shown in parentheses Element
Cav ± σ, ng/g
Balaram et al., 2006
Ru
33 ± 3 (8)
30 ± 3
Pd Ir Pt Au
2.7 ± 0.4 (8) 5.5 ± 1.1 (7) 482 ± 25 (5) −
9±2 5±2 450 ± 25 9±3
Axelsson et al., 2002 22 Pt @ Pd. Palladium is accumulated in ferromanganese deposits in lowest degree. The Pt/Pd ratio in seawater is 1−4.5 (Ravizza, 2001; Goldberg and Koide, 1990), whereas analysis of a ferromanganese nodule reference sample NOD-A-1 yielded a Pt/Pd ratio of up to 170. A variety of mechanisms were proposed explain this preferential uptake of Pt over Pd in ferromanganese nodules and crusts, including adsorption of Pt(OH) 02 onto the surface of Fe–Mn oxydroxide minerals (Stueben et al., 1999), reduction of Pt(II) to the elemental state and coprecipitation with MnO2 (Halbach et al., 1989), oxidative sorption Pt(II) → Pt(IV) onto Fe and Mn oxyhydroxides (Hodge et al., 1985; Koide et al., 1986; Goldberg and Koide, 1990; Baturin et al., 1991; Koschinsky et al., 2005; Hein et al., 2005; Banakar et al., 2007; Maeno et al., 2015), formation of organometallic complexes of Pt (Terashima et al., 2002; Kubrakova et al., 2010). Accumulation of Pt, Ir, and Ru in ferromanganese nodules may take place by the same mechanism. The GEOCHEMISTRY INTERNATIONAL
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Pt/Ru ratio in ferromanganese deposits is 7.4–24 (Koide et al., 1986), which is close to that of seawater (≈25). The Pt/Ir broadly similar to that of seawater was found only in hydrogenetic ferromanganese deposits (Goldberg et al., 1986). In this study, we considered the PGE data for international ferromanganese crust/nodule reference materials given in GeoRem database (http://georem.mpch-mainz.gwdg.de) and compared their Pt/Ir and Pt/Ru ratios (Fig. 2). Both Ir and Ru correlate strongly with Pt concentrations. The main trend is defined by high PGE concentrations in the Co-rich ferromanganese crust MCPt-2. Figure 3 shows a relationship between Pt and Co contents in international ferromanganese nodule reference materials. The observed correlation indicate that Ru, Ir, and Pt preferentially precipitate in the hydrogenetic component of ferromanganese deposits (Baturin et al., 1991) and follow the trend typical of the multivalent elements (Co and Ce). They display their highest concentrations in hydrogenetic ferromanganese crusts and nodules, lower concentrations in diagenetic nodules, and the lowest concentrations in hydrothermal Mn and Fe crusts (Stueben et al., 1999). The ferromanganese nodule NOD-A-1 is hydrogenetic, as indicated by its low Mn/Fe ratio (1.7) (Flanagan and Gottfried, 1980) and a strong positive Ce anomaly calculated as Ce an = Ce/CeNASC/(1/2La/LaNASC + 1/2Nd/NdNASC) = 3.0 (Dulski, 2001). If we assume that seawater alone is the main source of PGE in fer2017
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Ru, ng/g 100
Ir, ng/g 40
80 30 60 20 NOD-A-1 NOD-P-1 JMn-1 GSPN-2 GSPN-3 MCPt-1 MCPt-2
40 R = 1.00
R = 0.99 10
20
0
0 400
0
800
1200
1600 Pt, ng/g
0
400
800
1200
1600 Pt, ng/g
Fig. 2. Plots showing Pt/Ru and Pt/Ir concentration ratios of ferromanganese nodule/crust reference samples.
romanganese crusts then oxidative scavenging could be the most likely mechanism of PGE enrichment in marine sediments, which invokes adsorption of Pt, Ru, and Ir from seawater onto the surface of Fe and Mn oxyhydroxides and subsequent oxidation of Pt from +2 to +4 and Ru and Ir from +3 to +4 (Hein et al., 2005, Banakar et al., 2007). This mechanism is supported by sorption experiments with the Pt(II) species and model solutions consisting of pyrolusite and Pt, ng/g 1600
1200
OOPE601 OOPE602 OOPE603 OOPE604 NOD-A-1 NOD-P-1 JMn-1 GSPN-2 GSPN-3 MCPt-1 MCPt-2
R = 0.95
800
400
0
0.4
0.8
1.2
1.6 Co, %
Fig. 3. Relationship between Co and Pt concentrations in international ferromanganese nodule/crust reference samples.
Fe-bearing δ-MnO2, which showed that up to 70% of Pt was adsorbed as Pt(IV) on the sorbent phase (Koschinsky et al., 2005). Ir has a shorter residence time in seawater than Pt and is preferably bound to iron and manganese oxyhydroxides. This can explain the higher Ir/Pt ratios in the hydrogenetic ferromanganese crusts. However, the sorption of Ru, Ir, and Pt in the form of complex compounds in the oxidation state of 4+ onto iron and manganese oxyhydroxides cannot be ruled out. It is assumed that Pt is present in seawater as Pt(II) and Pt (IV) compounds, PtCl 24 − and PtCl5OH2– complexes (Cosden and Byrne, 2003), or even as divalent species (Pt(OH) 02 ) (Stueben et al., 1999). A recent work of Cobela-Garcia et al. (2013) showed that Pt(II) (as Pt(OH) 02 ) is oxidized in the presence of oxygen to Pt (IV) (Pt(Cl5OH–) in estuaries with an increase in salinity. Experimental results also confirmed the effective sorption of Pt(IV) onto freshly deposited oxyhydroxides (Kubrakova et al., 2010) and Ir(IV) onto the carbonate-free sediment fraction (Dai et al., 2000). The uptake of Pt, Ir, and Ru in ferromanganese deposits is likely to occur by a combination of several mechanisms, such oxidative and non-oxidative scavenging and coprecipitation. For example, accumulation of Rh in ferromanganese nodules, which has a 3+ oxidation state in seawater, can be explained by adsorption of Rh as an inner-sphere complex (Banakar et al., 2007). Palladium in seawater forms the stable complexes with chloride ions and organic ligands (Kump and Byrne, 1989; Terashima et al., 2002). Pd in ferromanganese crusts reflects in part the detrital fraction of the Fe—Mn crusts (Hein et al., 2005). In contrast to the PGE, the heterogeneous distribution of Au indicates an alternative mechanism by which it can
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be accumulated in marine sediments. For example, Baturin et al. (1984) demonstrated that Au is associated with a detrital component of Fe–Mn nodules. Ohashi et al. (2005a) suggested a mechanism by which Au(II) is reduced to Au(0) during adsorption onto δ-MnO2. CONCLUSIONS The concentrations of Ru, Pd, Ir, Pt, and Au in the Fe—Mn nodule reference sample NOD-A-1 were determined by inductively coupled plasma mass spectrometry after separation and preconcentration by anion exchange chromatography. The results on Ru, Pd, Ir, and Pt mass fractions are in agreement with previously published data. The detection limits obtained were 0.1 ng/g for Pd, Ir, and Pt, 0.2 ng/g for Au, and 1 ng/g for Ru. The methodology described here can be used for obtaining accurate and precise data on PGE and Au in ferromanganese nodules/crusts and pelagic sediments. ACKNOWLEDGMENTS This study was supported by the Russian Science Foundation (project no. 14-50-00095). REFERENCES Analytical Chemistry of Platinum Group, Ed. by Yu. A. Zlotova, G. M. Varshal, and V. M. Ivanova (URSS, Moscow, 2003) [in Russian]. P. J. Aruscavage, F. O. Simon, and R. Moore, “Flameless atomic absorption determination of platinum, palladium, and rhodium in geologic materials,” Geostand. Newsl. 8, 3–6 (1984). M. D. Axelsson, I. Rodushkin, J. Ingri, and B. Öhlander, “Multielemental analysis of Mn–Fe nodules by ICP-MS: optimisation of analytical method,” Analyst 127, 76–82 (2002). J. A. Baker and K. Krogh-Jensen, “Coupled 186Os-187Os enrichments in the Earth’s mantle core mantle interaction or recycling of ferromanganese crusts and nodules?” Earth Planet. Sci. Lett. 220, 277–286 (2004). V. Balaram, R. Mathur, V. K. Banakar, J. R. Hein, C. R. M. Rao, T. G. Rao, and B. Dasaram Determination of the platinum group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS. Indian J. Marine Sci. 35, 7–16 (2006). V. K. Banakar, J. R. Hein, R. P. Rajani, and A. R. Chodankar, “Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: sources and fractionation,” J. Earth System Sci. 116, 3–13 (2007). G. N. Baturin, E. I. Fisher, and V. L. Fisher, “Gold content in the oceanic ferromanganese nodules,” Dokl. Akad. Nauk SSSR 275 (2), 421–424 (1984). G. N. Baturin, L. V. Dmitriev, and A. N. Kurskii, “Noble metals in the ferromanganese crusts and nodules of the Atlantic Ocean,” Geokhimiya, No. 1, 142–148 (1991). GEOCHEMISTRY INTERNATIONAL
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GEOCHEMISTRY INTERNATIONAL
Translated by N. Kravets
Vol. 55
No. 2
2017
