Unlocking the secrets of Al-tobermorite in Roman seawater concrete

Handle URI:
http://hdl.handle.net/10754/563028
Title:
Unlocking the secrets of Al-tobermorite in Roman seawater concrete
Authors:
Jackson, Marie D.; Chae, Sejungrosie; Mulcahy, Sean R.; Meral, Cagla; Taylor, Rae; Li, Penghui; Emwas, Abdul-Hamid M.; Moon, Juhyuk; Yoon, Seyoon; Vola, Gabriele; Wenk, Hans Rudolf; Monteiro, Paulo José Meleragno
Abstract:
Ancient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al3+ substitution for Si4+ in Q 2(1Al), Q3(1Al), and Q3(2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na+ and K+ partially balance Al3+ substitution for Si4+. Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of sea-water and alkali- and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.
KAUST Department:
Advanced Nanofabrication, Imaging and Characterization Core Lab
Publisher:
GeoScienceWorld
Journal:
American Mineralogist
Issue Date:
1-Oct-2013
DOI:
10.2138/am.2013.4484
Type:
Article
ISSN:
0003004X
Sponsors:
This research was supported by Award No. KUS-11-004021, from King Abdullah University of Science and Technology (KAUST) and the Loeb Classical Library Foundation at Harvard University. Data were acquired at beamlines 5.3.2.1, 5.3.2.2, and 12.2.2 at the Advanced Light Source at the Lawrence Berkeley Laboratories supported by the Director of the Office of Science, Department of Energy, under Contract No. DE-AC02-05CH11231, and the Advanced Nanofabrication Imaging and Characterization Laboratories at King Abdullah University of Science and Technology. We thank the ROMACONS drilling program: J.P. Oleson, C. Brandon, R. Hohlfelder, and CTG Italcementi researchers and staff, especially B. Zanga, in Bergamo, Italy; A.D. Kilcoyne and T. Tyliszczak at the 5.3.2.1, 5.3.2.2 beamlines; and S. Clark at the 12.2.2 beamline. T. Teague, D. Hernandez, B. Black, C. Hagen, and C. Kosso provided research support. We thank M. Sintubin, G. Sposito, R-A. Itty, P. Brune, and J. Kirz for critical discussions, and the anonymous reviewers whose comments improved the manuscript. H.-R. Wenk acknowledges support by NSF (EAR-0836402). The Berkeley Research Impact Initiative provided funds for Open Acess.
Appears in Collections:
Articles; Advanced Nanofabrication, Imaging and Characterization Core Lab

Full metadata record

DC FieldValue Language
dc.contributor.authorJackson, Marie D.en
dc.contributor.authorChae, Sejungrosieen
dc.contributor.authorMulcahy, Sean R.en
dc.contributor.authorMeral, Caglaen
dc.contributor.authorTaylor, Raeen
dc.contributor.authorLi, Penghuien
dc.contributor.authorEmwas, Abdul-Hamid M.en
dc.contributor.authorMoon, Juhyuken
dc.contributor.authorYoon, Seyoonen
dc.contributor.authorVola, Gabrieleen
dc.contributor.authorWenk, Hans Rudolfen
dc.contributor.authorMonteiro, Paulo José Meleragnoen
dc.date.accessioned2015-08-03T11:34:04Zen
dc.date.available2015-08-03T11:34:04Zen
dc.date.issued2013-10-01en
dc.identifier.issn0003004Xen
dc.identifier.doi10.2138/am.2013.4484en
dc.identifier.urihttp://hdl.handle.net/10754/563028en
dc.description.abstractAncient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al3+ substitution for Si4+ in Q 2(1Al), Q3(1Al), and Q3(2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na+ and K+ partially balance Al3+ substitution for Si4+. Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of sea-water and alkali- and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.en
dc.description.sponsorshipThis research was supported by Award No. KUS-11-004021, from King Abdullah University of Science and Technology (KAUST) and the Loeb Classical Library Foundation at Harvard University. Data were acquired at beamlines 5.3.2.1, 5.3.2.2, and 12.2.2 at the Advanced Light Source at the Lawrence Berkeley Laboratories supported by the Director of the Office of Science, Department of Energy, under Contract No. DE-AC02-05CH11231, and the Advanced Nanofabrication Imaging and Characterization Laboratories at King Abdullah University of Science and Technology. We thank the ROMACONS drilling program: J.P. Oleson, C. Brandon, R. Hohlfelder, and CTG Italcementi researchers and staff, especially B. Zanga, in Bergamo, Italy; A.D. Kilcoyne and T. Tyliszczak at the 5.3.2.1, 5.3.2.2 beamlines; and S. Clark at the 12.2.2 beamline. T. Teague, D. Hernandez, B. Black, C. Hagen, and C. Kosso provided research support. We thank M. Sintubin, G. Sposito, R-A. Itty, P. Brune, and J. Kirz for critical discussions, and the anonymous reviewers whose comments improved the manuscript. H.-R. Wenk acknowledges support by NSF (EAR-0836402). The Berkeley Research Impact Initiative provided funds for Open Acess.en
dc.publisherGeoScienceWorlden
dc.subjectAl-tobermoriteen
dc.subjectAncient Roman concreteen
dc.subjectBonding environmentsen
dc.subjectThermal modelen
dc.subjectVolcanic pozzolanen
dc.titleUnlocking the secrets of Al-tobermorite in Roman seawater concreteen
dc.typeArticleen
dc.contributor.departmentAdvanced Nanofabrication, Imaging and Characterization Core Laben
dc.identifier.journalAmerican Mineralogisten
dc.contributor.institutionUniv Calif Berkeley, Dept Civil & Environm Engn, Berkeley, CA 94720 USAen
dc.contributor.institutionUniv Calif Berkeley, Dept Earth & Planetary Sci, Berkeley, CA 94720 USAen
dc.contributor.institutionTsinghua Univ, State Key Lab Hydrosci & Engn, Beijing 100084, Peoples R Chinaen
dc.contributor.institutionCimprogetti SpA, I-24044 Dalmine, Italyen
dc.contributor.institutionMiddle E Tech Univ, TR-06800 Ankara, Turkeyen
dc.contributor.institutionUniv Aberdeen, Kings Coll, Sch Engn, Aberdeen AB24 3UE, Scotlanden
kaust.authorEmwas, Abdul-Hamid M.en
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