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Release of metals from synthetic Cr-goethites under acidic and reductive conditions: Effect of aging and composition
The dissolution mechanism of pure and Cr-substituted, synthetic goethites with different aging times, as well as the changes in morphology, crystallinity and structural changes, were investigated. The Cr-goethites were obtained by synthesizing goethite in solutions that contained different concentra...
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Published in: | Applied clay science 2012-04, Vol.58, p.88-95 |
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description | The dissolution mechanism of pure and Cr-substituted, synthetic goethites with different aging times, as well as the changes in morphology, crystallinity and structural changes, were investigated. The Cr-goethites were obtained by synthesizing goethite in solutions that contained different concentrations of Cr(III) ions. The obtained suspensions were aged in the parent solutions for different time spans. Two samples of pure goethites, prepared using different KOH concentrations, were also studied for comparative purposes.
Chemical analyses showed that Cr-for-Fe substitution was greatest in samples aged for longer time. Rietveld simulation of XRD powder data indicated that the unit cell parameters of pure goethite increased for samples prepared at a higher KOH concentration, and decreased with Cr-incorporation. Simulation also showed that the mean coherence path dimension (MCP), or crystallite size, in the direction perpendicular to crystal plane (110), did not change much in the samples, whereas the crystallite size in the direction parallel to crystal plane (110) increased with Cr-content, KOH concentration and aging time. The obtained MCP values indicate an increasing elongated form in the domains.
Chromium substituted goethites presented a good capacity for immobilizating Cr when the dissolution rates were studied in 3.98M HCl, 0.10M oxalic acid (H2Oxal), and reductive media (H2Oxal/Fe(II)). The shape of the f vs. t profile, where f stands for the fraction of Fe dissolved (dissolved Fe mass/total Fe mass) and t refers to the dissolution time, follows a contracting bidimensional model, and when dissolved in similar acid concentrations, the reactivity follows the trend HCl |
doi_str_mv | 10.1016/j.clay.2012.01.018 |
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Chemical analyses showed that Cr-for-Fe substitution was greatest in samples aged for longer time. Rietveld simulation of XRD powder data indicated that the unit cell parameters of pure goethite increased for samples prepared at a higher KOH concentration, and decreased with Cr-incorporation. Simulation also showed that the mean coherence path dimension (MCP), or crystallite size, in the direction perpendicular to crystal plane (110), did not change much in the samples, whereas the crystallite size in the direction parallel to crystal plane (110) increased with Cr-content, KOH concentration and aging time. The obtained MCP values indicate an increasing elongated form in the domains.
Chromium substituted goethites presented a good capacity for immobilizating Cr when the dissolution rates were studied in 3.98M HCl, 0.10M oxalic acid (H2Oxal), and reductive media (H2Oxal/Fe(II)). The shape of the f vs. t profile, where f stands for the fraction of Fe dissolved (dissolved Fe mass/total Fe mass) and t refers to the dissolution time, follows a contracting bidimensional model, and when dissolved in similar acid concentrations, the reactivity follows the trend HCl<H2Oxal≪H2Oxal/Fe(II), indicating that dissolution is noticeably increased in complexing-reducing media. The dissolution rate constant k values were highly depend on crystallite size, and the dissolution rate decreased in the samples aged longest and in goethites containing higher concentrations of Cr. The release of Fe and Cr is congruent and shows a homogeneous distribution of Fe and Cr in the samples. The calculated activation energies values support a surface reaction control for the dissolution process.</description><identifier>ISSN: 0169-1317</identifier><identifier>EISSN: 1872-9053</identifier><identifier>DOI: 10.1016/j.clay.2012.01.018</identifier><identifier>CODEN: ACLSER</identifier><language>eng</language><publisher>Kidlington: Elsevier B.V</publisher><subject>Acid dissolution ; Chromium ; Clay (material) ; Composition effects ; Concentration (composition) ; Cr-goethite ; Crystallinity ; Crystallite size ; Dissolution ; Earth sciences ; Earth, ocean, space ; Exact sciences and technology ; Lattice parameters ; Mineralogy ; Morphology ; Parents ; Reductive dissolution ; Silicates</subject><ispartof>Applied clay science, 2012-04, Vol.58, p.88-95</ispartof><rights>2012 Elsevier B.V.</rights><rights>2015 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c407t-2d4975974ec90d522ae636b1c07370534a8dcbf5a43cd95152bcbd6c847af0a33</citedby><cites>FETCH-LOGICAL-c407t-2d4975974ec90d522ae636b1c07370534a8dcbf5a43cd95152bcbd6c847af0a33</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=25772314$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Tufo, Ana E.</creatorcontrib><creatorcontrib>Sileo, Elsa E.</creatorcontrib><creatorcontrib>Morando, Pedro J.</creatorcontrib><title>Release of metals from synthetic Cr-goethites under acidic and reductive conditions: Effect of aging and composition</title><title>Applied clay science</title><description>The dissolution mechanism of pure and Cr-substituted, synthetic goethites with different aging times, as well as the changes in morphology, crystallinity and structural changes, were investigated. The Cr-goethites were obtained by synthesizing goethite in solutions that contained different concentrations of Cr(III) ions. The obtained suspensions were aged in the parent solutions for different time spans. Two samples of pure goethites, prepared using different KOH concentrations, were also studied for comparative purposes.
Chemical analyses showed that Cr-for-Fe substitution was greatest in samples aged for longer time. Rietveld simulation of XRD powder data indicated that the unit cell parameters of pure goethite increased for samples prepared at a higher KOH concentration, and decreased with Cr-incorporation. Simulation also showed that the mean coherence path dimension (MCP), or crystallite size, in the direction perpendicular to crystal plane (110), did not change much in the samples, whereas the crystallite size in the direction parallel to crystal plane (110) increased with Cr-content, KOH concentration and aging time. The obtained MCP values indicate an increasing elongated form in the domains.
Chromium substituted goethites presented a good capacity for immobilizating Cr when the dissolution rates were studied in 3.98M HCl, 0.10M oxalic acid (H2Oxal), and reductive media (H2Oxal/Fe(II)). The shape of the f vs. t profile, where f stands for the fraction of Fe dissolved (dissolved Fe mass/total Fe mass) and t refers to the dissolution time, follows a contracting bidimensional model, and when dissolved in similar acid concentrations, the reactivity follows the trend HCl<H2Oxal≪H2Oxal/Fe(II), indicating that dissolution is noticeably increased in complexing-reducing media. The dissolution rate constant k values were highly depend on crystallite size, and the dissolution rate decreased in the samples aged longest and in goethites containing higher concentrations of Cr. The release of Fe and Cr is congruent and shows a homogeneous distribution of Fe and Cr in the samples. The calculated activation energies values support a surface reaction control for the dissolution process.</description><subject>Acid dissolution</subject><subject>Chromium</subject><subject>Clay (material)</subject><subject>Composition effects</subject><subject>Concentration (composition)</subject><subject>Cr-goethite</subject><subject>Crystallinity</subject><subject>Crystallite size</subject><subject>Dissolution</subject><subject>Earth sciences</subject><subject>Earth, ocean, space</subject><subject>Exact sciences and technology</subject><subject>Lattice parameters</subject><subject>Mineralogy</subject><subject>Morphology</subject><subject>Parents</subject><subject>Reductive dissolution</subject><subject>Silicates</subject><issn>0169-1317</issn><issn>1872-9053</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNp9kEFrGzEQhUVIIY6bP5CTLoVc1pW0u9aq9BJMmhYChZKchTwa2TK7kivJAf_7ynHIsfBgDvPNe8wj5JazBWd8-XW3gNEcF4JxsWC8arggMz5I0SjWt5dkViHV8JbLK3Kd845VcOjVjJQ_OKLJSKOjExYzZupSnGg-hrLF4oGuUrOJWLa-YKaHYDFRA97WjQmWJrQHKP4VKcRgffEx5G_0wTmEcvI0Gx82byTEaR_zG_GZfHI1CW_e55y8_Hh4Xv1snn4__lrdPzXQMVkaYTsleyU7BMVsL4TBZbtcc2CylfWtzgwW1q43XQtW9bwXa1jbJQydNI6Ztp2Tu7PvPsW_B8xFTz4DjqMJGA9ZcyH4oJhSsqLijEKKOSd0ep_8ZNJRc6ZPFeudPlWsTxVrxquGevTl3d9kMKNLJoDPH5eil1K0vKvc9zOH9dlXj0ln8BgArU-1J22j_1_MPwE8ky8</recordid><startdate>20120401</startdate><enddate>20120401</enddate><creator>Tufo, Ana E.</creator><creator>Sileo, Elsa E.</creator><creator>Morando, Pedro J.</creator><general>Elsevier B.V</general><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20120401</creationdate><title>Release of metals from synthetic Cr-goethites under acidic and reductive conditions: Effect of aging and composition</title><author>Tufo, Ana E. ; Sileo, Elsa E. ; Morando, Pedro J.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c407t-2d4975974ec90d522ae636b1c07370534a8dcbf5a43cd95152bcbd6c847af0a33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>Acid dissolution</topic><topic>Chromium</topic><topic>Clay (material)</topic><topic>Composition effects</topic><topic>Concentration (composition)</topic><topic>Cr-goethite</topic><topic>Crystallinity</topic><topic>Crystallite size</topic><topic>Dissolution</topic><topic>Earth sciences</topic><topic>Earth, ocean, space</topic><topic>Exact sciences and technology</topic><topic>Lattice parameters</topic><topic>Mineralogy</topic><topic>Morphology</topic><topic>Parents</topic><topic>Reductive dissolution</topic><topic>Silicates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tufo, Ana E.</creatorcontrib><creatorcontrib>Sileo, Elsa E.</creatorcontrib><creatorcontrib>Morando, Pedro J.</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Ceramic Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Applied clay science</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tufo, Ana E.</au><au>Sileo, Elsa E.</au><au>Morando, Pedro J.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Release of metals from synthetic Cr-goethites under acidic and reductive conditions: Effect of aging and composition</atitle><jtitle>Applied clay science</jtitle><date>2012-04-01</date><risdate>2012</risdate><volume>58</volume><spage>88</spage><epage>95</epage><pages>88-95</pages><issn>0169-1317</issn><eissn>1872-9053</eissn><coden>ACLSER</coden><abstract>The dissolution mechanism of pure and Cr-substituted, synthetic goethites with different aging times, as well as the changes in morphology, crystallinity and structural changes, were investigated. The Cr-goethites were obtained by synthesizing goethite in solutions that contained different concentrations of Cr(III) ions. The obtained suspensions were aged in the parent solutions for different time spans. Two samples of pure goethites, prepared using different KOH concentrations, were also studied for comparative purposes.
Chemical analyses showed that Cr-for-Fe substitution was greatest in samples aged for longer time. Rietveld simulation of XRD powder data indicated that the unit cell parameters of pure goethite increased for samples prepared at a higher KOH concentration, and decreased with Cr-incorporation. Simulation also showed that the mean coherence path dimension (MCP), or crystallite size, in the direction perpendicular to crystal plane (110), did not change much in the samples, whereas the crystallite size in the direction parallel to crystal plane (110) increased with Cr-content, KOH concentration and aging time. The obtained MCP values indicate an increasing elongated form in the domains.
Chromium substituted goethites presented a good capacity for immobilizating Cr when the dissolution rates were studied in 3.98M HCl, 0.10M oxalic acid (H2Oxal), and reductive media (H2Oxal/Fe(II)). The shape of the f vs. t profile, where f stands for the fraction of Fe dissolved (dissolved Fe mass/total Fe mass) and t refers to the dissolution time, follows a contracting bidimensional model, and when dissolved in similar acid concentrations, the reactivity follows the trend HCl<H2Oxal≪H2Oxal/Fe(II), indicating that dissolution is noticeably increased in complexing-reducing media. The dissolution rate constant k values were highly depend on crystallite size, and the dissolution rate decreased in the samples aged longest and in goethites containing higher concentrations of Cr. The release of Fe and Cr is congruent and shows a homogeneous distribution of Fe and Cr in the samples. The calculated activation energies values support a surface reaction control for the dissolution process.</abstract><cop>Kidlington</cop><pub>Elsevier B.V</pub><doi>10.1016/j.clay.2012.01.018</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
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subjects | Acid dissolution Chromium Clay (material) Composition effects Concentration (composition) Cr-goethite Crystallinity Crystallite size Dissolution Earth sciences Earth, ocean, space Exact sciences and technology Lattice parameters Mineralogy Morphology Parents Reductive dissolution Silicates |
title | Release of metals from synthetic Cr-goethites under acidic and reductive conditions: Effect of aging and composition |
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