In search of the lost zinc: A lesson from the Jabali (Yemen
Transcription
In search of the lost zinc: A lesson from the Jabali (Yemen
Journal of Geochemical Exploration 108 (2011) 209–219 Contents lists available at ScienceDirect Journal of Geochemical Exploration j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j g e o ex p In search of the lost zinc: A lesson from the Jabali (Yemen) nonsulfide zinc deposit N. Mondillo a, M. Boni a,⁎, G. Balassone a, B. Grist b a b Università di Napoli, Dipartimento Scienze della Terra, Via Mezzocannone 8, 80134 Napoli, Italy ZincOx Resources plc Knightway House Park Street Bagshot Surrey GU19 5AQ, United Kingdom a r t i c l e i n f o Article history: Received 13 December 2010 Accepted 24 February 2011 Available online 13 March 2011 Keywords: Jabali Zn-dolomite Mineralogy Geochemistry Evaluation Recovery a b s t r a c t The Jabali nonsulfide zinc deposit, located northeast of Sana'a (Yemen) contains a geological resource of 12.6 million tonnes of ore grading 8.9% zinc, 1.2% lead and 68 g/t silver, with a projected recovery of ca. 80% zinc. The primary sulfide deposit shows features of both Mississippi Valley and Carbonate Replacement types, and is believed to have been formed by circulating hydrothermal fluids, either associated with Mesozoic rifting, or generated from Tertiary igneous activity, developed in the area during the Red Sea crustal extension. An extension of this phenomenon should have also triggered the late uplift, which favored the oxidation of sulfides. Ore deposition has been accompanied by several dolomitization phases, some of which have been considered strictly hydrothermal. A complete quantitative (Rietveld) mineralogical and geochemical study of mineralized full-length core samples, carried out with the aim of possibly increasing zinc recovery, shows a discrepancy between the zinc grades recorded in the chemical assays, and those calculated from the sum of the ore minerals occurring in the same samples. The difference between the assayed and calculated zinc amounts in various parts of the deposit is due to the presence of Zn-rich dolomite phases (up to 20% Zn in the lattice), as well as of Mg-smithsonite (up to 12% Mg), both phases replacive of the earlier dolomites in the weathering environment. The Zn-enriched dolomite phases could be the “missing link” between pure dolomite and smithsonite. Zinc occurring in dolomite cannot be processed economically with today's methods. Analysis of the total zinc amount contained in Zn-dolomite, when compared with the zinc occurring in the processable ore minerals shows that there is a significant proportion of unrecoverable zinc. This explains why at Jabali the projected metallurgical recovery of around 80% is unlikely to be improved upon, due to the trapped zinc within the “supergene” dolomite phases. The extensive development of the Zn-dolomite bodies, which occur throughout the whole mining area, may be highly significant for the evaluation of nonsulfide zinc ores at Jabali and for the exploration philosophy of the region. The possible occurrence of Zn-dolomite has to be kept in mind when exploring for supergene Zn-nonsulfides in other mining districts where the ore is also dolomite-hosted, which may feature a significant nonrecoverable phase. © 2011 Elsevier B.V. All rights reserved. 1. Introduction “Zinc nonsulfides” is a very general term, which comprises a whole series of minerals (Boni, 2005; Hitzman et al., 2003; Large, 2001). However, the only ones considered so far of economic importance for zinc extraction are: the Zn-carbonates smithsonite and hydrozincite, the silicates hemimorphite and willemite, and the Zn-smectite (sauconite). Among silicates, zinc can be hosted also in other layered phases, as in the Zn-chlorite baileychlore (Blot et al., 1995; Rule and Radke, 1988), in the serpentines fraipontite and Zn-rich caryopilite or greenalite (Fransolet and Bourguignon, 1975; Guggenheim and Bailey, 1990) and in the hendricksite mica (Robert and Gaspérin, 1985). Variable amounts of zinc have been detected in Mn–Fe(hydr) ⁎ Corresponding author. Tel.: + 39 0812535068. E-mail addresses: nicolamondillo@libero.it (N. Mondillo), boni@unina.it (M. Boni), balasson@unina.it (G. Balassone), bgrist@zincox.com (B. Grist). 0375-6742/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.gexplo.2011.02.010 oxides (Boni et al., 2009; Hayes et al., 2000). However, the latter concentrations (with few exceptions) are relatively uncommon. The mineralogical association (franklinite, zincite and gahnite), occurring in the metamorphic high-temperature Franklin-Sterling Hill mine in North America (Johnson, 2001) is not very common either, being limited to a small group of deposits. Generally, nonsulfide zinc ores of both hypogene and supergene origin have been relatively poorly investigated (Hitzman et al., 2003). Consequently, the genetic understanding, regional knowledge, and the ability to explore these mineralogically and geochemically complex deposit types are still incomplete (Borg, 2010). However, with the development of solvent-extraction (SX), electrowinning (EW), and leach to chemical (LTC) processes there has been a renewed commercial (and scientific) interest for nonsulfide Zn mineralization throughout the world. Because even small differences in dissolution rates and in H2SO4 consumption (in the case of an acid leach) may have strong implications for the production strategies and 210 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Fig. 1. Geological sketch map of Yemen, with the location of the Zn–Pb–Ag Jabali nonsulfide deposit. metallurgical requirements, a thorough understanding of the mineralogy, but also of the petrographic associations is a “must” in exploration targeting and feasibility studies of nonsulfide deposits. Host rock composition also significantly influences the mineralogy (and therefore metallurgy) of nonsulfide ores. Those in limestone and dolomite tend to be dominated by smithsonite and hydrozincite, due to the interaction of low-pH Zn-rich fluids with host carbonates, whereas deposits in siliciclastic rocks tend to contain hemimorphiteand sauconite-bearing assemblages (Hitzman et al., 2003). However, even in the same category of host rocks, the mineralogy tends to be relatively simple (smithsonite, hemimorphite, and hydrozincite) in the oxidation products derived from low-temperature sulfide deposits. Most of the historical European Zn–Pb nonsulfide concentrations, the so-called “Calamine” (Boni and Large, 2003; Large, 2001), are carbonate-hosted, as well as other deposits of current economic importance throughout the world: Angouran (Boni et al., 2007), Accha (Boni et al., 2009) and Jabali (Al Ganad et al., 1994), which is the subject of this study. The Jabali zinc-lead-silver deposit is a dolomite-hosted mixed sulfide- and nonsulfide mineralization, currently under development by Jabal Salab Company (Yemen) Ltd., a joint venture between ZincOx Resources plc and a Yemeni company, Ansan Wikfs. The deposit Fig. 2. Representative results of the LTC — metallurgical test on 35 composite samples. The amount of zinc recovery vs. zinc grade has been plotted; the circles represent samples with Zn N5 wt.% and high recovery, rhombs indicate samples with Zn b5 wt.% and variable recovery (ZincOx Resources plc.). (Fig. 1) is located 100 km ENE of Sana'a, in a desert terrain, on the east side of the mountain range that runs along the length of the western border of the Arabian peninsula, at an altitude of 2000 m above sea level. In the Middle Ages (7th–9th century AD) this was considered one of the most important mining areas for silver in the Muslim world. The nonsulfide concentrations, derived from the supergene alteration of the primary sulfide deposit, with their 8.7 million tonnes of ore at an average grade of 9.2% zinc, are currently considered the major zinc resource of Yemen (Grist, 2006; Mineral Resources of Yemen, 2009; Watts, Griffis and McOuat Limited, 1993). After consideration of a number of mineral processing routes, a good recovery (80%) from the bulk ore was reached in metallurgical tests carried out on 35 composite nonsulfide samples with the LTC Fig. 3. Geological map of the Jabali mining site with the location of analyzed drillcores, and the future open pit area (modified from SRK Consultants, 2005). Description of the units is in Fig. 4. N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 211 mining industry, as recoveries are almost never 100%, but can often be improved by later work on recovery technique. In the case of Jabali however, the work shows that the current process is close to optimal and that further improvements to recovery are unlikely. We will briefly report on the causes of the above phenomenon in the Jabali deposit, which may be extended also to other dolomite-hosted nonsulfide concentrations (Boni et al., 2011). 2. Geological setting of the Jabali deposit Fig. 4. Schematic stratigraphic column of the Jabali area with the units established by Christmann et al., 1989 (modified). Unit 1 (7–20 m): sandstone and conglomerate, transgressive over the Late Proterozoic basement (unknown age); Unit 2 (30–35 m): gypsiferous mudstone overlain by dolomitized calcarenite, marl and nodular limestone (unknown age); Unit 3 (33–50 m): micritic and biomicritic limestone (Callovian) with nodular concretions and chert layers; Unit 4 (10–16 m): micritic limestone and finely bedded lagoonal/lacustrine dolomite (unknown age); Unit 5 (40–45 m): partly dolomitized bryozoan calcarenite (Late Oxfordian-Early Kimmeridgian), overlain by coral-bearing oolitic limestone. A local disconformity at the top of Unit 5; Unit 6 (45–100 m): greenish gypsiferous mudstone grading to micritic, ammonite-bearing limestone (Kimmeridgian) and marl with sandstone lenses; Unit 7 (60–90 m): massive bioclastic and biomicritic limestone, locally oolitic with coral bioherms (Kimmeridgian). The unit is dolomitized and affected by karstic erosion at the top; Unit 8 (0–30 m): black mudstone and argillite with gypsum crystals and dolomite intercalations, grading laterally to micritic ammonite-bearing limestone (Late Kimmeridgian–Tithonian); Unit 9 (N 120 m): biomicrite with oncolites and bio-oocalcarenite (Late Jurassic). (leach-to-chemical) method using ammonia-based solutions. It has proven impossible to raise the recovery above this level, especially in those samples bearing a low metal grade. Fig. 2 shows the most representative results of the LTC-recovery testwork, where the amount of zinc recovery is plotted against the zinc grade. The method selectively recovers the zinc contained in smithsonite and hydrozincite, and, when compared with the classical acid-leach, there is no interaction between the chemical solutions and the gangue minerals, which would cause a high acid consumption during metal extraction under an acid leach. It can be clearly seen that in the samples having a zinc ore grade higher than 5%, the recovery is very high (80% and above), whereas in the samples with ore grade below 5% Zn, the recovery is variable to very low. In order to investigate the possible cause of the remaining non-recoverable phase, it was necessary to carry out a wide mineralogical and geochemical study in the nonsulfide ore zone, to identify how the metal is trapped in this non-extractable phase. A key part of the original deposit evaluation by Jabal Salab was to apply the calculated recoveries when considering the recovered material that will be extracted from the reserve. This is normal in the Major extensional basins formed in Yemen during the Late Jurassic/ Early Cretaceous, linked to the separation of India/Madagascar from Afro-Arabia (Geological Survey and Minerals Exploration Board, 1994). The location and NW–SE orientation of these basins are controlled by the Precambrian structural grain of the Arabian shield (Fig. 1). During Triassic to middle Jurassic times, Yemen was part of the Afro-Arabian plate of western Gondwanaland. In the Toarcian–Bathonian western Yemen was a region of subsidence, in which continental deposits were accumulated. In the Bathonian, part of the marginal area between western and eastern Gondwanaland was subjected to a marine transgression leading to the deposition of the Amran Group. In the late Callovian, the sea transgressed, providing a passage between the Arabian and African Seas, including Somalia and Ethiopia. The sediments of the lower part of the Amran Group were deposited during the earlier part of the Marib-Al-Jawf basin development, prior to any significant rifting. The downwarping of the basin resulted in a deepening regime, which caused the deposition of thick carbonate sequences in a syn- to post-rift environment. Three facies associations occur in the middle-upper part of the Amran Group: (1) carbonate platform facies, (2) carbonate-marl facies, and (3) shallow water coral and stromatoporoid build-up facies (Al Thour, 1997). The Jurassic sediments are overlain by post-rift Cretaceous sandstone. The Cenozoic rift basins of Yemen are linked to the Oligocene/ Miocene rifting of the Gulf of Aden and of the Red Sea. They were filled with thick sedimentary successions displaying continental, evaporite, and shallow to deep marine facies, locally injected by alkali-basalt rift volcanic rocks (Geological Survey and Minerals Exploration Board, 1994). Lead and zinc ore deposits in Yemen occur in sequences consisting of Jurassic sediments accumulated in the major rift basins as Jabal Salab (Al Ganad et al., 1994; Christmann et al., 1989), Al Jabal AlAhmar, Dhi Bin etc., as well as in Palaeocene carbonates associated with the evolution of the same rifts (Fig. 3). Most of the metallic occurrences appear at the margins of the rifts or in rift-affected blocks (Mineral Resources of Yemen, 2009), and are mainly dolomite-hosted. At Jabali (Jabal Salab) the primary and secondary Zn–Pb ores are located on the southwestern flank of the NW-trending Sab'atayn Jurassic rift basin (Al Ganad et al., 1994), where the sediments of the Amran Group are locally condensed to some 300 m (Fig. 3). The majority of the Amran lithofacies comprise lagoonal, lacustrine, reef and biohermal carbonates. After Christmann et al. (1989), and Al Ganad (1991) the Jurassic succession in the mining area consists from bottom to top of nine units, whose characteristics are described in the legend of Fig. 4. 2.1. Sulfides and nonsulfides mineralization The mineralization is structurally and lithologically controlled, and this control is reflected in the morphology of the orebodies, which are variously tabular and parallel to stratigraphy, vertical along fractures and fissures and along the intersection of structures. The mineralized bodies may also occur as “keel” like features. The Jabali mineralization is particularly developed along structural planes (feeder zones?), which dip between 60° and 80°, and at their intersection. The same directions seem to have controlled the distribution of the epigenetic (hydrothermal) dolomitization phases. The stratiform bodies occur in two zones: a laterally extensive “Upper” zone, directly underlying the 212 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Fig. 5. a) General view of the Jabali minesite and future plant, looking northeast; typical ore facies in drillcore: b) J125-7: the oxidation proceeds from the fractures of the dolomite host rock (gray) causing the formation of Zn-dolomite, c) J125-15: typical oxidized ore (red-brown), consisting of replaced smithsonite and Zn-dolomite. White smithsonite in the cavities, d) J125-31: typical oxidized ore, with remnants of the original dolomite, replaced by finely intergrown Zn-dolomite and smithsonite. base of the Unit 7/Unit 8 contact and the more sporadic “Lower” and “Middle” zones, that occur as limbs off the “keel” type mineralization. These bodies are generally flat; however the dip increases to angles greater than 30° from the base of Jabal Salab to the Salab Fault (SRK Consultants, 2005) (Fig. 5a). The black argillites of Unit 8 appear to have acted as an impermeable barrier to the migration of fluids (Al Ganad et al., 1994). To the stratiform mineralization should be added a series of crosscutting bodies (the so-called “chimneys”), which are related to faults. The sulfide association consists of two generations of sphalerite (predominant), galena, pyrite/marcasite and other minor sulfide phases. Silver, cadmium, copper, germanium and mercury are generally contained in sphalerite. The primary sulfide deposit, which shows features of both Mississippi Valley type and Carbonate Replacement models, is believed to have formed by a combination of processes. After Al Ganad et al. (1994) the mineralization was deposited by fluids circulating in a karstic network related to the emersion surface at the top of Unit 7, and was possibly emplaced only slightly later than sedimentation of Unit 8 (Late Jurassic–Cretaceous), still in association with Mesozoic rifting. Ore deposition has been accompanied by several dolomitization phases, only some of which have been considered strictly hydrothermal. Sparry dolomite crystals (the baroque dolomite of Al Ganad et al., 1994, which is equivalent to the saddle dolomite of Radke and Mathis, 1980) occur within cavities, or fill fractures crosscutting the previous dolomite generations. Saddle dolomite is typically deposited by hydrothermal fluids and is generally a precursor phase for MVT or CRD-type carbonate-hosted Zn–Pb mineralization (Diehl et al., 2010). A different genetic concept has been presented in some unpublished reports. After this model the primary sulfides were deposited by circulating hydrothermal fluids, ascending along basinal faults, boosted 213 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Table 1 Mineral abundances in the Jabali cores samples, as deduced from X-ray quantitative phase analysis (QPA). Sample no. Drillcore interval J109-1 J109-2 J109-3 J109-4 J109-5 J125-1 J125-2 J125-3 J125-4 J125-5 J125-6 J125-7 J125-8 J125-9 J125-10 J125-11 J125-12 J125-13 J125-14 J125-15 J125-19 J125-20 J125-21 J125-22 J125-23 J125-24 J125-29 J125-30 J125-31 J125-32 J125-33 J125-34 J125-35 J138-4 J138-5 J138-6 J138-7 J138-8 J138-9 J138-10 57.30–58.30 58.30–59.30 59.30–60.30 60.30–61.65 61.65–62.70 50.78–51.78 51.78–53.10 53.10–54.73 54.73–55.73 55.73–56.73 57.92–59.45 59.45–60.97 60.97–62.00 62.00–64.00 64.00–65.00 65.00–66.00 66.00–67.00 67.00–68.00 68.00–69.00 69.00–70.00 74.50–75.50 75.50–76.50 76.50–77.50 77.50–78.50 78.50–79.50 79.50–80.50 84.50–85.50 85.50–86.50 86.50–87.50 87.50–88.50 88.50–89.50 89.50–90.50 90.50–91.50 68.00–69.00 69.00–70.00 70.00–71.00 71.00–72.00 72.00–73.00 73.00–74.00 74.00–75.00 Dol Cal Sm Cer Gp Ang Sp Gn Cha Hem Gth Kln Sau Ilt Qz (wt.%)a (meters) 82.3 85.1 76.9 86.5 78.6 94.0 83.6 2.7 92.9 77.9 19.5 46.0 2.6 61.1 94.0 95.1 91.3 93.7 95.7 53.2 56.4 15.6 30.6 20.8 47.9 76.3 55.0 85.6 16.9 59.4 93.9 97.5 86.9 95.9 82.8 76.9 89.4 83.8 62.1 8.0 9.8 15.3 4.0 1.3 0.1 0.2 0.4 0.1 41.4 32.9 38.1 76.9 50.5 16.6 0.1 0.1 8.9 3.4 29.7 1.5 3.5 5.2 7.8 17.7 0.1 3.3 38.0 0.9 5.9 63.3 36.8 82.5 82.8 34.5 2.4 1.7 2.2 1.9 2.9 0.1 0.7 0.8 0.3 4.0 0.9 2.6 7.8 52.5 3.2 7.7 8.7 11.1 8.9 5.1 1.7 1.1 0.3 3.7 2.6 0.6 2.6 3.1 2.8 4.7 0.1 2.1 7.6 0.7 2.0 0.2 0.2 0.1 0.3 0.3 0.5 0.4 0.6 1.1 1.0 3.2 1.3 0.1 0.2 0.4 9.8 16.1 6.4 10.1 2.0 0.2 0.3 0.4 0.6 0.1 0.2 0.7 0.2 1.3 0.5 0.1 1.8 0.7 0.6 0.4 0.4 5.8 45.4 10.4 4.1 39.0 10.5 78.1 35.6 0.5 4.7 0.1 0.2 0.3 0.4 0.4 0.2 0.1 0.2 0.1 1.6 3.2 1.6 1.2 1.2 2.1 0.4 0.3 3.0 0.1 1.4 0.6 0.1 2.3 0.9 1.6 3.2 1.2 3.8 2.4 1.7 1.1 1.6 2.1 1.8 1.2 3.6 4.4 7.7 5.5 2.0 1.7 2.8 2.1 3.8 4.6 4.3 4.9 2.5 3.3 2.5 4.2 2.4 2.3 2.1 3.9 1.6 1.7 2.2 0.5 1.1 0.1 0.5 30.8 15.0 0.4 0.3 0.5 0.3 0.4 3.3 1.6 0.5 Notes: mineral abbreviations mostly after Whitney and Evans (2010). Dol; dolomite; Cal, calcite; Sm, smithsonite; Cer, cerussite; Gp, gypsum; Ang, anglesite; Sp, sphalerite; Gn, galena; Cha, chalcophanite; Hem, hematite; Gth, goethite; Kln, kaolinite; Sau, sauconite; Ilt, illite; Qz, quartz. a Statistical indicator ranges: Rp 5.11–6.40%, wRp 6.65–8.85%, χ2 1.199–1.825, Dwd 0.398–1.711. by the heat generated during Tertiary igneous activity, developed in the area during the Red Sea crustal extension (~22 Ma). An extension of this phenomenon would have also triggered the late uplift, favoring the oxidation of sulfides (Allen, 2000). The supergene nonsulfide ore is massive, semi-massive and disseminated, and is characterized by vuggy to highly porous, buff, brown, and orange to white zinc nonsulfide minerals with variable densities, averaging 2.6 g/cm3 (SRK Consultants, 2005). A porous cellular boxwork structure accompanied by numerous cavities coated with zinc minerals, dolomite and calcite is quite common. Gypsum can be very abundant through the entire mineralized area. Kernels of partially oxidized galena are common in high-grade sections. Most of the host rock dolomites at Jabali are dedolomitized and patchily replaced by calcite. Manganese and iron, previously contained in the dolomite lattice, can be seen as newly deposited hydr(oxides) in the interstices of the crystals and in small vugs and fissures. Iron staining is common throughout the mining area, resulting again in variable concentrations of goethite, hematite, and Mn(hydr)oxides. The most common secondary zinc mineral is smithsonite, intimately intergrown with dolomite. Fine to granular amorphous aggregates of hydrozincite have been observed in outcrop, but are very uncommon at depth and in drill cores. Hemimorphite and relict sphalerite occur in minor amounts. Lead is present both as relict galena and cerussite. Silver is contained in argentite and galena, as well as native metal (Al Ganad et al., 1994). 3. Methods of study To investigate the mineralogy linked to the recovery problem, we have studied 40 samples from the Jabali cores J109, J125 and J138 (each sample consisting of a quarter core 1 m long) (Fig. 5b, c, d). We have carried out first a petrographical study in thin section of several core fragments (65), followed by scanning electron microscopy (SEM) observation and qualitative energy dispersive X-ray spectroscopy (EDS) analyses. SEM examination was carried out using a Jeol JSM 5310 instrument at the University of Napoli (CISAG). Element mapping and EDS spectra were obtained by the INCA microanalysis system (Oxford Instruments). The core samples have been crushed to 1 mm and fully homogenized. We have carried out X-ray diffraction on all samples (40), with the aim of identifying the occurring mineral phases. We have used a Philips PW 3020 automated diffractometer (XRD) at the University of Heidelberg, with CuKα radiation, 40 kV and 30 mA, 10 s/ step and a step scan of 0.02° 2θ. The data were collected from 3 to 110° 214 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Table 2 Major and minor element concentrations derived from the chemical assays (CA). Sample no. Zn J109-1 J109-2 J109-3 J109-4 J109-5 J125-1 J125-2 J125-3 J125-4 J125-5 J125-6 J125-7 J125-8 J125-9 J125-10 J125-11 J125-12 J125-13 J125-14 J125-15 J125-19 J125-20 J125-21 J125-22 J125-23 J125-24 J125-29 J125-30 J125-31 J125-32 J125-33 J125-34 J125-35 J138-4 J138-5 J138-6 J138-7 J138-8 J138-9 J138-10 4.55 5.31 5.98 6.29 14.16 1.30 11.49 21.78 3.15 12.16 24.44 19.41 37.62 38.02 25.43 2.30 2.76 3.55 3.09 5.93 1.06 12.43 29.10 15.53 1.13 2.27 8.05 24.93 14.42 37.14 29.32 5.03 4.32 3.77 4.66 6.32 9.45 9.96 11.53 5.42 a b Fe Mg Pb Ca Mn S Ag Cd (wt.%)a 3.86 2.74 1.99 2.30 2.32 5.05 2.39 2.99 3.57 1.92 2.14 1.91 5.52 2.21 2.74 2.44 1.87 3.56 3.40 2.06 2.15 3.61 7.36 4.57 1.99 1.97 3.32 4.73 3.44 3.93 3.54 5.78 2.60 3.60 3.42 4.05 3.18 3.59 2.99 3.18 8.94 9.26 8.73 10.08 8.36 8.84 8.71 0.69 10.58 8.88 4.02 5.73 0.75 0.54 6.13 12.27 12.17 11.37 11.32 10.71 6.85 5.29 1.83 2.36 2.10 7.38 8.56 3.93 7.45 2.72 4.67 9.48 10.26 8.46 10.14 7.51 8.66 8.63 7.22 6.35 1.05 0.13 5.55 0.12 0.06 0.02 1.37 9.33 1.18 2.75 3.65 3.36 4.11 13.20 1.58 0.18 0.16 0.39 0.07 0.10 0.06 0.43 0.68 1.10 0.25 0.45 0.91 3.63 0.95 0.83 1.91 0.97 0.64 0.68 0.75 1.31 2.38 1.41 10.12 4.60 Cu Ni P 30 5 5 5 5 10 5 5 10 5 20 5 20 10 20 5 5 10 10 5 5 20 60 40 5 5 20 20 20 20 20 10 5 5 10 30 20 20 20 20 300 50 50 50 50 500 100 100 200 200 300 100 300 300 200 200 200 100 100 200 300 400 600 500 300 300 400 500 500 300 200 300 200 100 100 600 200 400 200 200 (ppm)b 19.89 21.06 20.13 20.61 15.57 19.68 17.39 9.37 19.90 16.68 7.91 12.23 1.46 0.54 8.78 20.34 20.62 19.46 19.75 19.69 28.97 19.29 2.70 16.18 35.32 27.18 17.16 7.44 15.62 3.70 7.59 18.62 20.25 23.24 19.73 15.84 18.03 17.07 14.61 23.51 0.48 0.58 0.55 0.65 0.60 0.66 0.65 0.13 0.59 0.50 0.80 0.48 0.41 0.39 0.58 0.71 0.55 0.58 0.60 0.61 0.53 0.52 0.48 1.33 0.53 0.57 0.42 0.32 0.55 0.36 0.48 0.59 0.65 0.98 0.65 0.58 0.78 0.66 0.68 0.86 0.03 0.19 0.58 0.15 0.03 2.71 5.61 7.75 4.44 5.00 3.12 4.62 1.59 1.37 0.25 0.06 0.03 0.03 0.03 0.13 0.26 0.03 0.03 0.03 0.03 0.03 0.03 0.24 0.03 0.03 0.07 0.03 0.03 0.03 0.03 0.03 0.12 0.08 0.90 0.43 3 3 11 22 31 5 56 567 45 50 210 118 231 230 289 21 24 44 24 14 5 3 3 3 5 9 102 433 81 264 353 15 18 10 11 44 116 143 93 112 670 760 750 550 1330 90 1120 1380 130 760 1330 1250 1830 2550 1470 280 270 420 280 640 70 1290 1430 850 80 320 780 2060 1320 2120 1160 330 380 260 330 440 560 740 990 440 25 25 25 25 70 25 90 240 25 25 50 25 190 210 70 25 25 25 25 25 25 25 25 25 25 25 25 100 25 90 25 25 25 25 25 25 50 50 70 25 Detection limits (wt.%): Zn 0.0001, Fe 0.01, Mg 0.01, Pb 0.01, Ca 0.01, Mn 0.0001, S 0.05. Detection limits (ppm): Ag 0.5, Cd 0.5, Cu 0.5, Ni 0.5, P 5. 2θ. Quantitative phase analysis (QPA) was performed on the XRD traces using the Rietveld method (Bish and Howard, 1988; Bish and Post, 1993; Hill, 1991; Rietveld, 1969). X-ray powder diffraction data were analyzed using the GSAS package (General Structure Analysis System, Larson and Von Dreele, 2000) and its graphical interface EXPGUI (Toby, 2001). Whole rock chemical analyses (CA) of major and minor elements for the same core samples were committed by Jabal Salab Company (JSC) to OMAC Laboratories Ltd (Co Galway, Ireland). Diamond drill cores have been split and the entire half-core samples have been homogenized and pulverized to obtain 30 g of pulps for chemical analysis. After aqua regia digestion, the samples have been analyzed by multi-element inductively-coupled plasma mass spectrometry (ICP-MS). Samples holding N9% Zn have been also analyzed by atomic absorption spectrometry (AAS), with an excellent agreement between the two data sets (SRK Consultants, 2005). For our study, we have performed a quality check on the previous chemical analyses, testing 20 random samples from our cores at the ACME Laboratories (Vancouver) as well. The zinc values calculated by QPA through X-ray analyses (Rietveld method) have been compared with the chemical assay data of the same cores. Differential Thermal Analysis (DTA, TG) has been performed only on two dolomite samples, which were chosen with the aim of testing this technique for a future exploration perspective of nonsulfide deposits. The samples were analyzed on a Netsch Instrument model STA 409, under air atmosphere at the CISAG Laboratory of the University of Napoli. A sample mass of 100 mg was heated from room temperature to 1100 °C, at the rate of 10 °C min−1. Two pure dolomite samples from the Norian of Southern Apennines (Italy) have been analyzed for comparison. 4. Results Table 1 records the results from quantitative phase analysis (QPA) of the Jabali cores samples set, while Table 2 shows the data from the ICP-MS chemical assays (CA). Table 3 shows the zinc percentages calculated from the minerals indicated by the QPA Rietveld analyses of the core samples, the comparison with the amounts quoted in the chemical assays, and the difference between the two sets of data to indicate the excess or defect in metal contents. The most abundant zinc mineral in the Jabali cores (Fig. 5b, c, d) is the Zn-carbonate smithsonite (ZnCO3), which is generally averaging a few % to 20 wt.%, with a maximum abundance of about 80 wt.% in the J-125 drill core. Hemimorphite [Zn4Si2O7(OH)2H2O] was not detected in XRD, being probably very scarce in the Jabali deposit, as well as hydrozincite [Zn5(CO3)2(OH)6]. However, the latter is very abundant N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Table 3 Zinc amount (Zn%) calculated from whole rock chemical assays (CA), compared with the metal percentages derived from the Zn-bearing minerals measured by X-ray quantitative method (QPA). The columns CA-ΣQPA correspond to defect or excess of Zn percentages calculated with CA respect to QPA method. Sample no. Zn% CA QPA Sm J109-1 J109-2 J109-3 J109-4 J109-5 J125-1 J125-2 J125-3 J125-4 J125-5 J125-6 J125-7 J125-8 J125-9 J125-10 J125-11 J125-12 J125-13 J125-14 J125-15 J125-19 J125-20 J125-21 J125-22 J125-23 J125-24 J125-29 J125-30 J125-31 J125-32 J125-33 J125-34 J125-35 J138-4 J138-5 J138-6 J138-7 J138-8 J138-9 J138-10 4.55 5.31 5.98 6.29 14.16 1.30 11.49 21.78 3.15 12.16 24.44 19.41 37.62 38.02 25.43 2.30 2.76 3.55 3.09 5.93 1.06 12.43 29.10 15.53 1.13 2.27 8.05 24.93 14.42 37.14 29.32 5.03 4.32 3.77 4.66 6.32 9.45 9.96 11.53 5.42 0.78 1.83 2.71 4.07 9.23 0.05 1.72 19.82 0.47 3.08 33.01 19.19 43.02 43.18 17.99 1.25 0.89 1.15 0.99 1.51 Sp CA-ΣQPA Cha ΣQPAa 3.02 23.68 5.42 0.78 1.84 2.71 4.29 9.26 1.85 4.73 19.88 1.81 7.95 33.46 20.47 43.02 43.18 18.03 1.30 0.95 1.22 1.03 1.53 0.03 3.02 23.68 5.42 2.14 20.34 5.48 40.73 18.57 0.26 2.14 20.34 5.48 40.73 18.57 0.26 0.31 5.11 8.40 3.34 5.27 1.04 0.02 0.19 0.03 0.03 1.79 3.01 0.06 1.35 4.87 0.45 1.28 0.03 0.05 0.07 0.07 0.03 0.02 0.03 0.13 0.38 0.02 0.46 5.11 8.40 3.34 5.27 1.43 3.77 3.47 3.27 1.99 4.90 −0.55 6.76 1.90 1.34 4.21 −9.02 −1.06 −5.40 −5.16 7.40 1.00 1.81 2.33 2.06 4.40 1.03 9.41 5.42 10.11 1.13 2.27 5.91 4.59 8.94 −3.59 10.75 4.77 4.32 3.31 4.66 1.21 1.05 6.62 6.26 3.99 Notes: mineral abbreviations as in Table 1. a ΣQPA is the sum of Zn% coming from smithsonite (Sm), sphalerite (Sp) and chalcophanite (Cha). in the mineralized outcrops. Sauconite (Zn-smectite) and other clay minerals are of restricted distribution, and can locally reach values of a few %. Cerussite (PbCO3) is not always present but it may have values from 0.1 to 4 wt.%. Anglesite (PbSO4) (up to 4 wt.%) has been found only in five samples. Sphalerite (ZnS) (up to 8 wt.%) occurs in several samples. Galena (PbS) is ubiquitous but is normally present at levels below 3 wt.%. All the analyzed core samples contain dolomite, generally over 50 wt.% (Fig. 6a, b), seldom below 20%, together with variable amounts of calcite and Fe–Mn(hydr)oxides. A few samples from the J-125 core may contain up to 52 wt.% gypsum. The amount of Fe(hydr)oxides (goethiteNNhematite) is always below 5 wt.%. Zn–Mn(hydr)oxides and Pb-Mn(hydr)oxides as chalcophanite [(Zn,Fe2+,Mn2+)Mn4+3O7·3 (H2O)], and possibly less crystalline compounds occur in many samples (below 1 wt.%). Under microscopic observation, smithsonite can be seen in different forms, both replacing the dolomite host rock (Fig. 5d), and as zoned, colloidal-like cements growing in vugs (Figs. 5c and 6c). In a few samples, 215 smithsonite occurs as perfect rhombohedral crystals, mimicking dolomite. A sharp and/or gradational transition between the host dolomite and the (iron-stained) smithsonite replacing dolomite has been commonly observed. In most cases, however, it is very difficult to distinguish optically the difference between a “dirty”, oxidized dolomite and a “true” euhedral smithsonite. As in many other nonsulfide deposits of the world (Boni et al., 2003; Boni et al., 2007; Boni et al., 2009; Coppola et al., 2009), smithsonite can be also roughly intergrown with Fe(hydr)oxides in reddish agglomerates, as well as with Mn(hydr)oxides and thin layers of clays (Fig. 6d). Some of the concretionary smithsonites contain also variable proportions of MgO (up to 15 wt.% MgO) (Fig. 6e, f). Fe(hydr)oxides at Jabali are never pure goethite. EDS measurements have demonstrated the constant occurrence of ZnO (up to 12%), PbO (up to 7%) and SiO2 (up to 6%) together with Fe. Mn(hydr) oxides can also consist of small amounts of amorphous phases, containing Mn–Pb–Fe in variable proportions. SEM-EDS analyses of many dolomites sampled in nonsulfide ore zone have shown that this carbonate seems to be fairly pure, with only local impregnations of Fe- and Mn(hydr)oxides. However, most dolomites have a “spotty” texture (Fig. 6b). Chemical compositions of dolomite fabrics are variable. The most abundant phase is the typical hydrothermal “saddle” dolomite, which is likely to have replaced the host rock at the time or shortly before precipitation of primary sulfides. Its composition is stoichiometric, with only trace amounts of Mn (up to 0.6 wt.%) (Fig. 6a). Instead, the “spotty” dolomites can be very metal-enriched: their ZnO content ranges from 7–8 wt.% up to 17–22 wt.%, and CdO is around 1.5 wt.% (Fig. 6b and e). Cadmium-free, Zn-enriched dolomites have also been detected throughout the cores. These different phases are generally mixed in various proportions. Proper minrecordite (a dolomite where Mg is almost totally replaced by 29% Zn, Garavelli et al., 1982) has not been recorded in the Jabali samples. Thermal analysis is a quick method to provide additional information on specific minerals and/or mineral assemblages and can be useful in the exploration of nonsulfide ores in carbonate rocks (Zabinski, 1959), in comparison with other investigation methods. Therefore, thermodifferential/thermogravimetric analysis was carried out on two samples showing different zinc grade, i.e. samples J125-31 (14.4% Zn), and J125-34 (5.1% Zn). In J125-31, the DTA peaks were recorded at 400 °C, 500 °C, 685 °C, 750 °C and 870 °C (Fig. 7). The peaks at 400 °C and 500 °C are in the range of the dehydration values for smithsonite (Garcia-Guinea et al., 2009), while the 750 °C and 870 °C peaks are in the range of the dolomite dehydration signatures. In fact, the decomposition of dolomite takes place through two different steps: a first around 800 °C, which can be associated with the decomposition of the MgCO3 layers in the structure, and a second around 900 °C, bound to the decomposition of the CaCO3 layers. The 685 °C peak does not belong to any of the above-mentioned minerals. The Norian dolomite, analyzed as a standard compound, has two dehydration peaks at 810 °C and 890 °C. Both temperatures are perfectly comparable with existing literature data for pure dolomite (Gunasekaran and Anbalagan, 2007; Rowland and Beck, 1952 and references therein). The DTA trace of sample J125-34 exhibits some differences, showing the goethite peak (290 °C), and three peaks at 685 °C, 745 °C and 880 °C (Fig. 7). As in the previous sample, the peaks at 745 °C and 880 °C should correspond to the dolomite dehydration, whereas the 685 °C peak could again not be attributed to any of the minerals determined by XRD in the chosen samples (see Section 5). 5. Discussion Discrepancies have been commonly detected between the zinc contents recorded in the chemical assays and those stoichiometrically calculated by Rietveld analyses from the total amounts arising from the zinc minerals (smithsonite and locally also sphalerite and chalcophanite) detected in the Jabali core samples (Table 3). In fact, the 216 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Fig. 6. a) J125-33: stoichiometric Ca–Mg (hydrothermal) dolomite replaced along the border by Zn-rich (ZnO 13 to 19%) dolomite; b) J138-5: stoichiometric Ca–Mg dolomite patchily replaced by Zn-rich (ZnO 15–17%) dolomite; c) J109-5: concretions of zoned, locally Mg-enriched smithsonite around nuclei of Zn-rich dolomite; d) J109-5: zoned crystals of hydrothermal dolomite, internally replaced by Zn-rich dolomite. White spots are smithsonite intergrown with clays; e) J125-11: zoned crystals of hydrothermal dolomite, internally replaced by Zn-rich dolomite (13–18% ZnO) and then by smithsonite. The external border has also been patchily replaced along fractures, the cement between crystals consist of Mg-smithsonite. A crystal of weathered sphalerite (sphalerite ox.) also occurs; f) J125-11: enlargement of the quadrangle in e): zoned, variably enriched (4–19% MgO) Mg-smithsonite cement. quantitative mineralogy of the analyzed samples is not always in accord with the metal grade derived from the assays: in some samples the zinc values in the assay data are higher than the corresponding zinc content calculated from the mineralogy. This may be due either to a high proportion of zinc concealed in an unknown phase, or to sampling issues. In fact, the samples collected for the current work have been taken from the remaining quarter core available, half core having been used for assay, and another quarter being fragmented due to previous analyses. However, the latter issue cannot justify the wide discrepancy found in most of the considered samples, also because this discrepancy occurs also in the core fragments – analyzed by the ACME Laboratories – from which the thin sections have been made. We suggest the difference between the assayed and calculated zinc amounts in the cores is likely to be because of the presence of several dolomite phases with variable Zn content, as well as to the local occurrence of Mg-smithsonite, both of which have been detected with the SEM-EDS analyses. In fact, also the samples where smithsonite, or another zinc mineral was not detected by XRD have shown some zinc percentage in the assays (~5% Zn), and, from the EDS analyses we know they contain variable amounts of Zn-dolomite. In Fig. 8 we have depicted a diagram where the zinc values detected from the chemical assays of several drillcores are plotted versus those calculated from the amounts of Zn-minerals determined with XRD-QPA (data in Table 3). In a hypothetical case of a perfect stoichiometry of all the minerals occurring in the rocks, the zinc calculated by XRD-QPA minerals and that measured directly in the N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 Fig. 7. DTA-TG-DTG traces of the samples J125-31 and J125-34. 217 Fig. 9. Comparison between DTA traces from various sites: Jabali dolomites 1) J125-31, and 2) J125-34; 3) Tsumeb Zn-dolomite (Hurlbut, 1957); 4) Warynski Mine “Carbonate Zn-ore” (Zabinski, 1959); 5) Triassic dolomite from Southern Italy. The first endothermic peaks of the Zn-dolomite in the carbonate zinc ore from the Warynski mine (Poland) and the Tsumeb dolomite (Namibia) are located around 700 °C, about 100 °C below the first peak of the dolomite standard (Triassic of Southern Italy, 800 °C). The other endothermic peaks are compatible with the second peak of the dolomite standard (900 °C). The samples J125-31 and J125-34 have two “first” endothermic peaks: one is below 700 °C, and is related to the Zn-rich dolomite phases, the other is above 700 °C, and comprehends both Zn-poor and stoichiometric dolomites. The other peaks, which are around 900 °C, can be considered compatible with those of the standard dolomite. samples should be the same (excluding possible measurement errors) and, in this diagram, all the points should be in a straight line with a unitary coefficient. In contrast, many sample points lie away from this direct line. The samples located below the line contain more zinc than calculated from the stoichiometry of the Zn-minerals, detected by XRD (smithsonite, sphalerite and chalcophanite). The samples located above the line contain less zinc than calculated from the standard mineral chemistry of the above-mentioned minerals. The mentioned non-linear trend seems to be due to the fact that at least part of the zinc minerals are non-stoichiometric and different from the theoretical mineralogical phases (from XRD-QPA) used to calculate the amount of the zinc in the samples. The samples positioned below the line, which contain more zinc than the calculated values, point to the presence of zincian dolomite. Testified by SEM-EDS, this dolomite contains variable zinc amounts in the lattice. Minerals positioned above the bisector line have less zinc than calculated: this group may include Zn-minerals where zinc has been partially replaced by other elements, as indicated by the occurrence of Mg-smithsonites. Fig. 8. Zinc contents, calculated from the amounts of smithsonite, sphalerite and chalcophanite determined by QPA, vs. zinc contents measured in the assays. The dotted line is the bisector of the diagram and indicates the theoretical unitary correlation. Fig. 10. Compositions of the zincian carbonates (mol%) from Jabali drillcore samples in the system CaCO3-(Mg, Fe, Mn)CO3-ZnCO3. Circles: zincian dolomites; triangles: smithsonites. 218 N. Mondillo et al. / Journal of Geochemical Exploration 108 (2011) 209–219 The main problem encountered in the X-ray QPA is that the Zn-dolomite peaks could not be distinguished from those of the other dolomite phases in the analyzed samples. A better way to detect the possible zinc content in dolomite may arise from the use of thermodifferential/thermogravimetric (DTA/TG) analysis, as firstly mentioned by Hurlbut (1957) and Zabinski (1959) and confirmed by Zabinski (1980) and our preliminary data. However, the quantitative application of this method to nonsulfide exploration is still in the experimentation phase by our research group. As mentioned, the DTA of a pure dolomite sample is mirrored by a spectrum with two distinct dehydration peaks, which are related to the two cations Ca and Mg in the crystal structure. The position and dimensions of the peaks depend on the dolomite composition. There have been many attempts to register how the variations in composition, induced by the substitution of metals in the dolomite structure could modify the DTA trace, and if it was possible to clearly distinguish the related peaks. Several studies have been carried out to check the effects due to the substitution of certain metals (e.g. Pb) in the Ca positions (A sites, second endothermic reaction), and of others (e.g. Zn, Fe, Mn, Co) in the Mg positions (B sites, first endothermic reaction). The DTA analyses carried out by Hurlbut (1957) on Zn–Pb dolomites from Tsumeb (Namibia) showed a progressive decrease in temperature of the first endothermic reaction, with an increasing percent of ZnO in the dolomite (Fig. 9). A Mg:Zn substitution of 10:1 should reduce the temperature of the related peak from 815 °C to 740 °C and Mg:Zn of 3.3:1 to 725 °C. Fig. 9 also shows the DTA curve of a mixed nonsulfide zinc ore from the Warynski Mine in Upper Silesia (Poland) measured by Zabinski (1959), with the following endothermic peaks for the carbonate minerals: a peak at 400 °C caused by the dissociation of smithsonite, followed by two endothermic peaks at 680 °C and at 900 °C related to dolomite dissociation. Considering the marked drop in temperature of the first dissociation effect of the dolomite, in respect to the standard values (Rowland and Beck, 1952), a partial substitution of Mg by Zn in the structure of the Warynski dolomite can be assumed. In Fig. 9, our DTA traces are compared with those obtained by Hurlbut (1957) and Zabinski (1959), for the dolomites of Tsumeb and of the Warynski zinc mine, respectively. In the Jabali samples considered for this study, the above-mentioned unknown peak centered at 685 °C could be finally attributed to the first endothermic peak of a Zn-rich dolomite phase. The “zincification” of the Jabali dolomite is genetically related to supergene oxidation. This host rock alteration can take two different aspects. The first one (and the more common after the dedicated literature, Boni et al., 2011 and references therein) may consist of a strong alteration of the dolomite lattice by Ca-rich meteoric waters, followed by precipitation of calcite, and is called “dedolomitization” (Fairbridge, 1978). This is a common phenomenon at Jabali (Al Ganad et al., 1994), due to the abundance of gypsum in the sedimentary succession, which is easily water-soluble and can produce a Caenrichment of the groundwater. In the process of dedolomitization of hydrothermal, metal-bearing dolomites, the dolomite crystals are replaced by newly formed calcite, while Mn and Fe usually contained in the hydrothermal dolomite lattice precipitated as a network of hydr (oxides), giving the carbonate rocks of many mining districts their typical brownish, “rusty” appearance. However, at Jabali, as in other dolomitehosted Zn–Pb nonsulfide districts in the world, as Southwestern Sardinia (Italy) (Boni et al., 2011), the dedolomitization can take a very peculiar form, because the circulating supergene fluids are extremely Zn-rich. In this case the process starts with a partial replacement of Mg by Zn in the dolomite lattice, followed by the formation of new Zn-rich (up to 70 mol% Zn) dolomite phases (Fig. 10). The last step of this peculiar dedolomitization may be the total destruction of the dolomite lattice and the formation of the Zn-carbonate smithsonite. In our opinion, the supergene zincian dolomite can be considered the “missing link” between dolomite and smithsonite. This phenomenon had been already described, even if not fully understood, in the Upper Silesia (Poland) Zn–Pb mining district, by Zabinski (1980, 1986), Rosenberg and Champness (1989) and Coppola et al. (2009). In the latter case, however, some doubts have been raised if all the zincian dolomites are really supergene, or partly associated with the hydrothermal fluids, which have precipitated the Lower Silesian sulfide concentrations (Coppola et al., 2009). 6. Importance of mineralogy for detection of the “lost zinc” at Jabali In the Jabali nonsulfide zinc deposit the dolomite host rock has been partly modified through circulating zinc-rich fluids, during supergene weathering processes. One of the main changes consists of the substitution of part of the Mg component by Zn in the dolomite lattice. The mineralogical study that has been carried out at Jabali shows how widespread this process may be, and the importance of understanding the extent of its occurrence in the exploration of dolomite-hosted nonsulfide ores. This “concealed” zinc at Jabali reaches discrete amounts, up to several percents. A similar pattern may also be critical in making an economic evaluation of other supergene zinc deposits. As in many other nonsulfide zinc deposits (Boni et al., 2011), at Jabali it is extremely difficult to define with quantitative diffractometric methods alone the zinc contained in phases like Zn-dolomites (or Zngoethites), instead as that contained in the better-known nonsulfide Znminerals, like smithsonite, hemimorphite or hydrozincite. The DTA method, on the contrary, can show immediately if the chosen samples contain significant amounts of Zn-dolomite, mixed to stoichiometric dolomite. Further developments of this method could provide a quantitative evaluation of the Zn-dolomite (and hence of the so far non-extractable metal) contained in the ore. Considering that the LTC-metallurgical process chosen for the Jabali deposit is mineralogically specific, and recovers selectively only some zinc-nonsulfide minerals (predominantly smithsonite and hydrozincite) discarding the others, as dolomite, the zinc contained in the latter is currently a non-recoverable phase. For this reason, as discussed in Boni et al. (2011), we think that the potential for other nonsulfide Zn deposits to show the same phenomenon of anomalous zinc enrichment in the dolomite host rock during supergene processes would need careful investigation. Acknowledgements This study has been carried out partly with ZincOx funds, and partly with a PhD bursary of the University of Napoli to Nicola Mondillo. The authors would like to thank ZincOx for permission to publish, R. de'Gennaro of the CISAG Napoli for his support during SEM analyses and A. Colella from the Dipartimento di Scienze della Terra of the University of Napoli, for helping with the DTA-TG. 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