Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate
This study aimed to synthesize a green powdered layered double hydroxide (LDH) based on nickel-aluminum (Ni–Al-LDH) to evaluate its efficiency in the removal of rare earth elements (REEs), Praseodymium (Pr3+) and Samarium (Sm3+), from synthetic effluents and real leachate using phosphogypsum as a se...
- Autores:
-
dos Reis, Glaydson S.
Dotto, Guilherme Luiz
Vieillard, Julien
Silva Oliveira, Marcos Leandro
Frantz Lütke, Sabrina
Grimm, Alejandro
Silva Oliveira, Luis Felipe
Lima, Éder C.
Naushad, Mu.
Lassi, Ulla
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2023
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/10550
- Acceso en línea:
- https://hdl.handle.net/11323/10550
https://repositorio.cuc.edu.co/
- Palabra clave:
- Layered double hydroxide
Phosphogypsum leachate
Adsorption
Recovery
Rare earth elements
- Rights
- embargoedAccess
- License
- Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
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| dc.title.eng.fl_str_mv |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| title |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| spellingShingle |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate Layered double hydroxide Phosphogypsum leachate Adsorption Recovery Rare earth elements |
| title_short |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| title_full |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| title_fullStr |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| title_full_unstemmed |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| title_sort |
Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate |
| dc.creator.fl_str_mv |
dos Reis, Glaydson S. Dotto, Guilherme Luiz Vieillard, Julien Silva Oliveira, Marcos Leandro Frantz Lütke, Sabrina Grimm, Alejandro Silva Oliveira, Luis Felipe Lima, Éder C. Naushad, Mu. Lassi, Ulla |
| dc.contributor.author.none.fl_str_mv |
dos Reis, Glaydson S. Dotto, Guilherme Luiz Vieillard, Julien Silva Oliveira, Marcos Leandro Frantz Lütke, Sabrina Grimm, Alejandro Silva Oliveira, Luis Felipe Lima, Éder C. Naushad, Mu. Lassi, Ulla |
| dc.subject.proposal.eng.fl_str_mv |
Layered double hydroxide Phosphogypsum leachate Adsorption Recovery Rare earth elements |
| topic |
Layered double hydroxide Phosphogypsum leachate Adsorption Recovery Rare earth elements |
| description |
This study aimed to synthesize a green powdered layered double hydroxide (LDH) based on nickel-aluminum (Ni–Al-LDH) to evaluate its efficiency in the removal of rare earth elements (REEs), Praseodymium (Pr3+) and Samarium (Sm3+), from synthetic effluents and real leachate using phosphogypsum as a secondary source of REEs. Several characterization techniques were employed to evaluate the physicochemical properties of Ni-Al-LDH adsorbent, such as specific surface area and porosity, functional surface groups and phases, and point of zero charge. The characterization results indicated that Ni-Al-LDH exhibited a typical layered structure confirming the successful synthesis. The effect of key adsorption variables, such as pH, contact time, initial concentration, and temperature, on the REEs adsorption was extensively studied in single-factor experiments separately. The kinetic and equilibrium adsorption data agreeably fitted the Avrami and Sips models, respectively. The maximum adsorption capacities for Pr3+ and Sm3+ adsorption were 18.13 and 15.68 mg g−1 at 298 K, respectively. The thermodynamic parameters (ΔH0, ΔS0, ΔG0) indicated that the adsorption was spontaneous, favorable, and exothermic for both Pr3+ and Sm3+. The interactions between Pr3+ and Sm3+ onto Ni-Al-LDH suggest that multiple adsorption mechanisms are involved, such as ion exchange, precipitation, chelation, and pore filling. Finally, the Ni-Al-LDH could selectively recover REEs, specially Pr3+ and Sm3+, from the real phosphogypsum leachate. It has been demonstrated that Ni-Al-LDH is a promising adsorbent material that could be used as an adsorbent for the recovery of REEs from synthetic and real effluents. |
| publishDate |
2023 |
| dc.date.accessioned.none.fl_str_mv |
2023-10-19T20:26:09Z |
| dc.date.available.none.fl_str_mv |
2023-10-19T20:26:09Z 2025-10-15 |
| dc.date.issued.none.fl_str_mv |
2023-10-15 |
| dc.type.spa.fl_str_mv |
Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
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Text |
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info:eu-repo/semantics/article |
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http://purl.org/redcol/resource_type/ART |
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Glaydson S. dos Reis, Guilherme L. Dotto, Julien Vieillard, Marcos L.S. Oliveira, Sabrina F. Lütke, Alejandro Grimm, Luis F.O. Silva, Éder C. Lima, Mu. Naushad, Ulla Lassi, Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate, Journal of Alloys and Compounds, Volume 960, 2023, 170530, ISSN 0925-8388, https://doi.org/10.1016/j.jallcom.2023.170530 |
| dc.identifier.issn.spa.fl_str_mv |
0925-8388 |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/10550 |
| dc.identifier.doi.none.fl_str_mv |
10.1016/j.jallcom.2023.170530 |
| dc.identifier.eissn.spa.fl_str_mv |
1873-4669 |
| dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.spa.fl_str_mv |
REDICUC - Repositorio CUC |
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https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Glaydson S. dos Reis, Guilherme L. Dotto, Julien Vieillard, Marcos L.S. Oliveira, Sabrina F. Lütke, Alejandro Grimm, Luis F.O. Silva, Éder C. Lima, Mu. Naushad, Ulla Lassi, Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate, Journal of Alloys and Compounds, Volume 960, 2023, 170530, ISSN 0925-8388, https://doi.org/10.1016/j.jallcom.2023.170530 0925-8388 10.1016/j.jallcom.2023.170530 1873-4669 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/10550 https://repositorio.cuc.edu.co/ |
| dc.language.iso.spa.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.spa.fl_str_mv |
Journal of Alloys and Compounds |
| dc.relation.references.spa.fl_str_mv |
[1] M.A. de Boer, K. Lammertsma, Scarcity of rare earth elements, ChemSusChem 6 (2013) 2045–2055. [2] L. Omodara, S. Pitkaaho, E.-M. Turpeinen, P. Saavalainen, K. Oravisjarvi, R.L. Keiski, Recycling and substitution of light rare earth elements, cerium, lanthanum, neodymium, and praseodymium from end-of-life applications - A review, J. Clean. Prod. 236 (2019) 117573. [3] M.P.P. Mejame, D. King, Z. Banhalmi-zakar, Y. He, Circular economy: a sustainable management strategy for rare earth elements consumption in Australia, Curr. Res. Environ. Sustain. 4 (2022) 100157. [4] J. Li, K. Peng, P. Wang, N. Zhang, K. Feng, D. Guan, J. Meng, W. Wei, Q. Yang, Critical Rare-Earth Elements Mismatch Global WindPower Ambitions, One Earth 3 (2020) 116–125. [5] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, Anal., Recycl., Environ. Impact Geosci. Front 10 (2019) 1285–1303. [6] Q.M. Liang, H.M. Yin, J.M. Li, L. Zhang, B.S. Liping, R.M. Hou, S.D. Wang, Investigation of rare earth elements in urine and drinking water of children in mining area, Medicine 97 (2018) e12717. [7] H. Paulick, E. Machacek, The global rare earth element exploration boom: an analysis of resources outside of China and discussion of development perspectives, Resour. Policy 52 (2017) 134–153. [8] S.F. Lütke, M.L.S. Oliveira, S.R. Waechter, L.F.O. Silva, T.R.S. Cadaval Jr., F.A. Duarte, G.L. Dotto, Leaching of rare earth elements from phosphogypsum, Chemosphere 301 (2022) 134661. [9] J. Kulczycka, Z. Kowalski, M. Smol, H. Wirth, Evaluation of the recovery of rare earth elements (REE) from phosphogypsum waste case study of the WIZOW chemical plant (Poland), J. Clean. Prod. 113 (2016) 345–354. [10] V.N. Rychkov, E.V. Kirillov, S.V. Kirillov, V.S. Semenishchev, G.M. Bunkov, M.S. Botalov, D.V. Smyshlyaev, A.S. Malyshev, Recovery of rare earth elements from phosphogypsum, J. Clean. Prod. 196 (2018) 674–681. [11] I. Hammas-Nasri, K. Horchani-Naifer, M. Ferid, D. Barca, Production of a rare earths concentrate after phosphogypsum treatment with dietary NaCl and Na2CO3 solutions, Miner. Eng. 132 (2019) 169–174. [12] N. Haque, A. Hughes, S. Lim, C. Vernon. Rare earth elements: overview of mining, mineralogy, uses, sustainability and environmental impact, Resources 3 (2014) 614–635. [13] J.C. Callura, K.M. Perkins, C.W. Noack, N.R. Washburn, D.A. Dzombak, A.K. Karamalidis, Selective adsorption of rare earth elements onto functionalized silica particles, Green. Chem. 20 (7) (2018) 1515–1526. [14] S. Iftekhar, D.L. Ramasamy, V. Srivastava, M.B. Asif, M. Sillanpaa, Understanding the factors affecting the adsorption of lanthanum using different adsorbents: a critical review, Chemosphere 204 (2018) 413–430. [15] Y. Huang, H. He, X. Liang, Z. Bao, W. Tan, L. Ma, J. Zhu, J. Huang, H. Wang, Characteristics and genesis of ion adsorption type REE deposits in the weathering crusts of metamorphic rocks in Ningdu, Ganzhou, China, Ore Geol. Rev. 135 (2021) 104173. [16] G.S. dos Reis, D. Pinto, E.C. Lima, S. Knani, A. Grimm, L.F.O. Silva, T.R.S. Cadaval Jr, G.L. Dotto, Lanthanum uptake from water using chitosan with different configurations, React. Funct. Polym. 180 (2022) 105395. [17] E.C. Lima, D. Pinto, M.S. Netto, G.S. dos Reis, L.F.O. Silva, G.L. Dotto, Biosorption of Neodymium (Nd) from aqueous solutions using Spirulina platensis sp. Strains, Polymers 14 (2022) 4585. [18] J. Xiao, B. Li, R. Qiang, H. Qiu, J. Chen, Highly selective adsorption of rare earth elements by honeycomb-shaped covalent organic frameworks synthesized in deep eutectic solvents, Environ. Res. 214 (2022) 113977. [19] E.E. Abdel-Hady, R. Mahmoud, S.H.M. Hafez, H.F.M. Mohamed, Hierarchical ternary ZnCoFe layered double hydroxide as efficient adsorbent and catalyst for methanol electrooxidation, J. Mater. Res. Technol. 17 (2022) 1922–1941. [20] Bianca S. Marques, Keterli Dalmagro, Kelly S. Moreira, Marcos L.S. Oliveira, Sergio L. Jahn, Thiago A. de Lima Burgo, Guilherme L. Dotto, Ca-Al, Ni-Al and Zn-Al LDH powders as efficient materials to treat synthetic effluents containing o-nitrophenol, J. Alloy. Compd. 838 (2020) 155628. [21] R. Mahmoud, H.F.M. Mohamed, S.H.M. Hafez, Y.M. Gadelhak, E.E. Abdel-Hady, Valorization of spent double substituted Co–Ni–Zn–Fe LDH wastewater nanoadsorbent as methanol electro-oxidation catalyst, Sci. Rep. 12 (2022) 19354. [22] NFGM Cimirro, E.C. Lima, M.R Cunha, P.S. Thue, A. Grimm, G.S. dos Reis, N. Rabiee, M.R. Saeb, F. Keivanimehr, S. Habibzadeh, Removal of diphenols using pine biochar. Kinetics, equilibrium, thermodynamics, and mechanism of uptake, J. Mol. Liq. 364 (2022) 119979. [23] M. Guy, M. Mathieu, I.P. Anastopoulos, M.G. Martínez, F. Rousseau, G.L. Dotto, H.P. de Oliveira, E.C. Lima, M. Thyrel, S.H. Larsson, G.S. dos Reis, Process parameters optimization, characterization, and application of KOH-activated Norway spruce bark graphitic biochars for efficient azo dye adsorption, Molecules 27 (2022) 456. [24] M. Gonzalez-Hourcade, G.S. dos Reis, A. Grimm, V.M. Dinh, E.C. Lima, S.H. Larsson, F.G. Gentili, Microalgae biomass as a sustainable precursor to produce nitrogen-doped biochar for efficient removal of emerging pollutants from aqueous media, J. Clean. Prod. 348 (2022) 131280. [25] G.S. dos Reis, M. Guy, M. Mathieu, M. Jebrane, E.C. Lima, M. Thyrel, G.L. Dotto, S.H. Larsson, A comparative study of chemical treatment by MgCl2, ZnSO4, ZnCl2, and KOH on physicochemical properties and acetaminophen adsorption performance of biobased porous materials from tree bark residues, Colloids Surf. A Physicochem. Eng. Asp. 642 (2022) 642. [26] R.A. Teixeira, E.C. Lima, A.D. Benetti, P.S. Thue, M.R. Cunha, N. Cimirro, F. Sher, M.H. Dehghani, G.S. dos Reis, G.L. Dotto, Preparation of hybrids of wood sawdust with 3-aminopropyltriethoxysilane. Application as an adsorbent to remove reactive blue 4 dye from wastewater effluents, J. Taiwan Inst. Chem. Eng. 125 (2021) 141–152. [27] W. Li, R. Chen, Q. Liu, J. Liu, J. Yu, H. Zhang, R. Li, M. Zhang, J. Wang, Hierarchical Ni−Al Layered Double Hydroxide In Situ Anchored onto PolyethylenimineFunctionalized Fibers for Efficient U(VI) Capture, AS Sustain. Chem. Eng. 6 (2018) 13385–13394. [28] X. Yuan, X.Y. Jing, H. Xu, X. Zhang, J. Xu, Ni–Al layered double hydroxides modified sponge skeleton with polydopamine coating for enhanced U(VI) extraction from aqueous solution, Chemosphere 287 (2022) 131919. [29] M.S. Ahmed, M.S.J. Khan, S.B. Khan, K. Akhtar, E.M. Bakhsh, A. Khalil, S.A. Khan, A.M. Asiri, T. Kamal, Ni–Al-layered double-hydroxide photocatalyst for the visible light-assisted photodegradation of organic dye pollutants, Appl. Nanosci. 12 (2022) 3597–3606. [30] A.A.E. Sakr, T. Zaki, O. Saber, S.A. Hassan, A.K. Aboul-Gheit, S. Faramawy, Synthesis of Zn-Al LDHs intercalated with urea derived anions for capturing carbon dioxide from natural gas, J. Taiwan Inst. Chem. Eng. 44 (2013) 957–962. [31] C. Qi, J.C. Qmplett, B.A. Peppley, Product composition as a function of temperature over NiAl-layered double hydroxide derived catalysts in steam reforming of methanol, Appl. Catal. A: Gen. 302 (2006) 237–243. [32] H. Lu, J. Chen, Q. Tian, Wearable high-performance supercapacitors based on Nicoated cotton textile with low-crystalline Ni-Al layered double hydroxide nanoparticles, J. Colloid Interface Sci. 513 (2018) 342–348. [33] H. Zhang, M.U. Tahir, X. Yan, X. Liu, X. Su, L. Zhang, Ni-Al layered double hydroxide with regulated interlayer spacing as electrode for aqueous asymmetric supercapacitor, Chem. Eng. J. 368 (2019) 905–913. [34] G. Mishra, B. Dash, S. Pandey, Layered double hydroxides: a brief review from fundamentals to application as evolving biomaterials, Appl. Clay Sci. 153 (2017) 172–186. [35] H. Hatami, A. Fotovat, A. Halajnia, Comparison of adsorption and desorption of phosphate on synthesized Zn-Al LDH by two methods in a simulated soil solution, Appl. Clay Sci. 152 (2017) 333–341. [36] E.M. Seftel, R.G. Ciocarlan, B. Michielsen, V. Meynen, S. Mullens, P. Cool, Insights into phosphate adsorption behavior on structurally modified ZnAl layered double hydroxides, Appl. Clay Sci. 165 (2018) 234–246. [37] M. Zubair, M. Daud, Gordon McKayd, F. Shehzad, M.A. Al-Harthi, Recent progress in layered double hydroxides (LDH)-containing hybrids as adsorbents for water remediation, Appl. Clay Sci. 143 (2017) 279–292. [38] Y. Liu, C. Luo, G.J. Cui, S.Q. Yan, Synthesis of manganese dioxide/iron oxide/ graphene oxide magnetic nanocomposites for hexavalent chromium removal, RSC Adv. 5 (2015) 54156–54164. [39] X. Yuan, Y. Wang, J. Wang, C. Zhou, Q. Tang, X. Rao, Calcined graphene/ MgAllayered double hydroxides for enhanced Cr(VI) removal, Chem. Eng. J. 221 (2013) 204–213. [40] E.C. Lima, A. Hosseini-Bandegharaei, I. Anastopoulos, A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption, J. Mol. Liq. 273 (2019) 425–434 273. [41] U.S. Feitoza, P.S. Thue, E.C. Lima, G.S. dos Reis, N. Rabiee, W.S. de Alencar, B.L. Mello, Y. Dehmani, J. Rinklebe, S.L.P. Dias, Use of biochar prepared from the Açaí Seed as adsorbent for the uptake of catechol from synthetic effluents, Molecules 27 (2022) 7570. [42] E.H.M. Cavalcante, I.C.M. Candido, H.P. de Oliveira, K.B. Silveira, T. Victor de Souza Alvares, E.C. Lima, M. Thyrel, S.H. Larsson, G. Simoes, Dos Reis, 3- Aminopropyltriethoxysilane-functionalized tannin-rich grape biomass for the adsorption of methyl orange dye: synthesis, characterization, and the adsorption mechanism, ACS Omega 7 (2022) 18997–19009. [43] R. Chang, J.W. Thoman-Jr, 2014. Chapter 17- Intermolecular forces, in: "Physical Chemistry for Chemical Sciences," University Science Books, 2014, pp. 779– 808. [44] M.A. González, I. Pavlovic, R. Rojas-Delgado, C. Barriga, Removal of Cu2+, Pb2+ and Cd2+ by Layered Double Hydroxide– humate hybrid. Sorbate and sorbent comparative studies, Chem. Eng. J. 254 (2014) 605–611. [45] W. He, K. Ai, X. Ren, S. Wang, L. Lu, Inorganic layered ion-exchangers for decontamination of toxic metal ions in aquatic systems, J. Mater. Chem. A 5 (2017) 19593–19606. [46] X. Guan, X. Yuan, Y. Zhao, J. Bai, Y. Li, Y. Cao, Y. Chen, T. Xiong, Adsorption behaviors and mechanisms of Fe/Mg layered double hydroxide loaded on bentonite on Cd (II) and Pb (II) removal, J. Colloid Int. Sci. 612 (2022) 572–583. |
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Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)© 2023 Elsevier B.V. All rights reserved.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/embargoedAccesshttp://purl.org/coar/access_right/c_f1cfdos Reis, Glaydson S.Dotto, Guilherme LuizVieillard, JulienSilva Oliveira, Marcos LeandroFrantz Lütke, SabrinaGrimm, AlejandroSilva Oliveira, Luis FelipeLima, Éder C.Naushad, Mu.Lassi, Ulla2023-10-19T20:26:09Z2025-10-152023-10-19T20:26:09Z2023-10-15Glaydson S. dos Reis, Guilherme L. Dotto, Julien Vieillard, Marcos L.S. Oliveira, Sabrina F. Lütke, Alejandro Grimm, Luis F.O. Silva, Éder C. Lima, Mu. Naushad, Ulla Lassi, Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate, Journal of Alloys and Compounds, Volume 960, 2023, 170530, ISSN 0925-8388, https://doi.org/10.1016/j.jallcom.2023.1705300925-8388https://hdl.handle.net/11323/1055010.1016/j.jallcom.2023.1705301873-4669Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/This study aimed to synthesize a green powdered layered double hydroxide (LDH) based on nickel-aluminum (Ni–Al-LDH) to evaluate its efficiency in the removal of rare earth elements (REEs), Praseodymium (Pr3+) and Samarium (Sm3+), from synthetic effluents and real leachate using phosphogypsum as a secondary source of REEs. Several characterization techniques were employed to evaluate the physicochemical properties of Ni-Al-LDH adsorbent, such as specific surface area and porosity, functional surface groups and phases, and point of zero charge. The characterization results indicated that Ni-Al-LDH exhibited a typical layered structure confirming the successful synthesis. The effect of key adsorption variables, such as pH, contact time, initial concentration, and temperature, on the REEs adsorption was extensively studied in single-factor experiments separately. The kinetic and equilibrium adsorption data agreeably fitted the Avrami and Sips models, respectively. The maximum adsorption capacities for Pr3+ and Sm3+ adsorption were 18.13 and 15.68 mg g−1 at 298 K, respectively. The thermodynamic parameters (ΔH0, ΔS0, ΔG0) indicated that the adsorption was spontaneous, favorable, and exothermic for both Pr3+ and Sm3+. The interactions between Pr3+ and Sm3+ onto Ni-Al-LDH suggest that multiple adsorption mechanisms are involved, such as ion exchange, precipitation, chelation, and pore filling. Finally, the Ni-Al-LDH could selectively recover REEs, specially Pr3+ and Sm3+, from the real phosphogypsum leachate. It has been demonstrated that Ni-Al-LDH is a promising adsorbent material that could be used as an adsorbent for the recovery of REEs from synthetic and real effluents.9 páginasapplication/pdfengElsevier BVNetherlandshttps://www.sciencedirect.com/science/article/pii/S0925838823018339Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachateArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Journal of Alloys and Compounds[1] M.A. de Boer, K. Lammertsma, Scarcity of rare earth elements, ChemSusChem 6 (2013) 2045–2055.[2] L. Omodara, S. Pitkaaho, E.-M. Turpeinen, P. Saavalainen, K. Oravisjarvi, R.L. Keiski, Recycling and substitution of light rare earth elements, cerium, lanthanum, neodymium, and praseodymium from end-of-life applications - A review, J. Clean. Prod. 236 (2019) 117573.[3] M.P.P. Mejame, D. King, Z. Banhalmi-zakar, Y. He, Circular economy: a sustainable management strategy for rare earth elements consumption in Australia, Curr. Res. Environ. Sustain. 4 (2022) 100157.[4] J. Li, K. Peng, P. Wang, N. Zhang, K. Feng, D. Guan, J. Meng, W. Wei, Q. Yang, Critical Rare-Earth Elements Mismatch Global WindPower Ambitions, One Earth 3 (2020) 116–125.[5] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, Anal., Recycl., Environ. Impact Geosci. Front 10 (2019) 1285–1303.[6] Q.M. Liang, H.M. Yin, J.M. Li, L. Zhang, B.S. Liping, R.M. Hou, S.D. Wang, Investigation of rare earth elements in urine and drinking water of children in mining area, Medicine 97 (2018) e12717.[7] H. Paulick, E. Machacek, The global rare earth element exploration boom: an analysis of resources outside of China and discussion of development perspectives, Resour. Policy 52 (2017) 134–153.[8] S.F. Lütke, M.L.S. Oliveira, S.R. Waechter, L.F.O. Silva, T.R.S. Cadaval Jr., F.A. Duarte, G.L. Dotto, Leaching of rare earth elements from phosphogypsum, Chemosphere 301 (2022) 134661.[9] J. Kulczycka, Z. Kowalski, M. Smol, H. Wirth, Evaluation of the recovery of rare earth elements (REE) from phosphogypsum waste case study of the WIZOW chemical plant (Poland), J. Clean. Prod. 113 (2016) 345–354.[10] V.N. Rychkov, E.V. Kirillov, S.V. Kirillov, V.S. Semenishchev, G.M. Bunkov, M.S. Botalov, D.V. Smyshlyaev, A.S. Malyshev, Recovery of rare earth elements from phosphogypsum, J. Clean. Prod. 196 (2018) 674–681.[11] I. Hammas-Nasri, K. Horchani-Naifer, M. Ferid, D. Barca, Production of a rare earths concentrate after phosphogypsum treatment with dietary NaCl and Na2CO3 solutions, Miner. Eng. 132 (2019) 169–174.[12] N. Haque, A. Hughes, S. Lim, C. Vernon. Rare earth elements: overview of mining, mineralogy, uses, sustainability and environmental impact, Resources 3 (2014) 614–635.[13] J.C. Callura, K.M. Perkins, C.W. Noack, N.R. Washburn, D.A. Dzombak, A.K. Karamalidis, Selective adsorption of rare earth elements onto functionalized silica particles, Green. Chem. 20 (7) (2018) 1515–1526.[14] S. Iftekhar, D.L. Ramasamy, V. Srivastava, M.B. Asif, M. Sillanpaa, Understanding the factors affecting the adsorption of lanthanum using different adsorbents: a critical review, Chemosphere 204 (2018) 413–430.[15] Y. Huang, H. He, X. Liang, Z. Bao, W. Tan, L. Ma, J. Zhu, J. Huang, H. Wang, Characteristics and genesis of ion adsorption type REE deposits in the weathering crusts of metamorphic rocks in Ningdu, Ganzhou, China, Ore Geol. Rev. 135 (2021) 104173.[16] G.S. dos Reis, D. Pinto, E.C. Lima, S. Knani, A. Grimm, L.F.O. Silva, T.R.S. Cadaval Jr, G.L. Dotto, Lanthanum uptake from water using chitosan with different configurations, React. Funct. Polym. 180 (2022) 105395.[17] E.C. Lima, D. Pinto, M.S. Netto, G.S. dos Reis, L.F.O. Silva, G.L. Dotto, Biosorption of Neodymium (Nd) from aqueous solutions using Spirulina platensis sp. Strains, Polymers 14 (2022) 4585.[18] J. Xiao, B. Li, R. Qiang, H. Qiu, J. Chen, Highly selective adsorption of rare earth elements by honeycomb-shaped covalent organic frameworks synthesized in deep eutectic solvents, Environ. Res. 214 (2022) 113977.[19] E.E. Abdel-Hady, R. Mahmoud, S.H.M. Hafez, H.F.M. Mohamed, Hierarchical ternary ZnCoFe layered double hydroxide as efficient adsorbent and catalyst for methanol electrooxidation, J. Mater. Res. Technol. 17 (2022) 1922–1941.[20] Bianca S. Marques, Keterli Dalmagro, Kelly S. Moreira, Marcos L.S. Oliveira, Sergio L. Jahn, Thiago A. de Lima Burgo, Guilherme L. Dotto, Ca-Al, Ni-Al and Zn-Al LDH powders as efficient materials to treat synthetic effluents containing o-nitrophenol, J. Alloy. Compd. 838 (2020) 155628.[21] R. Mahmoud, H.F.M. Mohamed, S.H.M. Hafez, Y.M. Gadelhak, E.E. Abdel-Hady, Valorization of spent double substituted Co–Ni–Zn–Fe LDH wastewater nanoadsorbent as methanol electro-oxidation catalyst, Sci. Rep. 12 (2022) 19354.[22] NFGM Cimirro, E.C. Lima, M.R Cunha, P.S. Thue, A. Grimm, G.S. dos Reis, N. Rabiee, M.R. Saeb, F. Keivanimehr, S. Habibzadeh, Removal of diphenols using pine biochar. Kinetics, equilibrium, thermodynamics, and mechanism of uptake, J. Mol. Liq. 364 (2022) 119979.[23] M. Guy, M. Mathieu, I.P. Anastopoulos, M.G. Martínez, F. Rousseau, G.L. Dotto, H.P. de Oliveira, E.C. Lima, M. Thyrel, S.H. Larsson, G.S. dos Reis, Process parameters optimization, characterization, and application of KOH-activated Norway spruce bark graphitic biochars for efficient azo dye adsorption, Molecules 27 (2022) 456.[24] M. Gonzalez-Hourcade, G.S. dos Reis, A. Grimm, V.M. Dinh, E.C. Lima, S.H. Larsson, F.G. Gentili, Microalgae biomass as a sustainable precursor to produce nitrogen-doped biochar for efficient removal of emerging pollutants from aqueous media, J. Clean. Prod. 348 (2022) 131280.[25] G.S. dos Reis, M. Guy, M. Mathieu, M. Jebrane, E.C. Lima, M. Thyrel, G.L. Dotto, S.H. Larsson, A comparative study of chemical treatment by MgCl2, ZnSO4, ZnCl2, and KOH on physicochemical properties and acetaminophen adsorption performance of biobased porous materials from tree bark residues, Colloids Surf. A Physicochem. Eng. Asp. 642 (2022) 642.[26] R.A. Teixeira, E.C. Lima, A.D. Benetti, P.S. Thue, M.R. Cunha, N. Cimirro, F. Sher, M.H. Dehghani, G.S. dos Reis, G.L. Dotto, Preparation of hybrids of wood sawdust with 3-aminopropyltriethoxysilane. Application as an adsorbent to remove reactive blue 4 dye from wastewater effluents, J. Taiwan Inst. Chem. Eng. 125 (2021) 141–152.[27] W. Li, R. Chen, Q. Liu, J. Liu, J. Yu, H. Zhang, R. Li, M. Zhang, J. Wang, Hierarchical Ni−Al Layered Double Hydroxide In Situ Anchored onto PolyethylenimineFunctionalized Fibers for Efficient U(VI) Capture, AS Sustain. Chem. Eng. 6 (2018) 13385–13394.[28] X. Yuan, X.Y. Jing, H. Xu, X. Zhang, J. Xu, Ni–Al layered double hydroxides modified sponge skeleton with polydopamine coating for enhanced U(VI) extraction from aqueous solution, Chemosphere 287 (2022) 131919.[29] M.S. Ahmed, M.S.J. Khan, S.B. Khan, K. Akhtar, E.M. Bakhsh, A. Khalil, S.A. Khan, A.M. Asiri, T. Kamal, Ni–Al-layered double-hydroxide photocatalyst for the visible light-assisted photodegradation of organic dye pollutants, Appl. Nanosci. 12 (2022) 3597–3606.[30] A.A.E. Sakr, T. Zaki, O. Saber, S.A. Hassan, A.K. Aboul-Gheit, S. Faramawy, Synthesis of Zn-Al LDHs intercalated with urea derived anions for capturing carbon dioxide from natural gas, J. Taiwan Inst. Chem. Eng. 44 (2013) 957–962.[31] C. Qi, J.C. Qmplett, B.A. Peppley, Product composition as a function of temperature over NiAl-layered double hydroxide derived catalysts in steam reforming of methanol, Appl. Catal. A: Gen. 302 (2006) 237–243.[32] H. Lu, J. Chen, Q. Tian, Wearable high-performance supercapacitors based on Nicoated cotton textile with low-crystalline Ni-Al layered double hydroxide nanoparticles, J. Colloid Interface Sci. 513 (2018) 342–348.[33] H. Zhang, M.U. Tahir, X. Yan, X. Liu, X. Su, L. Zhang, Ni-Al layered double hydroxide with regulated interlayer spacing as electrode for aqueous asymmetric supercapacitor, Chem. Eng. J. 368 (2019) 905–913.[34] G. Mishra, B. Dash, S. Pandey, Layered double hydroxides: a brief review from fundamentals to application as evolving biomaterials, Appl. Clay Sci. 153 (2017) 172–186.[35] H. Hatami, A. Fotovat, A. Halajnia, Comparison of adsorption and desorption of phosphate on synthesized Zn-Al LDH by two methods in a simulated soil solution, Appl. Clay Sci. 152 (2017) 333–341.[36] E.M. Seftel, R.G. Ciocarlan, B. Michielsen, V. Meynen, S. Mullens, P. Cool, Insights into phosphate adsorption behavior on structurally modified ZnAl layered double hydroxides, Appl. Clay Sci. 165 (2018) 234–246.[37] M. Zubair, M. Daud, Gordon McKayd, F. Shehzad, M.A. Al-Harthi, Recent progress in layered double hydroxides (LDH)-containing hybrids as adsorbents for water remediation, Appl. Clay Sci. 143 (2017) 279–292.[38] Y. Liu, C. Luo, G.J. Cui, S.Q. Yan, Synthesis of manganese dioxide/iron oxide/ graphene oxide magnetic nanocomposites for hexavalent chromium removal, RSC Adv. 5 (2015) 54156–54164.[39] X. Yuan, Y. Wang, J. Wang, C. Zhou, Q. Tang, X. Rao, Calcined graphene/ MgAllayered double hydroxides for enhanced Cr(VI) removal, Chem. Eng. J. 221 (2013) 204–213.[40] E.C. Lima, A. Hosseini-Bandegharaei, I. Anastopoulos, A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption, J. Mol. Liq. 273 (2019) 425–434 273.[41] U.S. Feitoza, P.S. Thue, E.C. Lima, G.S. dos Reis, N. Rabiee, W.S. de Alencar, B.L. Mello, Y. Dehmani, J. Rinklebe, S.L.P. Dias, Use of biochar prepared from the Açaí Seed as adsorbent for the uptake of catechol from synthetic effluents, Molecules 27 (2022) 7570.[42] E.H.M. Cavalcante, I.C.M. Candido, H.P. de Oliveira, K.B. Silveira, T. Victor de Souza Alvares, E.C. Lima, M. Thyrel, S.H. Larsson, G. Simoes, Dos Reis, 3- Aminopropyltriethoxysilane-functionalized tannin-rich grape biomass for the adsorption of methyl orange dye: synthesis, characterization, and the adsorption mechanism, ACS Omega 7 (2022) 18997–19009.[43] R. Chang, J.W. Thoman-Jr, 2014. Chapter 17- Intermolecular forces, in: "Physical Chemistry for Chemical Sciences," University Science Books, 2014, pp. 779– 808.[44] M.A. González, I. Pavlovic, R. Rojas-Delgado, C. Barriga, Removal of Cu2+, Pb2+ and Cd2+ by Layered Double Hydroxide– humate hybrid. Sorbate and sorbent comparative studies, Chem. Eng. J. 254 (2014) 605–611.[45] W. He, K. Ai, X. Ren, S. Wang, L. Lu, Inorganic layered ion-exchangers for decontamination of toxic metal ions in aquatic systems, J. Mater. Chem. A 5 (2017) 19593–19606.[46] X. Guan, X. Yuan, Y. Zhao, J. Bai, Y. Li, Y. Cao, Y. Chen, T. Xiong, Adsorption behaviors and mechanisms of Fe/Mg layered double hydroxide loaded on bentonite on Cd (II) and Pb (II) removal, J. Colloid Int. Sci. 612 (2022) 572–583.91960Layered double hydroxidePhosphogypsum leachateAdsorptionRecoveryRare earth elementsPublicationORIGINALNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdfNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdfArtículosapplication/pdf5421048https://repositorio.cuc.edu.co/bitstreams/0402ded4-ef9b-4ebd-9868-60312aa76024/downloadf310c57280f7a625b26942505dec718eMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/e3995491-52e3-41f1-ae4c-79bd203329f2/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdf.txtNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdf.txtExtracted texttext/plain43404https://repositorio.cuc.edu.co/bitstreams/f1c107ae-9454-480f-940d-b830774904a7/downloadc3fa9b1b7cd7314029cdbf6f124e13faMD53THUMBNAILNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdf.jpgNickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate.pdf.jpgGenerated Thumbnailimage/jpeg14392https://repositorio.cuc.edu.co/bitstreams/5d488fac-19ae-4b09-bf41-1792155361b5/downloadce963d2cc59149572d77f522950038e6MD5411323/10550oai:repositorio.cuc.edu.co:11323/105502024-09-17 14:08:22.265https://creativecommons.org/licenses/by-nc-nd/4.0/© 2023 Elsevier B.V. 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CUCrepdigital@cuc.edu.coTEEgT0JSQSAoVEFMIFkgQ09NTyBTRSBERUZJTkUgTcOBUyBBREVMQU5URSkgU0UgT1RPUkdBIEJBSk8gTE9TIFRFUk1JTk9TIERFIEVTVEEgTElDRU5DSUEgUMOaQkxJQ0EgREUgQ1JFQVRJVkUgQ09NTU9OUyAo4oCcTFBDQ+KAnSBPIOKAnExJQ0VOQ0lB4oCdKS4gTEEgT0JSQSBFU1TDgSBQUk9URUdJREEgUE9SIERFUkVDSE9TIERFIEFVVE9SIFkvVSBPVFJBUyBMRVlFUyBBUExJQ0FCTEVTLiBRVUVEQSBQUk9ISUJJRE8gQ1VBTFFVSUVSIFVTTyBRVUUgU0UgSEFHQSBERSBMQSBPQlJBIFFVRSBOTyBDVUVOVEUgQ09OIExBIEFVVE9SSVpBQ0nDk04gUEVSVElORU5URSBERSBDT05GT1JNSURBRCBDT04gTE9TIFTDiVJNSU5PUyBERSBFU1RBIExJQ0VOQ0lBIFkgREUgTEEgTEVZIERFIERFUkVDSE8gREUgQVVUT1IuCgpNRURJQU5URSBFTCBFSkVSQ0lDSU8gREUgQ1VBTFFVSUVSQSBERSBMT1MgREVSRUNIT1MgUVVFIFNFIE9UT1JHQU4gRU4gRVNUQSBMSUNFTkNJQSwgVVNURUQgQUNFUFRBIFkgQUNVRVJEQSBRVUVEQVIgT0JMSUdBRE8gRU4gTE9TIFRFUk1JTk9TIFFVRSBTRSBTRcORQUxBTiBFTiBFTExBLiBFTCBMSUNFTkNJQU5URSBDT05DRURFIEEgVVNURUQgTE9TIERFUkVDSE9TIENPTlRFTklET1MgRU4gRVNUQSBMSUNFTkNJQSBDT05ESUNJT05BRE9TIEEgTEEgQUNFUFRBQ0nDk04gREUgU1VTIFRFUk1JTk9TIFkgQ09ORElDSU9ORVMuCjEuIERlZmluaWNpb25lcwoKYS4JT2JyYSBDb2xlY3RpdmEgZXMgdW5hIG9icmEsIHRhbCBjb21vIHVuYSBwdWJsaWNhY2nDs24gcGVyacOzZGljYSwgdW5hIGFudG9sb2fDrWEsIG8gdW5hIGVuY2ljbG9wZWRpYSwgZW4gbGEgcXVlIGxhIG9icmEgZW4gc3UgdG90YWxpZGFkLCBzaW4gbW9kaWZpY2FjacOzbiBhbGd1bmEsIGp1bnRvIGNvbiB1biBncnVwbyBkZSBvdHJhcyBjb250cmlidWNpb25lcyBxdWUgY29uc3RpdHV5ZW4gb2JyYXMgc2VwYXJhZGFzIGUgaW5kZXBlbmRpZW50ZXMgZW4gc8OtIG1pc21hcywgc2UgaW50ZWdyYW4gZW4gdW4gdG9kbyBjb2xlY3Rpdm8uIFVuYSBPYnJhIHF1ZSBjb25zdGl0dXllIHVuYSBvYnJhIGNvbGVjdGl2YSBubyBzZSBjb25zaWRlcmFyw6EgdW5hIE9icmEgRGVyaXZhZGEgKGNvbW8gc2UgZGVmaW5lIGFiYWpvKSBwYXJhIGxvcyBwcm9ww7NzaXRvcyBkZSBlc3RhIGxpY2VuY2lhLiBhcXVlbGxhIHByb2R1Y2lkYSBwb3IgdW4gZ3J1cG8gZGUgYXV0b3JlcywgZW4gcXVlIGxhIE9icmEgc2UgZW5jdWVudHJhIHNpbiBtb2RpZmljYWNpb25lcywganVudG8gY29uIHVuYSBjaWVydGEgY2FudGlkYWQgZGUgb3RyYXMgY29udHJpYnVjaW9uZXMsIHF1ZSBjb25zdGl0dXllbiBlbiBzw60gbWlzbW9zIHRyYWJham9zIHNlcGFyYWRvcyBlIGluZGVwZW5kaWVudGVzLCBxdWUgc29uIGludGVncmFkb3MgYWwgdG9kbyBjb2xlY3Rpdm8sIHRhbGVzIGNvbW8gcHVibGljYWNpb25lcyBwZXJpw7NkaWNhcywgYW50b2xvZ8OtYXMgbyBlbmNpY2xvcGVkaWFzLgoKYi4JT2JyYSBEZXJpdmFkYSBzaWduaWZpY2EgdW5hIG9icmEgYmFzYWRhIGVuIGxhIG9icmEgb2JqZXRvIGRlIGVzdGEgbGljZW5jaWEgbyBlbiDDqXN0YSB5IG90cmFzIG9icmFzIHByZWV4aXN0ZW50ZXMsIHRhbGVzIGNvbW8gdHJhZHVjY2lvbmVzLCBhcnJlZ2xvcyBtdXNpY2FsZXMsIGRyYW1hdGl6YWNpb25lcywg4oCcZmljY2lvbmFsaXphY2lvbmVz4oCdLCB2ZXJzaW9uZXMgcGFyYSBjaW5lLCDigJxncmFiYWNpb25lcyBkZSBzb25pZG/igJ0sIHJlcHJvZHVjY2lvbmVzIGRlIGFydGUsIHJlc8O6bWVuZXMsIGNvbmRlbnNhY2lvbmVzLCBvIGN1YWxxdWllciBvdHJhIGVuIGxhIHF1ZSBsYSBvYnJhIHB1ZWRhIHNlciB0cmFuc2Zvcm1hZGEsIGNhbWJpYWRhIG8gYWRhcHRhZGEsIGV4Y2VwdG8gYXF1ZWxsYXMgcXVlIGNvbnN0aXR1eWFuIHVuYSBvYnJhIGNvbGVjdGl2YSwgbGFzIHF1ZSBubyBzZXLDoW4gY29uc2lkZXJhZGFzIHVuYSBvYnJhIGRlcml2YWRhIHBhcmEgZWZlY3RvcyBkZSBlc3RhIGxpY2VuY2lhLiAoUGFyYSBldml0YXIgZHVkYXMsIGVuIGVsIGNhc28gZGUgcXVlIGxhIE9icmEgc2VhIHVuYSBjb21wb3NpY2nDs24gbXVzaWNhbCBvIHVuYSBncmFiYWNpw7NuIHNvbm9yYSwgcGFyYSBsb3MgZWZlY3RvcyBkZSBlc3RhIExpY2VuY2lhIGxhIHNpbmNyb25pemFjacOzbiB0ZW1wb3JhbCBkZSBsYSBPYnJhIGNvbiB1bmEgaW1hZ2VuIGVuIG1vdmltaWVudG8gc2UgY29uc2lkZXJhcsOhIHVuYSBPYnJhIERlcml2YWRhIHBhcmEgbG9zIGZpbmVzIGRlIGVzdGEgbGljZW5jaWEpLgoKYy4JTGljZW5jaWFudGUsIGVzIGVsIGluZGl2aWR1byBvIGxhIGVudGlkYWQgdGl0dWxhciBkZSBsb3MgZGVyZWNob3MgZGUgYXV0b3IgcXVlIG9mcmVjZSBsYSBPYnJhIGVuIGNvbmZvcm1pZGFkIGNvbiBsYXMgY29uZGljaW9uZXMgZGUgZXN0YSBMaWNlbmNpYS4KCmQuCUF1dG9yIG9yaWdpbmFsLCBlcyBlbCBpbmRpdmlkdW8gcXVlIGNyZcOzIGxhIE9icmEuCgplLglPYnJhLCBlcyBhcXVlbGxhIG9icmEgc3VzY2VwdGlibGUgZGUgcHJvdGVjY2nDs24gcG9yIGVsIHLDqWdpbWVuIGRlIERlcmVjaG8gZGUgQXV0b3IgeSBxdWUgZXMgb2ZyZWNpZGEgZW4gbG9zIHTDqXJtaW5vcyBkZSBlc3RhIGxpY2VuY2lhCgpmLglVc3RlZCwgZXMgZWwgaW5kaXZpZHVvIG8gbGEgZW50aWRhZCBxdWUgZWplcmNpdGEgbG9zIGRlcmVjaG9zIG90b3JnYWRvcyBhbCBhbXBhcm8gZGUgZXN0YSBMaWNlbmNpYSB5IHF1ZSBjb24gYW50ZXJpb3JpZGFkIG5vIGhhIHZpb2xhZG8gbGFzIGNvbmRpY2lvbmVzIGRlIGxhIG1pc21hIHJlc3BlY3RvIGEgbGEgT2JyYSwgbyBxdWUgaGF5YSBvYnRlbmlkbyBhdXRvcml6YWNpw7NuIGV4cHJlc2EgcG9yIHBhcnRlIGRlbCBMaWNlbmNpYW50ZSBwYXJhIGVqZXJjZXIgbG9zIGRlcmVjaG9zIGFsIGFtcGFybyBkZSBlc3RhIExpY2VuY2lhIHBlc2UgYSB1bmEgdmlvbGFjacOzbiBhbnRlcmlvci4KCjIuIERlcmVjaG9zIGRlIFVzb3MgSG9ucmFkb3MgeSBleGNlcGNpb25lcyBMZWdhbGVzLgpOYWRhIGVuIGVzdGEgTGljZW5jaWEgcG9kcsOhIHNlciBpbnRlcnByZXRhZG8gY29tbyB1bmEgZGlzbWludWNpw7NuLCBsaW1pdGFjacOzbiBvIHJlc3RyaWNjacOzbiBkZSBsb3MgZGVyZWNob3MgZGVyaXZhZG9zIGRlbCB1c28gaG9ucmFkbyB5IG90cmFzIGxpbWl0YWNpb25lcyBvIGV4Y2VwY2lvbmVzIGEgbG9zIGRlcmVjaG9zIGRlbCBhdXRvciBiYWpvIGVsIHLDqWdpbWVuIGxlZ2FsIHZpZ2VudGUgbyBkZXJpdmFkbyBkZSBjdWFscXVpZXIgb3RyYSBub3JtYSBxdWUgc2UgbGUgYXBsaXF1ZS4KCjMuIENvbmNlc2nDs24gZGUgbGEgTGljZW5jaWEuCkJham8gbG9zIHTDqXJtaW5vcyB5IGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEsIGVsIExpY2VuY2lhbnRlIG90b3JnYSBhIFVzdGVkIHVuYSBsaWNlbmNpYSBtdW5kaWFsLCBsaWJyZSBkZSByZWdhbMOtYXMsIG5vIGV4Y2x1c2l2YSB5IHBlcnBldHVhIChkdXJhbnRlIHRvZG8gZWwgcGVyw61vZG8gZGUgdmlnZW5jaWEgZGUgbG9zIGRlcmVjaG9zIGRlIGF1dG9yKSBwYXJhIGVqZXJjZXIgZXN0b3MgZGVyZWNob3Mgc29icmUgbGEgT2JyYSB0YWwgeSBjb21vIHNlIGluZGljYSBhIGNvbnRpbnVhY2nDs246CgphLglSZXByb2R1Y2lyIGxhIE9icmEsIGluY29ycG9yYXIgbGEgT2JyYSBlbiB1bmEgbyBtw6FzIE9icmFzIENvbGVjdGl2YXMsIHkgcmVwcm9kdWNpciBsYSBPYnJhIGluY29ycG9yYWRhIGVuIGxhcyBPYnJhcyBDb2xlY3RpdmFzLgoKYi4JRGlzdHJpYnVpciBjb3BpYXMgbyBmb25vZ3JhbWFzIGRlIGxhcyBPYnJhcywgZXhoaWJpcmxhcyBww7pibGljYW1lbnRlLCBlamVjdXRhcmxhcyBww7pibGljYW1lbnRlIHkvbyBwb25lcmxhcyBhIGRpc3Bvc2ljacOzbiBww7pibGljYSwgaW5jbHV5w6luZG9sYXMgY29tbyBpbmNvcnBvcmFkYXMgZW4gT2JyYXMgQ29sZWN0aXZhcywgc2Vnw7puIGNvcnJlc3BvbmRhLgoKYy4JRGlzdHJpYnVpciBjb3BpYXMgZGUgbGFzIE9icmFzIERlcml2YWRhcyBxdWUgc2UgZ2VuZXJlbiwgZXhoaWJpcmxhcyBww7pibGljYW1lbnRlLCBlamVjdXRhcmxhcyBww7pibGljYW1lbnRlIHkvbyBwb25lcmxhcyBhIGRpc3Bvc2ljacOzbiBww7pibGljYS4KTG9zIGRlcmVjaG9zIG1lbmNpb25hZG9zIGFudGVyaW9ybWVudGUgcHVlZGVuIHNlciBlamVyY2lkb3MgZW4gdG9kb3MgbG9zIG1lZGlvcyB5IGZvcm1hdG9zLCBhY3R1YWxtZW50ZSBjb25vY2lkb3MgbyBxdWUgc2UgaW52ZW50ZW4gZW4gZWwgZnV0dXJvLiBMb3MgZGVyZWNob3MgYW50ZXMgbWVuY2lvbmFkb3MgaW5jbHV5ZW4gZWwgZGVyZWNobyBhIHJlYWxpemFyIGRpY2hhcyBtb2RpZmljYWNpb25lcyBlbiBsYSBtZWRpZGEgcXVlIHNlYW4gdMOpY25pY2FtZW50ZSBuZWNlc2FyaWFzIHBhcmEgZWplcmNlciBsb3MgZGVyZWNob3MgZW4gb3RybyBtZWRpbyBvIGZvcm1hdG9zLCBwZXJvIGRlIG90cmEgbWFuZXJhIHVzdGVkIG5vIGVzdMOhIGF1dG9yaXphZG8gcGFyYSByZWFsaXphciBvYnJhcyBkZXJpdmFkYXMuIFRvZG9zIGxvcyBkZXJlY2hvcyBubyBvdG9yZ2Fkb3MgZXhwcmVzYW1lbnRlIHBvciBlbCBMaWNlbmNpYW50ZSBxdWVkYW4gcG9yIGVzdGUgbWVkaW8gcmVzZXJ2YWRvcywgaW5jbHV5ZW5kbyBwZXJvIHNpbiBsaW1pdGFyc2UgYSBhcXVlbGxvcyBxdWUgc2UgbWVuY2lvbmFuIGVuIGxhcyBzZWNjaW9uZXMgNChkKSB5IDQoZSkuCgo0LiBSZXN0cmljY2lvbmVzLgpMYSBsaWNlbmNpYSBvdG9yZ2FkYSBlbiBsYSBhbnRlcmlvciBTZWNjacOzbiAzIGVzdMOhIGV4cHJlc2FtZW50ZSBzdWpldGEgeSBsaW1pdGFkYSBwb3IgbGFzIHNpZ3VpZW50ZXMgcmVzdHJpY2Npb25lczoKCmEuCVVzdGVkIHB1ZWRlIGRpc3RyaWJ1aXIsIGV4aGliaXIgcMO6YmxpY2FtZW50ZSwgZWplY3V0YXIgcMO6YmxpY2FtZW50ZSwgbyBwb25lciBhIGRpc3Bvc2ljacOzbiBww7pibGljYSBsYSBPYnJhIHPDs2xvIGJham8gbGFzIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEsIHkgVXN0ZWQgZGViZSBpbmNsdWlyIHVuYSBjb3BpYSBkZSBlc3RhIGxpY2VuY2lhIG8gZGVsIElkZW50aWZpY2Fkb3IgVW5pdmVyc2FsIGRlIFJlY3Vyc29zIGRlIGxhIG1pc21hIGNvbiBjYWRhIGNvcGlhIGRlIGxhIE9icmEgcXVlIGRpc3RyaWJ1eWEsIGV4aGliYSBww7pibGljYW1lbnRlLCBlamVjdXRlIHDDumJsaWNhbWVudGUgbyBwb25nYSBhIGRpc3Bvc2ljacOzbiBww7pibGljYS4gTm8gZXMgcG9zaWJsZSBvZnJlY2VyIG8gaW1wb25lciBuaW5ndW5hIGNvbmRpY2nDs24gc29icmUgbGEgT2JyYSBxdWUgYWx0ZXJlIG8gbGltaXRlIGxhcyBjb25kaWNpb25lcyBkZSBlc3RhIExpY2VuY2lhIG8gZWwgZWplcmNpY2lvIGRlIGxvcyBkZXJlY2hvcyBkZSBsb3MgZGVzdGluYXRhcmlvcyBvdG9yZ2Fkb3MgZW4gZXN0ZSBkb2N1bWVudG8uIE5vIGVzIHBvc2libGUgc3VibGljZW5jaWFyIGxhIE9icmEuIFVzdGVkIGRlYmUgbWFudGVuZXIgaW50YWN0b3MgdG9kb3MgbG9zIGF2aXNvcyBxdWUgaGFnYW4gcmVmZXJlbmNpYSBhIGVzdGEgTGljZW5jaWEgeSBhIGxhIGNsw6F1c3VsYSBkZSBsaW1pdGFjacOzbiBkZSBnYXJhbnTDrWFzLiBVc3RlZCBubyBwdWVkZSBkaXN0cmlidWlyLCBleGhpYmlyIHDDumJsaWNhbWVudGUsIGVqZWN1dGFyIHDDumJsaWNhbWVudGUsIG8gcG9uZXIgYSBkaXNwb3NpY2nDs24gcMO6YmxpY2EgbGEgT2JyYSBjb24gYWxndW5hIG1lZGlkYSB0ZWNub2zDs2dpY2EgcXVlIGNvbnRyb2xlIGVsIGFjY2VzbyBvIGxhIHV0aWxpemFjacOzbiBkZSBlbGxhIGRlIHVuYSBmb3JtYSBxdWUgc2VhIGluY29uc2lzdGVudGUgY29uIGxhcyBjb25kaWNpb25lcyBkZSBlc3RhIExpY2VuY2lhLiBMbyBhbnRlcmlvciBzZSBhcGxpY2EgYSBsYSBPYnJhIGluY29ycG9yYWRhIGEgdW5hIE9icmEgQ29sZWN0aXZhLCBwZXJvIGVzdG8gbm8gZXhpZ2UgcXVlIGxhIE9icmEgQ29sZWN0aXZhIGFwYXJ0ZSBkZSBsYSBvYnJhIG1pc21hIHF1ZWRlIHN1amV0YSBhIGxhcyBjb25kaWNpb25lcyBkZSBlc3RhIExpY2VuY2lhLiBTaSBVc3RlZCBjcmVhIHVuYSBPYnJhIENvbGVjdGl2YSwgcHJldmlvIGF2aXNvIGRlIGN1YWxxdWllciBMaWNlbmNpYW50ZSBkZWJlLCBlbiBsYSBtZWRpZGEgZGUgbG8gcG9zaWJsZSwgZWxpbWluYXIgZGUgbGEgT2JyYSBDb2xlY3RpdmEgY3VhbHF1aWVyIHJlZmVyZW5jaWEgYSBkaWNobyBMaWNlbmNpYW50ZSBvIGFsIEF1dG9yIE9yaWdpbmFsLCBzZWfDum4gbG8gc29saWNpdGFkbyBwb3IgZWwgTGljZW5jaWFudGUgeSBjb25mb3JtZSBsbyBleGlnZSBsYSBjbMOhdXN1bGEgNChjKS4KCmIuCVVzdGVkIG5vIHB1ZWRlIGVqZXJjZXIgbmluZ3VubyBkZSBsb3MgZGVyZWNob3MgcXVlIGxlIGhhbiBzaWRvIG90b3JnYWRvcyBlbiBsYSBTZWNjacOzbiAzIHByZWNlZGVudGUgZGUgbW9kbyBxdWUgZXN0w6luIHByaW5jaXBhbG1lbnRlIGRlc3RpbmFkb3MgbyBkaXJlY3RhbWVudGUgZGlyaWdpZG9zIGEgY29uc2VndWlyIHVuIHByb3ZlY2hvIGNvbWVyY2lhbCBvIHVuYSBjb21wZW5zYWNpw7NuIG1vbmV0YXJpYSBwcml2YWRhLiBFbCBpbnRlcmNhbWJpbyBkZSBsYSBPYnJhIHBvciBvdHJhcyBvYnJhcyBwcm90ZWdpZGFzIHBvciBkZXJlY2hvcyBkZSBhdXRvciwgeWEgc2VhIGEgdHJhdsOpcyBkZSB1biBzaXN0ZW1hIHBhcmEgY29tcGFydGlyIGFyY2hpdm9zIGRpZ2l0YWxlcyAoZGlnaXRhbCBmaWxlLXNoYXJpbmcpIG8gZGUgY3VhbHF1aWVyIG90cmEgbWFuZXJhIG5vIHNlcsOhIGNvbnNpZGVyYWRvIGNvbW8gZXN0YXIgZGVzdGluYWRvIHByaW5jaXBhbG1lbnRlIG8gZGlyaWdpZG8gZGlyZWN0YW1lbnRlIGEgY29uc2VndWlyIHVuIHByb3ZlY2hvIGNvbWVyY2lhbCBvIHVuYSBjb21wZW5zYWNpw7NuIG1vbmV0YXJpYSBwcml2YWRhLCBzaWVtcHJlIHF1ZSBubyBzZSByZWFsaWNlIHVuIHBhZ28gbWVkaWFudGUgdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIGVuIHJlbGFjacOzbiBjb24gZWwgaW50ZXJjYW1iaW8gZGUgb2JyYXMgcHJvdGVnaWRhcyBwb3IgZWwgZGVyZWNobyBkZSBhdXRvci4KCmMuCVNpIHVzdGVkIGRpc3RyaWJ1eWUsIGV4aGliZSBww7pibGljYW1lbnRlLCBlamVjdXRhIHDDumJsaWNhbWVudGUgbyBlamVjdXRhIHDDumJsaWNhbWVudGUgZW4gZm9ybWEgZGlnaXRhbCBsYSBPYnJhIG8gY3VhbHF1aWVyIE9icmEgRGVyaXZhZGEgdSBPYnJhIENvbGVjdGl2YSwgVXN0ZWQgZGViZSBtYW50ZW5lciBpbnRhY3RhIHRvZGEgbGEgaW5mb3JtYWNpw7NuIGRlIGRlcmVjaG8gZGUgYXV0b3IgZGUgbGEgT2JyYSB5IHByb3BvcmNpb25hciwgZGUgZm9ybWEgcmF6b25hYmxlIHNlZ8O6biBlbCBtZWRpbyBvIG1hbmVyYSBxdWUgVXN0ZWQgZXN0w6kgdXRpbGl6YW5kbzogKGkpIGVsIG5vbWJyZSBkZWwgQXV0b3IgT3JpZ2luYWwgc2kgZXN0w6EgcHJvdmlzdG8gKG8gc2V1ZMOzbmltbywgc2kgZnVlcmUgYXBsaWNhYmxlKSwgeS9vIChpaSkgZWwgbm9tYnJlIGRlIGxhIHBhcnRlIG8gbGFzIHBhcnRlcyBxdWUgZWwgQXV0b3IgT3JpZ2luYWwgeS9vIGVsIExpY2VuY2lhbnRlIGh1YmllcmVuIGRlc2lnbmFkbyBwYXJhIGxhIGF0cmlidWNpw7NuICh2LmcuLCB1biBpbnN0aXR1dG8gcGF0cm9jaW5hZG9yLCBlZGl0b3JpYWwsIHB1YmxpY2FjacOzbikgZW4gbGEgaW5mb3JtYWNpw7NuIGRlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBkZWwgTGljZW5jaWFudGUsIHTDqXJtaW5vcyBkZSBzZXJ2aWNpb3MgbyBkZSBvdHJhcyBmb3JtYXMgcmF6b25hYmxlczsgZWwgdMOtdHVsbyBkZSBsYSBPYnJhIHNpIGVzdMOhIHByb3Zpc3RvOyBlbiBsYSBtZWRpZGEgZGUgbG8gcmF6b25hYmxlbWVudGUgZmFjdGlibGUgeSwgc2kgZXN0w6EgcHJvdmlzdG8sIGVsIElkZW50aWZpY2Fkb3IgVW5pZm9ybWUgZGUgUmVjdXJzb3MgKFVuaWZvcm0gUmVzb3VyY2UgSWRlbnRpZmllcikgcXVlIGVsIExpY2VuY2lhbnRlIGVzcGVjaWZpY2EgcGFyYSBzZXIgYXNvY2lhZG8gY29uIGxhIE9icmEsIHNhbHZvIHF1ZSB0YWwgVVJJIG5vIHNlIHJlZmllcmEgYSBsYSBub3RhIHNvYnJlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBvIGEgbGEgaW5mb3JtYWNpw7NuIHNvYnJlIGVsIGxpY2VuY2lhbWllbnRvIGRlIGxhIE9icmE7IHkgZW4gZWwgY2FzbyBkZSB1bmEgT2JyYSBEZXJpdmFkYSwgYXRyaWJ1aXIgZWwgY3LDqWRpdG8gaWRlbnRpZmljYW5kbyBlbCB1c28gZGUgbGEgT2JyYSBlbiBsYSBPYnJhIERlcml2YWRhICh2LmcuLCAiVHJhZHVjY2nDs24gRnJhbmNlc2EgZGUgbGEgT2JyYSBkZWwgQXV0b3IgT3JpZ2luYWwsIiBvICJHdWnDs24gQ2luZW1hdG9ncsOhZmljbyBiYXNhZG8gZW4gbGEgT2JyYSBvcmlnaW5hbCBkZWwgQXV0b3IgT3JpZ2luYWwiKS4gVGFsIGNyw6lkaXRvIHB1ZWRlIHNlciBpbXBsZW1lbnRhZG8gZGUgY3VhbHF1aWVyIGZvcm1hIHJhem9uYWJsZTsgZW4gZWwgY2Fzbywgc2luIGVtYmFyZ28sIGRlIE9icmFzIERlcml2YWRhcyB1IE9icmFzIENvbGVjdGl2YXMsIHRhbCBjcsOpZGl0byBhcGFyZWNlcsOhLCBjb21vIG3DrW5pbW8sIGRvbmRlIGFwYXJlY2UgZWwgY3LDqWRpdG8gZGUgY3VhbHF1aWVyIG90cm8gYXV0b3IgY29tcGFyYWJsZSB5IGRlIHVuYSBtYW5lcmEsIGFsIG1lbm9zLCB0YW4gZGVzdGFjYWRhIGNvbW8gZWwgY3LDqWRpdG8gZGUgb3RybyBhdXRvciBjb21wYXJhYmxlLgoKZC4JUGFyYSBldml0YXIgdG9kYSBjb25mdXNpw7NuLCBlbCBMaWNlbmNpYW50ZSBhY2xhcmEgcXVlLCBjdWFuZG8gbGEgb2JyYSBlcyB1bmEgY29tcG9zaWNpw7NuIG11c2ljYWw6CgppLglSZWdhbMOtYXMgcG9yIGludGVycHJldGFjacOzbiB5IGVqZWN1Y2nDs24gYmFqbyBsaWNlbmNpYXMgZ2VuZXJhbGVzLiBFbCBMaWNlbmNpYW50ZSBzZSByZXNlcnZhIGVsIGRlcmVjaG8gZXhjbHVzaXZvIGRlIGF1dG9yaXphciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIG8gbGEgZWplY3VjacOzbiBww7pibGljYSBkaWdpdGFsIGRlIGxhIG9icmEgeSBkZSByZWNvbGVjdGFyLCBzZWEgaW5kaXZpZHVhbG1lbnRlIG8gYSB0cmF2w6lzIGRlIHVuYSBzb2NpZWRhZCBkZSBnZXN0acOzbiBjb2xlY3RpdmEgZGUgZGVyZWNob3MgZGUgYXV0b3IgeSBkZXJlY2hvcyBjb25leG9zIChwb3IgZWplbXBsbywgU0FZQ08pLCBsYXMgcmVnYWzDrWFzIHBvciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIG8gcG9yIGxhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBkZSBsYSBvYnJhIChwb3IgZWplbXBsbyBXZWJjYXN0KSBsaWNlbmNpYWRhIGJham8gbGljZW5jaWFzIGdlbmVyYWxlcywgc2kgbGEgaW50ZXJwcmV0YWNpw7NuIG8gZWplY3VjacOzbiBkZSBsYSBvYnJhIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBvcmllbnRhZGEgcG9yIG8gZGlyaWdpZGEgYSBsYSBvYnRlbmNpw7NuIGRlIHVuYSB2ZW50YWphIGNvbWVyY2lhbCBvIHVuYSBjb21wZW5zYWNpw7NuIG1vbmV0YXJpYSBwcml2YWRhLgoKaWkuCVJlZ2Fsw61hcyBwb3IgRm9ub2dyYW1hcy4gRWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSByZWNvbGVjdGFyLCBpbmRpdmlkdWFsbWVudGUgbyBhIHRyYXbDqXMgZGUgdW5hIHNvY2llZGFkIGRlIGdlc3Rpw7NuIGNvbGVjdGl2YSBkZSBkZXJlY2hvcyBkZSBhdXRvciB5IGRlcmVjaG9zIGNvbmV4b3MgKHBvciBlamVtcGxvLCBsb3MgY29uc2FncmFkb3MgcG9yIGxhIFNBWUNPKSwgdW5hIGFnZW5jaWEgZGUgZGVyZWNob3MgbXVzaWNhbGVzIG8gYWxnw7puIGFnZW50ZSBkZXNpZ25hZG8sIGxhcyByZWdhbMOtYXMgcG9yIGN1YWxxdWllciBmb25vZ3JhbWEgcXVlIFVzdGVkIGNyZWUgYSBwYXJ0aXIgZGUgbGEgb2JyYSAo4oCcdmVyc2nDs24gY292ZXLigJ0pIHkgZGlzdHJpYnV5YSwgZW4gbG9zIHTDqXJtaW5vcyBkZWwgcsOpZ2ltZW4gZGUgZGVyZWNob3MgZGUgYXV0b3IsIHNpIGxhIGNyZWFjacOzbiBvIGRpc3RyaWJ1Y2nDs24gZGUgZXNhIHZlcnNpw7NuIGNvdmVyIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBkZXN0aW5hZGEgbyBkaXJpZ2lkYSBhIG9idGVuZXIgdW5hIHZlbnRhamEgY29tZXJjaWFsIG8gdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIHByaXZhZGEuCgplLglHZXN0acOzbiBkZSBEZXJlY2hvcyBkZSBBdXRvciBzb2JyZSBJbnRlcnByZXRhY2lvbmVzIHkgRWplY3VjaW9uZXMgRGlnaXRhbGVzIChXZWJDYXN0aW5nKS4gUGFyYSBldml0YXIgdG9kYSBjb25mdXNpw7NuLCBlbCBMaWNlbmNpYW50ZSBhY2xhcmEgcXVlLCBjdWFuZG8gbGEgb2JyYSBzZWEgdW4gZm9ub2dyYW1hLCBlbCBMaWNlbmNpYW50ZSBzZSByZXNlcnZhIGVsIGRlcmVjaG8gZXhjbHVzaXZvIGRlIGF1dG9yaXphciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIGRpZ2l0YWwgZGUgbGEgb2JyYSAocG9yIGVqZW1wbG8sIHdlYmNhc3QpIHkgZGUgcmVjb2xlY3RhciwgaW5kaXZpZHVhbG1lbnRlIG8gYSB0cmF2w6lzIGRlIHVuYSBzb2NpZWRhZCBkZSBnZXN0acOzbiBjb2xlY3RpdmEgZGUgZGVyZWNob3MgZGUgYXV0b3IgeSBkZXJlY2hvcyBjb25leG9zIChwb3IgZWplbXBsbywgQUNJTlBSTyksIGxhcyByZWdhbMOtYXMgcG9yIGxhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBkZSBsYSBvYnJhIChwb3IgZWplbXBsbywgd2ViY2FzdCksIHN1amV0YSBhIGxhcyBkaXNwb3NpY2lvbmVzIGFwbGljYWJsZXMgZGVsIHLDqWdpbWVuIGRlIERlcmVjaG8gZGUgQXV0b3IsIHNpIGVzdGEgZWplY3VjacOzbiBww7pibGljYSBkaWdpdGFsIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBkaXJpZ2lkYSBhIG9idGVuZXIgdW5hIHZlbnRhamEgY29tZXJjaWFsIG8gdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIHByaXZhZGEuCgo1LiBSZXByZXNlbnRhY2lvbmVzLCBHYXJhbnTDrWFzIHkgTGltaXRhY2lvbmVzIGRlIFJlc3BvbnNhYmlsaWRhZC4KQSBNRU5PUyBRVUUgTEFTIFBBUlRFUyBMTyBBQ09SREFSQU4gREUgT1RSQSBGT1JNQSBQT1IgRVNDUklUTywgRUwgTElDRU5DSUFOVEUgT0ZSRUNFIExBIE9CUkEgKEVOIEVMIEVTVEFETyBFTiBFTCBRVUUgU0UgRU5DVUVOVFJBKSDigJxUQUwgQ1VBTOKAnSwgU0lOIEJSSU5EQVIgR0FSQU5Uw41BUyBERSBDTEFTRSBBTEdVTkEgUkVTUEVDVE8gREUgTEEgT0JSQSwgWUEgU0VBIEVYUFJFU0EsIElNUEzDjUNJVEEsIExFR0FMIE8gQ1VBTFFVSUVSQSBPVFJBLCBJTkNMVVlFTkRPLCBTSU4gTElNSVRBUlNFIEEgRUxMQVMsIEdBUkFOVMONQVMgREUgVElUVUxBUklEQUQsIENPTUVSQ0lBQklMSURBRCwgQURBUFRBQklMSURBRCBPIEFERUNVQUNJw5NOIEEgUFJPUMOTU0lUTyBERVRFUk1JTkFETywgQVVTRU5DSUEgREUgSU5GUkFDQ0nDk04sIERFIEFVU0VOQ0lBIERFIERFRkVDVE9TIExBVEVOVEVTIE8gREUgT1RSTyBUSVBPLCBPIExBIFBSRVNFTkNJQSBPIEFVU0VOQ0lBIERFIEVSUk9SRVMsIFNFQU4gTyBOTyBERVNDVUJSSUJMRVMgKFBVRURBTiBPIE5PIFNFUiBFU1RPUyBERVNDVUJJRVJUT1MpLiBBTEdVTkFTIEpVUklTRElDQ0lPTkVTIE5PIFBFUk1JVEVOIExBIEVYQ0xVU0nDk04gREUgR0FSQU5Uw41BUyBJTVBMw41DSVRBUywgRU4gQ1VZTyBDQVNPIEVTVEEgRVhDTFVTScOTTiBQVUVERSBOTyBBUExJQ0FSU0UgQSBVU1RFRC4KCjYuIExpbWl0YWNpw7NuIGRlIHJlc3BvbnNhYmlsaWRhZC4KQSBNRU5PUyBRVUUgTE8gRVhJSkEgRVhQUkVTQU1FTlRFIExBIExFWSBBUExJQ0FCTEUsIEVMIExJQ0VOQ0lBTlRFIE5PIFNFUsOBIFJFU1BPTlNBQkxFIEFOVEUgVVNURUQgUE9SIERBw5FPIEFMR1VOTywgU0VBIFBPUiBSRVNQT05TQUJJTElEQUQgRVhUUkFDT05UUkFDVFVBTCwgUFJFQ09OVFJBQ1RVQUwgTyBDT05UUkFDVFVBTCwgT0JKRVRJVkEgTyBTVUJKRVRJVkEsIFNFIFRSQVRFIERFIERBw5FPUyBNT1JBTEVTIE8gUEFUUklNT05JQUxFUywgRElSRUNUT1MgTyBJTkRJUkVDVE9TLCBQUkVWSVNUT1MgTyBJTVBSRVZJU1RPUyBQUk9EVUNJRE9TIFBPUiBFTCBVU08gREUgRVNUQSBMSUNFTkNJQSBPIERFIExBIE9CUkEsIEFVTiBDVUFORE8gRUwgTElDRU5DSUFOVEUgSEFZQSBTSURPIEFEVkVSVElETyBERSBMQSBQT1NJQklMSURBRCBERSBESUNIT1MgREHDkU9TLiBBTEdVTkFTIExFWUVTIE5PIFBFUk1JVEVOIExBIEVYQ0xVU0nDk04gREUgQ0lFUlRBIFJFU1BPTlNBQklMSURBRCwgRU4gQ1VZTyBDQVNPIEVTVEEgRVhDTFVTScOTTiBQVUVERSBOTyBBUExJQ0FSU0UgQSBVU1RFRC4KCjcuIFTDqXJtaW5vLgoKYS4JRXN0YSBMaWNlbmNpYSB5IGxvcyBkZXJlY2hvcyBvdG9yZ2Fkb3MgZW4gdmlydHVkIGRlIGVsbGEgdGVybWluYXLDoW4gYXV0b23DoXRpY2FtZW50ZSBzaSBVc3RlZCBpbmZyaW5nZSBhbGd1bmEgY29uZGljacOzbiBlc3RhYmxlY2lkYSBlbiBlbGxhLiBTaW4gZW1iYXJnbywgbG9zIGluZGl2aWR1b3MgbyBlbnRpZGFkZXMgcXVlIGhhbiByZWNpYmlkbyBPYnJhcyBEZXJpdmFkYXMgbyBDb2xlY3RpdmFzIGRlIFVzdGVkIGRlIGNvbmZvcm1pZGFkIGNvbiBlc3RhIExpY2VuY2lhLCBubyB2ZXLDoW4gdGVybWluYWRhcyBzdXMgbGljZW5jaWFzLCBzaWVtcHJlIHF1ZSBlc3RvcyBpbmRpdmlkdW9zIG8gZW50aWRhZGVzIHNpZ2FuIGN1bXBsaWVuZG8gw61udGVncmFtZW50ZSBsYXMgY29uZGljaW9uZXMgZGUgZXN0YXMgbGljZW5jaWFzLiBMYXMgU2VjY2lvbmVzIDEsIDIsIDUsIDYsIDcsIHkgOCBzdWJzaXN0aXLDoW4gYSBjdWFscXVpZXIgdGVybWluYWNpw7NuIGRlIGVzdGEgTGljZW5jaWEuCgpiLglTdWpldGEgYSBsYXMgY29uZGljaW9uZXMgeSB0w6lybWlub3MgYW50ZXJpb3JlcywgbGEgbGljZW5jaWEgb3RvcmdhZGEgYXF1w60gZXMgcGVycGV0dWEgKGR1cmFudGUgZWwgcGVyw61vZG8gZGUgdmlnZW5jaWEgZGUgbG9zIGRlcmVjaG9zIGRlIGF1dG9yIGRlIGxhIG9icmEpLiBObyBvYnN0YW50ZSBsbyBhbnRlcmlvciwgZWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGEgcHVibGljYXIgeS9vIGVzdHJlbmFyIGxhIE9icmEgYmFqbyBjb25kaWNpb25lcyBkZSBsaWNlbmNpYSBkaWZlcmVudGVzIG8gYSBkZWphciBkZSBkaXN0cmlidWlybGEgZW4gbG9zIHTDqXJtaW5vcyBkZSBlc3RhIExpY2VuY2lhIGVuIGN1YWxxdWllciBtb21lbnRvOyBlbiBlbCBlbnRlbmRpZG8sIHNpbiBlbWJhcmdvLCBxdWUgZXNhIGVsZWNjacOzbiBubyBzZXJ2aXLDoSBwYXJhIHJldm9jYXIgZXN0YSBsaWNlbmNpYSBvIHF1ZSBkZWJhIHNlciBvdG9yZ2FkYSAsIGJham8gbG9zIHTDqXJtaW5vcyBkZSBlc3RhIGxpY2VuY2lhKSwgeSBlc3RhIGxpY2VuY2lhIGNvbnRpbnVhcsOhIGVuIHBsZW5vIHZpZ29yIHkgZWZlY3RvIGEgbWVub3MgcXVlIHNlYSB0ZXJtaW5hZGEgY29tbyBzZSBleHByZXNhIGF0csOhcy4gTGEgTGljZW5jaWEgcmV2b2NhZGEgY29udGludWFyw6Egc2llbmRvIHBsZW5hbWVudGUgdmlnZW50ZSB5IGVmZWN0aXZhIHNpIG5vIHNlIGxlIGRhIHTDqXJtaW5vIGVuIGxhcyBjb25kaWNpb25lcyBpbmRpY2FkYXMgYW50ZXJpb3JtZW50ZS4KCjguIFZhcmlvcy4KCmEuCUNhZGEgdmV6IHF1ZSBVc3RlZCBkaXN0cmlidXlhIG8gcG9uZ2EgYSBkaXNwb3NpY2nDs24gcMO6YmxpY2EgbGEgT2JyYSBvIHVuYSBPYnJhIENvbGVjdGl2YSwgZWwgTGljZW5jaWFudGUgb2ZyZWNlcsOhIGFsIGRlc3RpbmF0YXJpbyB1bmEgbGljZW5jaWEgZW4gbG9zIG1pc21vcyB0w6lybWlub3MgeSBjb25kaWNpb25lcyBxdWUgbGEgbGljZW5jaWEgb3RvcmdhZGEgYSBVc3RlZCBiYWpvIGVzdGEgTGljZW5jaWEuCgpiLglTaSBhbGd1bmEgZGlzcG9zaWNpw7NuIGRlIGVzdGEgTGljZW5jaWEgcmVzdWx0YSBpbnZhbGlkYWRhIG8gbm8gZXhpZ2libGUsIHNlZ8O6biBsYSBsZWdpc2xhY2nDs24gdmlnZW50ZSwgZXN0byBubyBhZmVjdGFyw6EgbmkgbGEgdmFsaWRleiBuaSBsYSBhcGxpY2FiaWxpZGFkIGRlbCByZXN0byBkZSBjb25kaWNpb25lcyBkZSBlc3RhIExpY2VuY2lhIHksIHNpbiBhY2Npw7NuIGFkaWNpb25hbCBwb3IgcGFydGUgZGUgbG9zIHN1amV0b3MgZGUgZXN0ZSBhY3VlcmRvLCBhcXXDqWxsYSBzZSBlbnRlbmRlcsOhIHJlZm9ybWFkYSBsbyBtw61uaW1vIG5lY2VzYXJpbyBwYXJhIGhhY2VyIHF1ZSBkaWNoYSBkaXNwb3NpY2nDs24gc2VhIHbDoWxpZGEgeSBleGlnaWJsZS4KCmMuCU5pbmfDum4gdMOpcm1pbm8gbyBkaXNwb3NpY2nDs24gZGUgZXN0YSBMaWNlbmNpYSBzZSBlc3RpbWFyw6EgcmVudW5jaWFkYSB5IG5pbmd1bmEgdmlvbGFjacOzbiBkZSBlbGxhIHNlcsOhIGNvbnNlbnRpZGEgYSBtZW5vcyBxdWUgZXNhIHJlbnVuY2lhIG8gY29uc2VudGltaWVudG8gc2VhIG90b3JnYWRvIHBvciBlc2NyaXRvIHkgZmlybWFkbyBwb3IgbGEgcGFydGUgcXVlIHJlbnVuY2llIG8gY29uc2llbnRhLgoKZC4JRXN0YSBMaWNlbmNpYSByZWZsZWphIGVsIGFjdWVyZG8gcGxlbm8gZW50cmUgbGFzIHBhcnRlcyByZXNwZWN0byBhIGxhIE9icmEgYXF1w60gbGljZW5jaWFkYS4gTm8gaGF5IGFycmVnbG9zLCBhY3VlcmRvcyBvIGRlY2xhcmFjaW9uZXMgcmVzcGVjdG8gYSBsYSBPYnJhIHF1ZSBubyBlc3TDqW4gZXNwZWNpZmljYWRvcyBlbiBlc3RlIGRvY3VtZW50by4gRWwgTGljZW5jaWFudGUgbm8gc2UgdmVyw6EgbGltaXRhZG8gcG9yIG5pbmd1bmEgZGlzcG9zaWNpw7NuIGFkaWNpb25hbCBxdWUgcHVlZGEgc3VyZ2lyIGVuIGFsZ3VuYSBjb211bmljYWNpw7NuIGVtYW5hZGEgZGUgVXN0ZWQuIEVzdGEgTGljZW5jaWEgbm8gcHVlZGUgc2VyIG1vZGlmaWNhZGEgc2luIGVsIGNvbnNlbnRpbWllbnRvIG11dHVvIHBvciBlc2NyaXRvIGRlbCBMaWNlbmNpYW50ZSB5IFVzdGVkLgo= 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