Browsing by Author "Adams, Adrian Richard"

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    The degradation of atrazine by soil minerals : effects of drying mineral surfaces
    (Stellenbosch : Stellenbosch University, 2014-04) Adams, Adrian Richard; Clarke, Catherine E.; Roychoudhury, Alakendra N.; Stellenbosch University. Faculty of AgriSciences. Dept. of Soil Science.
    ENGLISH ABSTRACT: The herbicide atrazine (ATZ, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) has been identified as an environmental endocrine disruptor and possible human carcinogen. The presence of atrazine, along with its degradation products, in soils and water supplies therefore raises concern. Atrazine biodegradation in soils is well-covered to date, however, atrazine degradation by abiotic mineral surfaces, and the chemical mechanism by which it occurs, is not fully understood. Furthermore, with a changing global climate, the effects of wetting and drying cycles on soil processes (e.g. atrazine degradation) is largely unknown, but increasing in importance. This study therefore investigated atrazine degradation on six common soil mineral surfaces, namely birnessite, goethite, ferrihydrite, gibbsite, Al3+-saturated smectite and quartz, as well as the effects that drying these surfaces has on atrazine degradation. In the first part, a comparison was conducted between the reactivity of fully hydrated and drying mineral surfaces toward atrazine, by reacting atrazine-mineral mixtures under both moist and ambient drying conditions, in parallel, for 14 days. Under moist conditions, none of the mineral surfaces degraded atrazine, but under drying, birnessite and goethite degraded atrazine to non-phytotoxic hydroxyatrazine (ATZ-OH, 2-hydroxy-4-ethylamino-6-isopropylamino-1,3,5-triazine) as major product and phytotoxic deethylatrazine (DEA, 2-chloro-4-amino-6-isopropylamino-1,3,5-triazine) as minor product. The mineral surface reactivity was birnessite (66% degradation) > goethite (18% degradation) >> other mineral surfaces (negligible degradation), indicating possible atrazine oxidation. In the second part, the effects of drying rate were investigated on birnessite only (the most reactive surface), by conducting the drying (1) gradually at ambient rates, (2) rapidly under an air stream, and (3) gradually in the absence of water using only organic solvent. After 30 days of ambient drying, 90% of the atrazine was degraded to ATZ-OH and DEA, but the same extent of degradation was achieved after only 4 days of rapid drying with an air stream. Thirty days of gradual drying using only organic solvent did not increase atrazine degradation compared to the water-moist drying surface. In each case, degradation initiated at a critical moisture content of 10% of the original moisture content. In the third part, the degradation mechanism was further investigated. To test for the possible oxidation of atrazine by the birnessite surface, moist atrazine-birnessite mixtures were dried under a nitrogen (N2) stream to eliminate possible oxidation by atmospheric oxygen (O2). Dissolved Mn2+ was extracted at the end of the experiment to observe any reduction of birnessite. Under N2, the same products were formed as before, with no appreciable Mn2+ production, indicating non-oxidative atrazine degradation by birnessite. The final part investigated the effects ultraviolet (UV) radiation has on the degradation of atrazine by drying mineral surfaces. The UV-radiation enhanced the degradation of atrazine, but no other degradation products were formed. It was therefore concluded that atrazine degradation on redox-active soil mineral surfaces is enhanced by drying, via a net non-oxidative mechanism. Furthermore, this drying-induced degradation is an atrazine detoxification mechanism which could be easily applied through agricultural practices such as windrowing, ploughing and any other practice that (rapidly) dries a Mn- or Fe-oxide rich agricultural soil.
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    Lipid humification by soil clays
    (Stellenbosch : Stellenbosch University, 2019-04) Adams, Adrian Richard; Clarke, Catherine E.; Hardie-Pieters, Ailsa G.; Stellenbosch University. Faculty of Agrisciences. Dept. of Soil Science.
    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.