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Lipid humification by soil clays

Thesis (PhDAgric)--Stellenbosch University, 2019.

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Main Author: Adams, Adrian Richard
Other Authors: Clarke, Catherine E.
Format: Thesis
Language:en_ZA
Published: Stellenbosch : Stellenbosch University 2019
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access_status_str Open Access
author Adams, Adrian Richard
author2 Clarke, Catherine E.
author_browse Adams, Adrian Richard
Clarke, Catherine E.
author_facet Clarke, Catherine E.
Adams, Adrian Richard
author_sort Adams, Adrian Richard
collection Thesis
dc_rights_str_mv Stellenbosch University
description Thesis (PhDAgric)--Stellenbosch University, 2019.
format Thesis
id oai:scholar.sun.ac.za:10019.1/105826
institution Stellenbosch University (South Africa)
language en_ZA
last_indexed 2026-06-10T12:41:07.950Z
license_str Other — see source repository
provenance_str_mv Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository
publishDate 2019
publishDateRange 2019
publishDateSort 2019
publisher Stellenbosch : Stellenbosch University
publisherStr Stellenbosch : Stellenbosch University
record_format dspace
source_str SUNScholar — Stellenbosch University Repository
spelling oai:scholar.sun.ac.za:10019.1/105826 Lipid humification by soil clays Adams, Adrian Richard Clarke, Catherine E. Hardie-Pieters, Ailsa G. Stellenbosch University. Faculty of Agrisciences. Dept. of Soil Science. humification, lipids, soil minerals, polyesters, complexation, RGB colour analysis Polymerisation of lipids Humification in soils Soil clays Red, green, blue (RGB) colour analysis UCTD Thesis (PhDAgric)--Stellenbosch University, 2019. ENGLISH ABSTRACT: We studied three aspects of the natural polymerisation (humification) of lipids by soil clays – namely, the products formed, reaction mechanism and kinetics – at environmental temperatures (c. 20–50°C). Various clays were reacted with oleic acid (our chosen model lipid). The Mn-oxide birnessite was the most reactive toward oleic acid, polymerising it into quasi-solid polyesters. A probing of the birnessite-oleic acid reaction mechanism revealed that the formation of a surface exchange complex between oleic acid carboxyl groups and birnessite surface sites (>Mn(III)/>Mn(IV)) is a crucial first step of the reaction. Subsequent chelation and one-electron reduction of Mn(III) to Mn(II) forms radical oleic acid species which couple and thereby polymerise. Kinetic studies revealed that the birnessite-oleic acid reaction was near-linearly dependent on birnessite mass-loading (rate order ~ 0.75) but virtually independent of birnessite surface pH (rate order ~ 0.2). A determined activation energy for the reaction of 12.8 ± 4.2 kJ/mol revealed that it is energetically more spontaneous than the usual autoxidation pathways. These findings broaden our understanding of the role soil clays play in lipid humification in soils. AFRIKAANS OPSOMMING: Ons het drie aspekte van die natuurlike polimerisasie (humifikasie) van lipiede deur grond kleie bestudeer – naamlik, die produkte gevorm, reaksie meganisme en kinetika – teen omgewings-temperature (ong. 20–50°C). Verskeie kleie is met oleïen suur (ons gekose model lipied) gereageer. Die Mn-oksied birnessiet was die mees reaktief teenoor oleïen suur, deur dit te polimeriseer na kwasi-soliede poliësters. 'n Ondersoek na die birnessiet-oleïen suur reaksie meganisme toon dat die formasie van 'n oppervlaks-uitruilingskompleks tussen oleïen suur karboksiel groepe en birnessiet oppervlaks-liggings (>Mn(III)/>Mn(IV)) 'n noodsaaklike eerste stap van die reaksie is. Gevolglike chelasie en een-elektron reduksie van Mn(III) na Mn(II) form radikaal oleïen suur spesies wat koppel en daardeur polimeriseer. Kinetika studies toon dat die birnessiet-oleïen suur reaksie naby-liniêr afhanklik is op birnessiet massa-lading (tempo orde ~ 0.75) maar so te sê onafhanklik is van birnessiet oppervlaks-pH (tempo orde ~ 0.2). 'n Bepaalde aktiverings-energie vir dié reaksie van 12.8 ± 4.2 kJ/mol toon dat dit energiek meer spontaan is as die gewone outoksidasie roetes. Hierdie bevindings verbreed ons begrip van die rol wat grond kleie in lipied humifikasie in gronde speel. National Research Foundation (NRF) Doctoral 2019-02-16T14:51:28Z 2019-04-17T08:14:36Z 2019-02-16T14:51:28Z 2019-04-17T08:14:36Z 2019-04 Thesis http://hdl.handle.net/10019.1/105826 en_ZA Stellenbosch University 201 pages : illustrations application/pdf Stellenbosch : Stellenbosch University
spellingShingle humification, lipids, soil minerals, polyesters, complexation, RGB colour analysis
Polymerisation of lipids
Humification in soils
Soil clays
Red, green, blue (RGB) colour analysis
UCTD
Adams, Adrian Richard
Lipid humification by soil clays
title Lipid humification by soil clays
title_full Lipid humification by soil clays
title_fullStr Lipid humification by soil clays
title_full_unstemmed Lipid humification by soil clays
title_short Lipid humification by soil clays
title_sort lipid humification by soil clays
topic humification, lipids, soil minerals, polyesters, complexation, RGB colour analysis
Polymerisation of lipids
Humification in soils
Soil clays
Red, green, blue (RGB) colour analysis
UCTD
url http://hdl.handle.net/10019.1/105826
work_keys_str_mv AT adamsadrianrichard lipidhumificationbysoilclays