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Article

In Situ U–Th–Pb Dating of Parisite: Implication for the Age of Mineralization of Colombian Emeralds

by
Uwe Altenberger
1,
Yamirka Rojas-Agramonte
2,3,*,
Yueheng Yang
4,
Jimmy Fernández-Lamus
5,
Tobias Häger
3,
Christina Guenter
1,
Alejandra Gonzalez-Pinzón
6,
Felipe Charris-Leal
6 and
Julia Artel
1
1
Institute of Geosciences, University of Potsdam, Karl-Liebknecht Str. 24-25, House 27, D-14476 Potsdam-Golm, Germany
2
Institut für Geowissenschaften, Christian-Albrechts-Universität zu Kiel, Ludewig-Meyn-Straße 10, D-24118 Kiel, Germany
3
Institut für Geowissenschaften, Johannes Gutenberg-Universität Mainz, J.-J. Becherweg 21, D-55099 Mainz, Germany
4
State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, No. 19, Beitucheng Western Road, Chaoyang District, Beijing 100029, China
5
Departamento de Geosciencias, Universidad Nacional de Colombia, Bogotá 11001, Colombia
6
Natural Colombia Mineral SAS, Bogotá, Colombia
*
Author to whom correspondence should be addressed.
Minerals 2022, 12(10), 1232; https://doi.org/10.3390/min12101232
Submission received: 6 July 2022 / Revised: 10 September 2022 / Accepted: 22 September 2022 / Published: 28 September 2022
(This article belongs to the Section Mineral Geochemistry and Geochronology)
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Abstract

:
Parisite-Ce (Ca(Ce,La)2(CO3)3F2) is a rare-earth (REE) fluorocarbonate mineral first described from the world-famous emerald mines of the Muzo district, Boyacá Province, Colombia. Four samples of parisite-Ce collected from outcrops near Muzo have been geochemically studied and dated using the in situ laser ablation U–Th–Pb method. Our study shows that the REE abundance of parisite is controlled by the leaching of the wall rocks (black schist). Furthermore, we show that the parisite-Ce crystals formed in textural equilibrium with the emeralds, suggesting a similar time of crystallization. Our analysis demonstrates the capability of parisite as a geochronometer and shows that precise and accurate U–Th–Pb ages can be obtained from parisite after common 207Pb correction. A higher precision date was obtained with the Th–Pb ratio rather than with the U–Pb ratio because of the relatively higher content of Th than U in the samples. The samples yielded 208Th–232Pb ages ranging from ~47 to 51 Ma. The new ages are ~10 Ma older than previously reported Ar–Ar ages and ~10 Ma younger than previously reported Rb/Sr ages. These results will have significant implications for understanding the timing of mineralization and crystallization of emerald deposits in Colombia. Furthermore, this study opens new avenues for dating similar deposits worldwide.

1. Introduction

For much of recorded history, Colombia has produced the largest and highest-quality emerald crystals in the world. More than 200 emerald deposits and occurrences in the country are located in two narrow belts on either side of the Eastern Cordillera (Figure 1). The two mineralization belts are located some 80 km apart. In the western emerald belt (western zone) are the districts of Peñas Blancas, Coscuez, Muzo and Yacopí, while in the eastern emerald belt (eastern zone) are the major mining districts of Gachalá, Chivor and Macanal (Figure 1). Colombian emeralds are unique in their genesis and differ from other emerald deposits in the world, by the fact that they are located in sedimentary to low-grade metamorphic rocks [1] (Figure 1). Several non-magmatic genetic models have been proposed for the formation of the emerald deposits. The most accepted is the epigenetic hydrothermal–sedimentary model of Giuliani et al. [2], in which magmatic processes as suggested by Oppenheim [3] are not necessary.
Emerald deposits in the eastern zone (Figure 1) are estimated to be 61 million years old and are associated in time with a Cretaceous extensional tectonic regime [4,5]. The deposits in the western zone have been dated at 32 and 35–38 million years and are associated with tear and thrust faults which predate the main uplift of the mountain range during the mid-Miocene [6]. Romero-Ordoñez et al. [5] obtained ages ranging from 61 to 67 Ma using the Rb–Sr isotopic method for emeralds from both the eastern and western zones. 40Ar/39Ar ages reveal 38–32 Ma in muscovite [6]. In addition, an unpublished BSc showed similar muscovite ages for the western zone (Muzo district), indicating two stages of hydrothermal activity around 62 Ma and 30 Ma [7]. Therefore, the published results so far indicate that the age of emerald formation is poorly constrained.
Parisite-CaCe2(CO3)3F2 is a rare-earth fluorocarbonate with cerium, lanthanum or neodymium as the dominant rare-earth element. The mineral crystalizes in the monoclinic system and was first described in the emerald mines of the Muzo district by Lavinio de Medici-Spada, a poet and mineralogist, and J.J. Paris in 1848 [8,9]. The parisite in the Muzo region is the Ce-type [10], and appears to have formed at the same time as the emeralds (Figure 2a,b). The fluorocarbonate also occurs as inclusions within the emeralds [11]; therefore, it is used as a mineral indicator for emerald crystallization [12]. Parisite is part of the bastnäsite group [13], where bastnäsite, REE(CO3)F, and synchysite, CaREE(CO3)2F, represent the end members [14].The bastnäsite group minerals, including parisite, contain U and Th [14], and thus have potential to be used as geochronometers.
Recent studies by Artel et al. [15] and Zeug et al. [14] reveal the possible complex internal structure of the parisite crystals from the Muzo region. The mineral can be internally composed of polycrystalline aggregates and can also consist of various polytypic and polysomatic intergrowths of several fluorocarbonate phases of the bastnäsite group (La Pita Mine [14]). In the present study, we show for the first time in situ U–Th–Pb dating of parisite from the Muzo district. In addition, we report in situ trace element and Sm–Nd isotope analysis in order to better understand and constrain the time and genesis of emerald mineralization in the western zone of the Eastern Cordillera.

2. Geological Setting and Emerald Formation

The Eastern Cordillera of Colombia constitutes the relic of an uplifted Cretaceous marine sedimentary basin with a unique tectono-sedimentary evolution ([16,17,18], Figure 1b). The emerald mineralization is hosted in Lower Cretaceous (135–116 Ma) sedimentary rocks composed of a thick succession of sandstone, limestone, black shale and evaporites [6,19,20]. The up to ten-kilometer-thick Cretaceous and overlying Eocene sediments were deposited in a back-arc basin, that is segmented into various sub-basins [17,18,21]. The subsidence of the basin has been explained as an early rifting phase in the Early Cretaceous, followed by a thermal decay after rifting in the Late Cretaceous [16,19]. Deposition was followed by fault inversion and overthrusting onto the Los Llanos basin in the east and the Magdalena basin to the west (Figure 1b,d; [18,19]).
The mineralization in each of the two flanks of the Eastern Cordillera is suggested to have occurred in two different tectonic settings [22] and ages [6,23,24]: In the eastern zone (Chivor area), emerald deposits formed during the Paleocene (61 Ma, 87Rb/86Sr) in a thin-skinned extensional tectonic regime controlled by gravity-driven evaporite dissolution [6,22]. In the western zone (Muzo area), the emerald deposits are linked to listric faults and associated thrusts developed during an Eocene–Oligocene (structural data) compressional tectonic phase, prior to the major uplift of the Cordillera during the middle Miocene [22], supported by 40Ar/39Ar ages of 38–32 Ma [6]. However, Paleocene Rb–Sr ages of emeralds are similar for both zones, 61 Ma in the eastern zone and 67 Ma in the western zone (Rb/Sr in emeralds [6]), although the structures controlling emerald formation in the western zone are suggested to be Eocene–Oligocene in age [6,22].
Nevertheless, in both emerald zones, saline hydrothermal brines and their interaction with black shales are the major controls responsible for the origin of the epigenetic emerald-bearing systems [25]. Fluid inclusion studies [25] show the mixing of two chlorine-rich saline fluids that dominate both emerald zones, despite the differing ages. Whereas one fluid is Na-rich, coming from the solution of underlying halite beds, the other one is more Ca-rich, which is controlled by dissolution of anhydrite and/or by leaching of the wall rocks [25]. The strong influence of halite is due to the Lower Cretaceous salt deposits, locally exhumed during the Tertiary. Beryllium (Be) was transported in the form of Be-F complexes in a NaCl fluid and precipitated as emeralds after mixing with calcium brines causing the precipitation of fluorite and parisite [25].
The emerald deposits of the eastern zone (Chivor district) are hosted in Lower Cretaceous black shales (142–137 Ma) at the base of the Macanal series (137–132 Ma). According to [20,22], the deposits in the Chivor district formed in a series of siliceous or carbonated black shales, limestones and minor siltstones. Most emerald deposits of the Muzo district on the western flank of the Cordillera occur epigenetically in Lower Cretaceous (ca 132–127 Ma) carbonated black shales and the underlying dolomitic limestones (Rosablanca Formation). Minor deposits occur in Lower Cretaceous siliceous black shales and rarely in younger schists (ca 121–112 Ma) [20,22].
Emerald crystals are found in carbonate-, silicate-, pyrite-rich veins, pockets and extensional breccia, black graphite-rich shales and carbonate rocks (e.g., [3,9]). Although these mineralogical and geochemical parameters in both zones are basically the same, they differ in their structural relationship to the wall rocks [22]. In the western zone, the emerald deposits form after the fracturing and brecciation of the hanging wall rock sequence. In contrast, in the eastern zone, the hydrothermal fluids and evaporites are scattered along a regional-scale stratiform brecciated zone [22].
For the western zone, Giuliani et al. [2] describe two major phases of mineralization, which they correlate with two compressional tectonic stages. The first phase crystallized albite, calcite, green mica (fuchsite) and pyrite, while the second phase formed calcite/dolomite, quartz, fluorite and emerald in the veins and breccias. Banks et al. [25] describe 3 stages of mineralization: the initial one, with fibrous calcite, pyrite 1, albite, quartz and green mica, a second one with rhombohedral calcite, dolomite, albite, pyrite 2 and kerogens, and a third one, with emeralds, pyrite 3 and parisite-Ce with REE—dolomite, fluorite and quartz. However, both studies indicate the growth of emerald and parisite in one stage. According to Banks et al. [25], the mineralizing fluids were derived from the interaction of low-salinity fluids with halite and anhydrite. Beryllium, chromium and vanadium were derived from the black shales. The rare-earth elements necessary to form parisite-Ce are also mainly leached from the black shales ([15] and present study).
Alonso-Perez et al. [26] compare the rare-earth element and incompatible trace element abundances of emeralds that have formed in different environments. They confirmed that the emerald deposits in Colombia or “type IIb emeralds” are generated in a sedimentary environment characterized by flat, crustal-normalized, REE patterns very similar to shales and loess (Figure 3). In contrast, magmatic-originated emeralds (Type Ia) show a steep negative slope, i.e., Lacrust/Ybcrust of ca. 0.3 (e.g., Madagascar and Brazil).

3. Analytical Methods

The four parisite-Ce samples were collected in outcrops (PA-01, PA-02) and mines (PA-03, PA-04) near Muzo (Figure 1c) and are part of emerald–parisite–calcite–albite-veins, hosted in graphite-bearing shales (Figure 2a–c). In general, the sampled localities are characterized by the presence of hydraulic breccias, mainly massive calcite–albite mineralization cutting through the bedding with evidence of hydrothermal alteration (Figure 2c). The bed rock contained crystals of pyrite and iron oxides, with minor presence of calcite vein with albite, malachite/azurite.
The parisite crystals were mechanically broken out of the rock and polished for thin sections. They were further analyzed with a Jeol Superprobe JXA-8200 electron microprobe (EMP), and by a scanning electron microscope Jeol JSM-651 (SEM) with an Oxford Inca X-act energy-dispersive spectrometer (EDX) at the University of Potsdam. For the EMP analyses, artificial standards from the Smithsonian Institute and natural monazite were used. Rare-earth element (REE) analyses of the wall rock and coexisting calcite were performed by inductively coupled plasma optical emission spectrometry (ICP-OES) with an ICP 5100 from Agilent at the University of Potsdam and by inductively coupled plasma mass spectrometry Agilent 7500a Q-ICP-MS at the State Key Laboratory, Beijing (supplementary material and Table 1).
Small slices of the separated grains were embedded in epoxy, sectioned to expose their interiors to the surface, polished and mapped by optical microscopy and backscattered imaging. The analytical procedure for in situ trace elements, including REE, and U–Th–Pb age analysis by LA-ICP-MS and Sm–Nd isotopic measurement by LA-MC-ICP-MS has been described by [27]. Detailed description on the U–Th–Pb methodology can be found in the supplementary material.

4. Results

4.1. Mineralogy and Chemistry

The studied parisites are part of the common calcite/dolomite–emerald–quartz–albite–white mica (Wma) paragenesis, as defined by [20] (stage 2) and [25] (stage 3) and earlier described by [3,28]. Additionally, fluorite, pyrite and baryte are the most common accessory minerals. The wall rocks are graphite-bearing carbonaceous black shales with metasomatized, i.e., albite and pyrite-rich border zones. Whole rock samples collected 1 m away from the veins do not show any alteration either macroscopically or microscopically (see Figure 3). Figure 2a shows the intimate relationship of emeralds, parisite and calcite/dolomite as well as albite in a fractured black shale from the sample locality.
The up to 1.2 cm × 0.6 cm large parisite crystals in samples PA-01contain thin aligned inclusions of baryte, dolomite and calcite (Figure 2b,d, Table 2). Baryte forms the tips of calcite–dolomite inclusions (Figure 2d). In contrast to earlier described possible polycrystalline parisite aggregates [15], the analyzed parisites are monocrystalline, as indicated by back-scattered electron analysis (Figure 2d).
The parisite samples are chemically dominated by Ce (ca. 30 wt.% Ce2O3) (parisite-Ce). However, La2O3 and Nd2O3 reach concentrations of up to 15 wt.% (Table 2). The crystals are fluorine-rich (Table 2) and show subtle variations between the core and rim (Table 2). In addition, they contain rare inclusions of baryte, calcite and dolomite. In contrast to parisite, the inclusions are nearly free of rare-earth elements and fluorine.

4.2. REE Characteristics of the Parisite Environment

Figure 3 shows upper crust normalized REE pattern of the parisite compared to emeralds [26], calcite and the wall rock composition 1m and 1cm away from the veins (Table 3). Emerald, parisite and calcite formed at the same time. In contrast to parisite, as a pure REE-F-carbonate, emeralds (mean data from [26]) and the wall rock (this study) show relatively low REE concentrations. However, parisite reflects the negative Eu anomaly of the wall rock (Figure 3). In contrast, emeralds display no Eu anomaly and calcite indicate a weak positive Eu anomaly. The REE deflection in the wall rock, with decreasing distance to the parisite-bearing veins, suggests that the black schists are the major source of these elements in parisite.

4.3. Isotopic Data (232Th/208Pb and Sm/Nd)

As shown in Figure 4 and Table 1, the four parisite samples yielded 232Th/208Pb ages of 47.88 ± 0.46 Ma (2s, n = 12), 50.13 ± 0.65, Ma (2s, n = 17), 50.93 ± 0.52 (2s, n = 17) and 46.77 ± 0.36 Ma (2s, n = 19), for samples PA-01, PA-02, PA-03 and PA-04, respectively. The ages are very similar and cluster around 47 and 50 Ma.
Our analysis demonstrates that precise and accurate U–Th–Pb ages can be obtained from parisite after common 207Pb correction. A higher precision date was obtained with the 232Th/208Pb ratio rather than with the U–Pb ratio because of the relatively higher content of Th than U in the samples (see Table 1). Parisite has not been dated before; therefore, the potential of this mineral as a U–Th–Pb geochronometer has not been properly investigated. According to this study, parisite has sufficient concentrations of U and Th (Table 1), which makes it possible to precisely measure the U–Th–Pb isotopic composition by in situ (laser or ion probe) technique [27]. It is important to note that the U–Pb decay system with two independent decay chains (206Pb/238U, 207Pb/235U), offers an internal check on a closed system. This is the main advantage of the U–Pb system over the Th–Pb system (208Pb/232Th) (see [27] for more details). However, our dating of Colombian parisite produced more precise results with the Th–Pb system than with the U–Pb.
The intermediate daughter isotope 230Th decays with a half-life of ~7500 a in the 238U–206Pb decay chain. Our samples incorporated excess 230Th during crystallization. This excess 230 Th will completely decay into 206Pb, which is not the daughter isotope of the 238U within the mineral [29]. Thus, the U–Pb method is not applicable to parisite grains with relatively high Th/U ratios [30]. This problem does not exist for the Th–Pb system because each of the intermediate nuclei of the 232Th–208Pb decay chain have a very short half-life. Hence, we used the Th–Pb age rather than the U–Pb age to date the parisite samples in the present study.
Additionally, the Sm and Nd concentrations and Nd isotopic ratios are listed in Table 4 and plotted in Figure 4. The data points display some differences for sample PA-02 compared to the other samples in the 147Sm/144Nd versus 143Nd/144Nd diagram (Supplementary Figure S1, Table 4) with higher 147Sm/144Nd. The difference affecting sample PA-02 might be related to an ablation bias due to differing volatilities of Sm and Nd. The initial εNd(t) is very similar (−8.10 to −8.90), indicating similar genetic evolution of rock chemistry.

5. Discussion

The two large emerald districts in Colombia, especially that of Muzo, are famous for their high-quality crystals, and for their unique genesis. In contrast to other great emerald deposits worldwide, such as in Brazil [26], which are due to metasomatic interaction between acid magmatism and basic–ultrabasic rocks, the Colombian ones are formed by low-temperature hydrothermal brines that provide the necessary elements from the wall rocks that are of sedimentary origin. Flat crustal normalized REE and incompatible trace element patterns of emeralds [26], as well as the REE leaching of the wall rock (this study), support the theory of a non-magmatic controlled environment to form parisite.
The motivation to carry out the present study comes from the observation that parisite and emerald grew almost simultaneously in the western district. Our new and well constrained Th–Pb ages of parisite and, by inference, also for the emeralds of the Muzo region of approximately 47–51 Ma, reduces the confusion stemming from different ages for the Colombian emerald deposits. Cheilletz et al. [6] and Svadlenak [7]) describe calculated Ar/Ar white-mica ages of 32–30 Ma and 62 Ma for the western zone and Cheilletz et al. [23] describe ages of 65 Ma for the eastern zone. The 87Sr/86Sr in the 87Rb/86Sr system calculations [6] gave ages around 61 Ma for the eastern zone and 67 Ma for the western zone of the Eastern Cordillera. Except for the Rb/Sr data, the ages are derived from white micas that are not proven to be co-genetic. The difference between the Rb–Sr emerald ages and the Th–Pb ages of parisite are not well understood.
The originally estimated differences of Ar/Ar ages of white micas and Rb/Sr ages of emeralds of the eastern and western zones were up to 30 Ma [6,23,24]. The new Th–Pb data from the western domain, which grew simultaneously with the emerald, reduces the age difference to ca 10 Ma. Unfortunately, there are no known parisite occurrences in the eastern emerald belt to compare the new ages. The tectonic scenario during the genesis of the emerald deposit should be reevaluated in the framework of the known mica ages. The new age of the western deposit suggests a possible revision to a similar tectonic and geodynamic situation as in the east, i.e., during a thin-skinned extensional tectonic period. However, the formation of both emerald zones is clearly of Paleogene age.

6. Conclusions

Th–Pb isotopic analysis of parasite has been proven to be a reliable geochronological tool in dating primary geological or overprinted systems where common datable minerals (e.g., Ar–Ar in Mica, U–Pb in zircon) are lacking. The parisites and, therefore, the emeralds in the world-famous Muzo area are now dated to an age between 47 and 51 Ma. This is in contrast to former estimates, which are mainly based on non-syngenetic minerals such as white mica or the Rb/Sr data of emeralds. The new ages require a new structural model which is beyond the scope of this study. Assuming these ages, either an extensive tectonic regime in the western zone similar to that in the eastern zone must be expected, or an emerald formation in a different tectonic setting, as proposed so far (e.g., [24]).

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min12101232/s1, Figure S1: Plot of 147Sm/144Nd vs. 143Nd/144Nd for parisite samples.docx [31,32,33,34,35,36,37,38].

Author Contributions

Conceptualization, U.A., Y.R.-A. and J.F.-L.; Project administration: Y.R.-A., U.A. and T.H.; Writing and editing: U.A., Y.R.-A., T.H. and J.F.-L.; Trace element analytics and data handling: Microprobe: SEM/EDX: C.G., J.A. and U.A.; Mass spectrometry: Y.Y.; Sampling and field work: J.F.-L., F.C.-L., A.G.-P. and F.C.-L.; Literature research: J.F.-L. and U.A. All authors have read and agreed to the published version of the manuscript.

Funding

U.A. was funded by the University of Potsdam grant KoUP-program. Y.R.-A. acknowledges financial support to the FAPA funding from Universidad de los Andes. Y.Y.-H. acknowledges financial support by the Natural Science Foundation of China.

Acknowledgments

We would like to specially thank all the traditional miners in Colombia, who invited us not only to their mines but also to their homes. Thanks to them, we were able to enter their mines, some of them very small and with few resources but with the great dream of finding the big emerald that will get them out of their poverty and needs. (41525012). We thank C. Kallich for drawing Figure 1 and A.E. Concha Perdomo for the wonderful support during the stays in Colombia (U.A.).

Conflicts of Interest

The authors declare no conflict of interest.

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Minerals 12 01232 g001 550
Figure 1. (a,b) Simplified map showing the major tectonic provinces of northwestern Colombia and its location in South America (inset a). (c) Detailed geological map of the sample area with sample localities. (d) Cross-section through the bivergent fold and thrust belt of the Eastern Cordillera. The over-thrusting of the two foreland basins containing the emerald deposits is shown: western zone (WZ, Muzo, Coscuez, Yacopí and Peñas Blancas) and eastern zone (EZ; Chivor, Gachalá and Macanal). (a,b) Modified after Branquet et al. (1999) and Cooper (1995).
Figure 1. (a,b) Simplified map showing the major tectonic provinces of northwestern Colombia and its location in South America (inset a). (c) Detailed geological map of the sample area with sample localities. (d) Cross-section through the bivergent fold and thrust belt of the Eastern Cordillera. The over-thrusting of the two foreland basins containing the emerald deposits is shown: western zone (WZ, Muzo, Coscuez, Yacopí and Peñas Blancas) and eastern zone (EZ; Chivor, Gachalá and Macanal). (a,b) Modified after Branquet et al. (1999) and Cooper (1995).
Minerals 12 01232 g001
Minerals 12 01232 g002 550
Figure 2. Parisite samples: (a) Parisite–emerald-bearing sample from Muzo; BS = black shale, Ab = albite, Pa = parisite, Cc = calcite, Do = dolomite, Brt = baryte. (b) Photo showing two of the analyzed parisite crystals from sample PA-01. (c) Sample locality with carbonate-rich dikes cutting the bedding planes of black shales (PA-03). (d) Back-scattered electron image (BSE) of inclusions in parasite (baryte (light), calcite (black) and dolomite (grey)).
Figure 2. Parisite samples: (a) Parisite–emerald-bearing sample from Muzo; BS = black shale, Ab = albite, Pa = parisite, Cc = calcite, Do = dolomite, Brt = baryte. (b) Photo showing two of the analyzed parisite crystals from sample PA-01. (c) Sample locality with carbonate-rich dikes cutting the bedding planes of black shales (PA-03). (d) Back-scattered electron image (BSE) of inclusions in parasite (baryte (light), calcite (black) and dolomite (grey)).
Minerals 12 01232 g002
Minerals 12 01232 g003 550
Figure 3. Mean REE concentrations of four parisites (mean of 13–23 samples) and their coexisting minerals and wall rock system. REE are upper crustal-normalized (Rudnick et al., 2003).
Figure 3. Mean REE concentrations of four parisites (mean of 13–23 samples) and their coexisting minerals and wall rock system. REE are upper crustal-normalized (Rudnick et al., 2003).
Minerals 12 01232 g003
Minerals 12 01232 g004 550
Figure 4. Mean In situ Th–Pb ages obtained by LA-ICP-MS for parisite samples PA-01 (A), PA-02 (B), PA-03 (C) and PA-04 (D).
Figure 4. Mean In situ Th–Pb ages obtained by LA-ICP-MS for parisite samples PA-01 (A), PA-02 (B), PA-03 (C) and PA-04 (D).
Minerals 12 01232 g004
Table
Table 1. U–Th–Pb isotope data of parisite using laser ablation.
Table 1. U–Th–Pb isotope data of parisite using laser ablation.
ppmppmppm Ratio Ratio Ratio Ratio Ratio Age (Ma)
207Pb Corr.
PbThUTh/UU238/Pb2061sPb207/Pb2061sPb207/U2351sPb206/U2381sPb208/Th2321sPb208/Th2321s
PA-01-019.4736011.961775.91.80.03330.00250.06050.00430.013180.000310.002360.0000447.70.8
PA-01-029.3777412.363173.31.90.03410.00280.06400.00510.013640.000350.002380.0000448.10.8
PA-01-038.9745211.962951.31.40.27380.01040.73470.02330.019480.000520.002380.0000448.00.9
PA-01-049.5736011.862371.01.90.03700.00300.07170.00560.014080.000370.002370.0000447.90.8
PA-01-059.2696911.162773.21.90.03330.00290.06260.00530.013660.000350.002380.0000448.10.8
PA-01-068.5648610.859972.21.80.03790.00280.07240.00520.013860.000340.002380.0000448.00.8
PA-01-079.9705210.765865.21.80.03040.00300.06430.00620.015340.000430.002400.0000448.40.9
PA-01-0810.2729810.967068.61.90.02820.00310.05670.00610.014570.000410.002410.0000448.60.9
PA-01-098.6635710.262169.81.90.02830.00280.05590.00540.014320.000390.002350.0000447.40.9
PA-01-109.4683110.763769.82.00.04830.00390.09550.00730.014330.000410.002380.0000448.00.9
PA-01-119.0655510.960456.71.50.18520.00750.44980.01590.017630.000460.002390.0000448.10.9
PA-01-128.4722211.562766.72.00.06830.00510.14110.01000.014990.000450.002280.0000446.10.9
PA-02-014.248538.4578117.64.60.06680.00710.07810.00790.008500.000330.002530.0000551.11.1
PA-02-024.863028.7728107.94.10.04480.00570.05720.00700.009270.000350.002420.0000549.01.0
PA-02-035.679358.296599.33.60.04820.00530.06690.00710.010070.000370.002340.0000547.31.0
PA-02-044.561188.1751114.74.50.05430.00650.06520.00750.008720.000340.002480.0000550.11.1
PA-02-054.257738.7665113.64.40.08020.00790.09720.00900.008800.000340.002480.0000550.11.1
PA-02-063.853827.9680114.74.50.05010.00700.06020.00810.008720.000340.002560.0000551.61.1
PA-02-074.667168.6781114.34.40.06090.00720.07340.00840.008750.000340.002520.0000550.81.1
PA-02-084.569238.5812110.34.30.08000.00760.09990.00890.009070.000350.002510.0000550.61.1
PA-02-094.670157.2978102.54.10.05160.00680.06940.00880.009760.000390.002390.0000548.31.0
PA-02-104.160958.4725118.54.80.06930.00750.08060.00830.008440.000340.002480.0000550.01.1
PA-02-114.356128.1690111.15.60.05890.00940.07300.01110.009000.000450.002560.0000651.61.2
PA-02-124.254518.3656111.24.30.06850.00690.08490.00810.008990.000350.002540.0000551.31.1
PA-02-134.053598.0672117.04.90.05820.00790.06860.00890.008550.000360.002540.0000551.31.1
PA-02-143.762798.1771122.75.00.04960.00760.05580.00830.008150.000330.002400.0000548.51.0
PA-02-153.865789.1721123.34.90.05770.00710.06450.00760.008110.000320.002500.0000550.41.1
PA-02-164.071539.0795118.64.50.07530.00760.08750.00840.008430.000320.002490.0000550.41.1
PA-02-174.191089.4971118.34.60.06020.00690.07010.00780.008450.000330.002500.0000550.51.1
PA-03-014.9223413.017283.82.90.22730.01200.37380.01660.011940.000410.002540.0000651.31.1
PA-03-025.0233815.015598.73.00.12640.00690.17650.00860.010130.000310.002510.0000550.71.0
PA-03-032.196611.38697.33.10.14450.00840.20460.01060.010280.000330.002480.0000650.01.2
PA-03-045.6251016.615184.72.70.21520.01020.35020.01410.011810.000370.002550.0000551.61.1
PA-03-054.6207213.415587.02.50.25770.01060.40840.01420.011500.000330.002560.0000551.61.0
PA-03-061.354310.25397.73.80.16030.01140.22610.01400.010240.000400.002530.0000851.01.6
PA-03-076.5300315.7192107.43.30.05660.00470.07250.00570.009310.000290.002510.0000550.71.0
PA-03-085.1237816.0149107.63.00.07170.00430.09180.00510.009290.000260.002480.0000550.11.0
PA-03-091.250310.44898.03.30.19160.01090.26900.01320.010200.000340.002540.0000751.21.5
PA-03-104.6207412.916184.32.40.18450.00840.30130.01190.011860.000340.002520.0000550.91.0
PA-03-114.4194514.613386.52.60.24810.01100.39520.01470.011560.000350.002550.0000551.51.1
PA-03-124.1184513.0142102.03.10.07140.00510.09650.00640.009800.000300.002530.0000551.11.0
PA-03-133.8169812.6135108.73.80.09310.00700.11790.00810.009200.000320.002540.0000551.31.1
PA-03-143.3143213.710596.92.80.14390.00720.20450.00910.010320.000300.002540.0000551.31.1
PA-03-153.0135913.6100110.43.20.08260.00500.10300.00580.009060.000260.002510.0000550.61.0
PA-03-163.1142612.6113110.13.50.08960.00600.11200.00690.009080.000290.002550.0000551.41.1
PA-03-171.983611.672111.03.30.09450.00600.11730.00680.009010.000270.002460.0000649.71.1
PA-04-0114.112,80417.971582.02.00.04000.00280.06700.00460.012190.000300.002350.0000447.40.9
PA-04-0213.412,14117.669085.52.10.03600.00280.05800.00440.011690.000290.002360.0000447.70.9
PA-04-0313.712,38716.475669.31.90.09210.00470.18290.00860.014430.000390.002340.0000447.20.9
PA-04-0411.410,63614.672879.32.10.03700.00300.06420.00510.012610.000330.002290.0000446.30.8
PA-04-0510.7998713.972083.62.10.03440.00290.05660.00470.011960.000300.002280.0000446.10.8
PA-04-0612.311,06415.272779.62.00.03210.00270.05560.00470.012570.000320.002380.0000448.00.9
PA-04-0713.211,91316.173876.81.90.05290.00310.09490.00530.013020.000320.002360.0000447.70.9
PA-04-0810.910,16614.271884.12.10.02900.00310.04740.00490.011890.000300.002280.0000446.10.8
PA-04-0910.0929213.071685.82.20.03430.00330.05500.00520.011660.000300.002300.0000446.40.8
PA-04-1011.5998313.872660.81.70.20730.00900.46990.01750.016460.000470.002360.0000447.60.9
PA-04-1112.811,53416.968381.32.00.07810.00370.13220.00590.012300.000300.002370.0000447.80.9
PA-04-1219.610,15214.072481.82.00.03070.00270.05160.00440.012230.000300.002320.0000446.80.9
PA-04-1311.810,86015.171784.52.10.03910.00300.06360.00470.011830.000300.002310.0000446.70.9
PA-04-1411.610,73815.170983.32.10.03160.00290.05230.00470.012000.000300.002310.0000446.70.9
PA-04-1511.510,52714.870943.91.10.39920.01251.25080.03240.022760.000580.002320.0000446.80.9
PA-04-1611.210,14514.470477.91.90.06160.00360.10880.00600.012830.000320.002290.0000446.20.8
PA-04-1712.010,94814.873782.62.10.03520.00290.05870.00480.012110.000310.002280.0000446.10.8
PA-04-1811.710,84314.972880.82.00.03170.00270.05390.00440.012370.000310.002270.0000445.70.8
PA-04-1911.410,67115.071280.32.00.04020.00270.06880.00450.012450.000310.002250.0000445.40.8
Table
Table 2. Electron microprobe analyses of parisite sample PA 01 and calcite. CO2 is calculated. B.d.l.: below detection limit.
Table 2. Electron microprobe analyses of parisite sample PA 01 and calcite. CO2 is calculated. B.d.l.: below detection limit.
PA-01Calcite
wt.%CoreRimCoreRimCoarse
Core		Inclusion
in Dolomite
FeOb.d.l.b.d.l.b.d.l.b.d.l.0.370.39
MgOb.d.l.b.d.l.0.01b.d.l.0.060.05
CaO11.4011.8311.8511.4258.8559.35
SrO0.220.290.280.320.120.13
La2O314.9314.5814.6815.31b.d.lb.d.l.
Ce2O330.6729.8630.2329.440.01b.d.l
Nd2O310.8110.8610.7911.840.02b.d.l
Sm2O31.171.171.161.21b.d.lb.d.l
Eu2O30.540.460.450.54b.d.l0.04
Gd2O31.451.461.441.220.010.01
Pr2O33.183.213.203.31b.d.l0.02
Y2O30.740.670.740.50b.d.lb.d.l
ThO20.881.091.260.95u.d.l.0.02
F4.584.474.444.52b.d.l.b.d.l
Cl0.020.020.020.02b.d.lb.d.l
CO221.3321.9021.3321.2940.2039.60
Table
Table 3. REE concentrations of the wall rock, emeralds and calcite. ICP-OES technique was used for calcite and wall rock analyses. Parisites and emeralds were analyzed by ICP-MS. (1) Emerald values are the mean of seven samples of Alonso-Perez et al. (2021). (2) Upper crustal values are from Rudnik et al. (2003). All concentrations in ppm.
Table 3. REE concentrations of the wall rock, emeralds and calcite. ICP-OES technique was used for calcite and wall rock analyses. Parisites and emeralds were analyzed by ICP-MS. (1) Emerald values are the mean of seven samples of Alonso-Perez et al. (2021). (2) Upper crustal values are from Rudnik et al. (2003). All concentrations in ppm.
CalciteLaCePrNdSmEuGdTbDyHoErTmYbLu
5.119.22.717.565.4530.26.4408243.8263.5
Black shale. 1 cm distant1.91.50.20.80.20.10.60.10.60.10.30.10.40.1
Black shale. 1 m distant9.78.31.03.91.20.21.60.32.20.51.70.32.00.4
PA-01 (mean of 18)82,454149,38517,63265,05783997544171327115313419011311
PA-02 (mean of 17)85,103149,38517,34563,53580647543819298106612618211312
PA-03 (mean of 23)84,154150,60617,17860,36379487004516347121813418111323
PA-04 (mean of 13)85,140150,60618,49569,7378746694469232210481101448202
Emerald (mean of 7) (1)0.17740.383060.04460.16950.0380.0080.0320.0040.0220.0030.0090.0020.0120.003
Upper crust (2)31637.1274.7140.73.90.832.30.320.31
Table
Table 4. 147Sm/144Nd, 143Nd/144Nd and 145Nd/144Nd data.
Table 4. 147Sm/144Nd, 143Nd/144Nd and 145Nd/144Nd data.
SampleAge (Ma)2s147Sm/144Nd2se143Nd/144Nd2se145Nd/144Nd2seeNd(t)
PA-01
PA-01 0147.910.07910.00040.5121470.0000260.3484060.000027−8.86
PA-01 0247.910.07790.00010.5121560.0000300.3483910.000026−8.68
PA-01 0347.910.07820.00020.5121370.0000270.3483770.000027−9.05
PA-01 0447.910.07970.00030.5121440.0000300.3484010.000029−8.91
PA-01 0547.910.07900.00020.5121630.0000300.3483810.000025−8.55
PA-01 0647.910.07820.00030.5121360.0000270.3483930.000027−9.07
PA-01 0747.910.07840.00020.5121460.0000310.3483850.000026−8.87
PA-01 0847.910.07760.00010.5121640.0000300.3484050.000026−8.53
PA-01 0947.910.07680.00010.5121540.0000300.3483980.000031−8.71
PA-01 1047.910.07960.00020.5121320.0000280.3483850.000024−9.17
PA-01 1147.910.07810.00020.5121550.0000290.3483830.000026−8.69
PA-01 1247.910.07920.00030.5121660.0000280.3484090.000025−8.49
PA-01 1347.910.07950.00020.5121720.0000280.3483890.000025−8.37
PA-01 1447.910.07900.00030.5121620.0000290.3483790.000023−8.57
PA-01 1547.910.07940.00020.5121680.0000310.3484020.000025−8.45
PA-01 1647.910.08020.00030.5121660.0000300.3483830.000027−8.50
PA-01 1747.910.07840.00020.5121480.0000280.3483850.000025−8.84
PA-01 1847.910.07900.00030.5121670.0000310.3484080.000025−8.48
PA-01 1947.910.07840.00020.5121580.0000300.3483900.000029−8.65
PA-01 2047.910.07890.00020.5121140.0000260.3484010.000026−9.50
Mean47.910.07870.00160.5121530.0000300.348393 −8.75
PA-02
PA-02 0150.110.08550.00010.5121640.0000310.3483770.000027−8.53
PA-02 0250.110.08330.00040.5121300.0000300.3483850.000024−9.19
PA-02 0350.110.08490.00030.5121430.0000300.3483680.000026−8.94
PA-02 0450.110.08340.00040.5121730.0000330.3483980.000027−8.35
PA-02 0550.110.08000.00040.5121810.0000310.3483690.000028−8.17
PA-02 0650.110.08020.00040.5121470.0000320.3483770.000027−8.83
PA-02 0750.110.07760.00020.5121740.0000280.3483410.000030−8.29
PA-02 0850.110.07880.00010.5121650.0000290.3483820.000033−8.47
PA-02 0950.110.07810.00030.5121210.0000340.3483760.000034−9.33
PA-02 1050.110.08750.00010.5121650.0000330.3483890.000030−8.54
PA-02 1150.110.08190.00050.5121310.0000310.3483850.000024−9.16
PA-02 1250.110.08480.00030.5121620.0000320.3483840.000026−8.57
PA-02 1350.110.08620.00010.5121690.0000310.3484060.000023−8.44
PA-02 1450.110.07650.00010.5121390.0000310.3483900.000033−8.97
PA-02 1550.110.07690.00010.5121520.0000310.3483580.000029−8.72
PA-02 1650.110.07760.00010.5121480.0000300.3483690.000032−8.80
PA-02 1750.110.07880.00030.5121370.0000330.3483650.000033−9.03
PA-02 1850.110.07750.00010.5121560.0000350.3483840.000030−8.63
PA-02 1950.110.07730.00010.5121300.0000310.3483880.000030−9.15
PA-02 2050.110.07700.00000.5121390.0000330.3483740.000031−8.96
Mean50.110.08070.00720.5121510.0000350.348378 −8.75
PA-03
PA-03 0150.910.08020.000100.5121940.0000310.3484150.000009−7.91
PA-03 0250.910.07980.000100.5121780.0000400.3484110.000011−8.22
PA-03 0350.910.07830.000100.5121880.0000440.3484080.000012−8.01
PA-03 0450.910.07970.000100.5121690.0000420.3484090.000011−8.39
PA-03 0550.910.07960.000100.5121800.0000480.3484130.000011−8.17
PA-03 0650.910.07910.000100.5121840.0000460.3484100.000011−8.09
PA-03 0750.910.08100.000100.5121950.0000450.3484000.000012−7.89
PA-03 0850.910.08040.000100.5121950.0000430.3484040.000013−7.89
PA-03 0950.910.07980.000100.5122000.0000460.3484080.000012−7.79
PA-03 1050.910.07850.000100.5121740.0000410.3484140.000010−8.28
PA-03 1150.910.08090.000100.5121990.0000470.3484100.000012−7.81
PA-03 1250.910.08070.000100.5121790.0000350.3484070.000010−8.20
PA-03 1350.910.07850.000100.5121730.0000390.3484070.000010−8.30
PA-03 1450.910.08090.000100.5121880.0000360.3484100.000011−8.03
PA-03 1550.910.07830.000100.5121740.0000400.3484240.000011−8.28
PA-03 1650.910.07920.000100.5121880.0000420.3484150.000011−8.02
PA-03 1750.910.07930.000100.5121990.0000460.3484160.000012−7.80
PA-03 1850.910.07920.000100.5121770.0000340.3484060.000010−8.23
PA-03 1950.910.08060.000100.5121680.0000390.3484110.000010−8.42
PA-03 2050.910.07970.000100.5121770.0000380.3484060.000010−8.23
Mean50.910.07970.00180.5121840.0000210.348410 −8.10
PA-04
PA-04 0146.810.07630.00000.5121660.0000290.3484010.000029−8.49
PA-04 0246.810.07580.00000.5121500.0000300.3484000.000034−8.80
PA-04 0346.810.07700.00010.5121540.0000310.3483880.000033−8.74
PA-04 0446.810.07630.00010.5121750.0000310.3484040.000033−8.32
PA-04 0546.810.07670.00010.5121330.0000280.3484170.000031−9.14
PA-04 0646.810.07690.00010.5121250.0000270.3484080.000034−9.29
PA-04 0746.810.07680.00010.5121630.0000270.3484110.000033−8.55
PA-04 0846.810.07630.00010.5121340.0000260.3483930.000034−9.11
PA-04 0946.810.07660.00000.5121510.0000250.3484030.000033−8.78
PA-04 1046.810.07630.00000.5121450.0000260.3483950.000039−8.91
PA-04 1146.810.07580.00000.5121800.0000270.3484180.000035−8.20
PA-04 1246.810.07660.00010.5121450.0000280.3484040.000032−8.89
PA-04 1346.810.07650.00000.5121240.0000250.3483900.000034−9.31
PA-04 1446.810.07580.00000.5121460.0000260.3483990.000033−8.87
PA-04 1546.810.07630.00010.5121220.0000270.3484050.000035−9.34
PA-04 1646.810.07620.00010.5121440.0000260.3483950.000034−8.92
PA-04 1746.810.07590.00000.5121320.0000250.3483950.000035−9.15
PA-04 1846.810.07740.00010.5121350.0000250.3484010.000038−9.10
PA-04 1946.810.07680.00000.5121440.0000270.3483990.000038−8.93
PA-04 2046.810.07650.00010.5121330.0000270.3483900.000038−9.14
Mean46.810.07640.00090.5121450.0000330.348401 −8.90
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MDPI and ACS Style

Altenberger, U.; Rojas-Agramonte, Y.; Yang, Y.; Fernández-Lamus, J.; Häger, T.; Guenter, C.; Gonzalez-Pinzón, A.; Charris-Leal, F.; Artel, J. In Situ U–Th–Pb Dating of Parisite: Implication for the Age of Mineralization of Colombian Emeralds. Minerals 2022, 12, 1232. https://doi.org/10.3390/min12101232

AMA Style

Altenberger U, Rojas-Agramonte Y, Yang Y, Fernández-Lamus J, Häger T, Guenter C, Gonzalez-Pinzón A, Charris-Leal F, Artel J. In Situ U–Th–Pb Dating of Parisite: Implication for the Age of Mineralization of Colombian Emeralds. Minerals. 2022; 12(10):1232. https://doi.org/10.3390/min12101232

Chicago/Turabian Style

Altenberger, Uwe, Yamirka Rojas-Agramonte, Yueheng Yang, Jimmy Fernández-Lamus, Tobias Häger, Christina Guenter, Alejandra Gonzalez-Pinzón, Felipe Charris-Leal, and Julia Artel. 2022. "In Situ U–Th–Pb Dating of Parisite: Implication for the Age of Mineralization of Colombian Emeralds" Minerals 12, no. 10: 1232. https://doi.org/10.3390/min12101232

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