Three field sites were chosen to study the environmental assimilative capacity of heavy metals in soil. These sites were the Werribee Farm and the Myome Farm in Australia and Shenyang Zhangshi Irrigation Area in China. The Werribee Farm and the Shenyang Zhangshi Irrigation Area received sewage treatment and application on land for a long time. The Myome farm is an experimental site in which investigations on land application of municipal wastewater on water repellent soils is currently being trailed. Heavy metal contamination, in particular Cr, Cu and Zn, in the Land Filtration soil of Werribee Farm was widespread. More than a century of sewage irrigation has occurred in the Werribee Farm. The temporal distribution pattern of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in the soil at this site follow an exponential trend with time and the spatial distribution pattern of accumulation of heavy metals in different paddocks correlates with the number of years of sewage irrigation at that site in the Farm. Extensive sewage irrigation at Shenyang Zhangshi Irrigation Area resulted in significant Cd pollution in soil-plant (rice) system and poses a significant threat to the health of local people. Even after eight years since cessation of sewage irrigation, the bioavailable fractions of Cd in the soil as analyzed by sequential extraction techniques were very high thus illustrating long-term persistence. The simultaneous competitive adsorption of metals in water repellent soils (at Myome Farm in South Australia) was studied. In the competitive situation, Cr, Pb and Cu are the heavy metal cations more strongly adsorbed by the soil, whereas Cd, Ni and Zn are the least adsorbed. The increase in Freundlich adsorption capacity by clay amendment suggested that clayed soils are capable sorption of higher heavy metal loadings compared to the non-clayed water repellent soil, which is more vulnerable to heavy metal inputs. A simple model of environmental assimilative capacity is proposed. The results of comparison of the three field sites shows that the Werribee Farm has a higher environmental assimilative capacity of heavy metals in soil than the soils at Shenyang Zhangshi Irrigation Area and Myome Farm, however heavy metal contamination at Werribee Farm is still a concern. The model of environmental assimilative capacity of heavy metals in soil is an effective tool to assist management of effluent applied land irrigation systems and can be used to better design environmental engineering systems.

Copies of author's previously published articles inserted. Bibliography: leaves 195-230. In this study the soil aqueous phase chemistry of Zn and Cu in alkaline sodic soils are investigated. The chemistry of trace metal ions at indigenous concentrations in alkaline sodic soils are reported. Metal ions at low concentrations are measured by the graphite furnace atomic absorption spectrometry (GFAAS) technique.

In der vorliegenden Arbeit wurde die Nähr- und Schadstoffdynamik flugaschebeeinflusster Waldböden der Dübener Heide bezüglich ihres aktuellen Zustandes und der zu erwartenden zukünftigen Entwicklung untersucht. In der Dübener Heide wurden jahrzehntelang große Mengen an Flugasche abgelagert, die die Eigenschaften des Bodens entscheidend und nachhaltig prägten. Selbst 15 Jahre nach dem abrupten Ende der Einträge kann eine Flugaschebeeinflussung noch immer deutlich nachgewiesen werden. Das Ökosystem hat sich an die durch die Flugasche veränderten Umweltbedingungen angepasst. Nach Wegfall der Einträge unterliegt das System nun allerdings wieder neuen Veränderungen, deren Auswirkungen auf die Bestände noch unklar sind. Als Grundlage für nachhaltige forstliche Planungen und ein angepasstes Naturparkmanagement wurden deshalb im Rahmen des ENFORCHANGE-Teilprojektes Bodenprozesse der aktuelle bodenchemische Zustand der Dübener Heide untersucht und Prognosen über die zukünftige Entwicklung abgeleitet. Für die Ermittlung des Ist-Zustandes wurden 12 Kernversuchsflächen ausgewählt, die entlang eines Entfernungsgradienten ausgehend vom angenommenen Hauptemittenten, Kraftwerk Zschornewitz, gelegen sind und die typischen Bodentypen und Bestände der Dübener Heide repräsentieren. 2 m tiefe Bodenprofile wurden angelegt und in Tiefenstufen beprobt. Die Bodenproben wurden mit Standardmethoden auf verschiedene bodenchemische Parameter untersucht. Die Ergebnisse wurden sowohl hinsichtlich der Überschreitung von Mittel-, Vorsorge- und Grenzwerten als auch bezüglich der Ausbildung von Tiefen- und Entfernungsabhängigkeiten beurteilt. Darüber wurden die eindeutig flugaschebeeinflussten Parameter und die am stärksten beeinflussten Tiefenstufen identifiziert. Diese Informationen wurden anschließend genutzt, um die Standorte statistisch in unterschiedlich stark flugaschebeeinflusste Gruppen einzuteilen. Weiterhin wurden aktuelle Potentiale und Risiken abgeschätzt und über den Vergleich mit Literaturdaten die vergangene Entwicklung beurteilt. Die Ergebnisse zum derzeitigen bodenchemischen Ist-Zustand der Dübener Heide können wie folgt zusammengefasst werden: Als eindeutig flugaschebeeinflusst sind der pH-Wert, die Basensättigung sowie die Gesamtgehalte der Metalle Aluminium, Eisen, Calcium, Magnesium, Cadmium, Cobalt, Nickel und Zink identifiziert worden. Für diese bodenchemischen Parameter liegen klare, abnehmende Gradienten mit zunehmender Entfernung vom Hauptemittenten vor. So sind die pH-Werte im Mittel in den emittentennahen Auflagen um 1,5 pH-Einheiten höher als bei den emittentenfernen Auflagen. Während die emittentenfernen Auflagen dabei bereits etwa über den standorttypischen pH-Wert verfügen, sind die der nahen Standorte noch deutlich durch die Flugasche angehoben. Ebenso liegen in den Auflagen der emittentennahen Standorte sehr hohe Basensättigungen um 90 % und gegenüber den fernen Standorten um etwa 20 - 400 % höhere Metall-Gesamtgehalte vor. Der pH-Gradient ist außerdem die Ursache dafür, dass Metalle mit pH-abhängigen Mobilitäten sehr deutlich ausgebildete Entfernungsgradienten in ihren verfügbaren Gehalten aufweisen, wobei die verfügbaren Gehalte im Gegensatz zu den Gesamtgehalten mit zunehmender Entfernung zum Emittenten ansteigen. Anhand der Gesamtgehalte lässt sich nachweisen, dass die Flugaschebeeinflussung vor allem die Auflagen betrifft. Der Transport ganzer Flugaschepartikel in den Mineralboden wird anhand der vorliegenden Ergebnisse als unbedeutend angesehen. Dagegen erfolgt aber eine Verlagerung gelöster Flugaschebestandteile mit dem Sickerwasser. Diese führt dazu, dass ein flugaschebedingter Einfluss auf die pH-Werte, die Basensättigungen und die verfügbaren Gehalte der Basenkationen teilweise noch in 30 cm Tiefe feststellbar ist. Im tieferen Mineralboden überwiegen dann aber andere Standortfaktoren. Für die Analyse des Flugascheeinflusses ist der Oh-Horizont am besten geeignet. Hier liegen die eindeutigsten und stärksten Gradienten von allen beeinflussten bodenchemischen Parametern vor. Der Of-Horizont ist dagegen bereits durch den Einfluss der Vegetation (Basenpumpe) teilweise überprägt. Entsprechend der aktuellen Werte der eindeutig flugaschebeeinflussten Parameter lassen sich die Standorte zu drei unterschiedlich stark beeinflussten Gruppen zusammenfassen. Diese Gruppen spiegeln den Entfernungsgradienten wider und wurden deshalb als nahe, mittlere und ferne Standorte bezeichnet. Die in der vorliegenden Arbeit gefundene Gruppierung weist aber Veränderungen gegenüber der anhand der Rauchschäden der Bestände vorgenommenen Einteilung der Dübener Heide in vier Rauchschadenszonen auf [LUX 1965b]. So wird heute der ehemals stark beeinflusste Standort Ochsenkopf-BDF (RSZ 1) nicht mehr den nahen, sondern den mittleren Standorten zugeordnet, während ein Teil ehemals mäßig beeinflusster Standorte (RSZ 3) mit früher gering geschädigten Standorten (RSZ 4) zu einer Gruppe zusammengefasst werden. Ein Vergleich mit vorhandenen Literaturdaten zur Dübener Heide zeigt, dass die Unterschiede zwischen den Zonen (z. B. im pH-Wert) mit der Zeit mehr und mehr abnehmen und Nährstoffe (wie Calcium) langsam ausgewaschen werden. Bezüglich der Potentiale und Risiken kann angegeben werden, dass abgesehen von Cadmium, welches in der gesamten Dübener Heide erhöhte Werte aufweist, der Großteil der untersuchten Standorte über standorttypische mittlere Werte und Gehalte verfügt. Nur an den nahen Standorten treten überdurchschnittlich hohe pH-Werte, Basensättigungen, Calcium-Gesamtgehalte und Vorsorgewertüberschreitungen bei den Gesamtgehalten von Cadmium und Zink auf. Die hohen pH-Werte dieser Standorte führen aber dazu, dass die mobilen Schwermetall-Gehalte derzeit noch niedrige Werte aufweisen und die positive Wirkung der verbesserten Nährstoffsituation überwiegt. Dabei nimmt der Standort Burgkemnitz eine Sonderrolle ein, da er selbst gegenüber dem ebenfalls nahen Standort Buchholz über extrem hohe Calcium-Gehalte und in Verbindung mit seiner sehr mächtigen Auflage auch über sehr hohe Elementvorräte verfügt. Aufgrund der bereits zu beobachtenden Wiederversauerung und Abnahme der Calcium-Gehalte sind besonders für die nahen Standorte eine Verschlechterung der Nährstoffsituation und eine zunehmende Mobilisierung der Schwermetalle zu erwarten. Als Grundlage für die Abschätzung der Wirkung zukünftiger Veränderungen auf das Waldökosystem und die Bestände wurden deshalb Prognosen über die Entwicklung der relevanten flugaschebeeinflussten Parameter in den Auflagen der Dübener Heide aufgestellt. Mit Hilfe dieser Prognosen sollten sowohl das zu erwartende Ausmaß der Veränderung als auch deren zeitlicher Rahmen besser einschätzbar werden. Für die Prognosen wurden Altdaten, aktuelle Messwerte und die Ergebnisse eines Freisetzungsexperimentes genutzt, um daraus Trends über die mittlere Entwicklung in den beim Ist-Zustand gefundenen Entfernungsgruppen ableiten zu können. Zusätzlich wurden die Einflüsse verschiedener, in der Prognose nicht berücksichtigter Faktoren diskutiert. Mit der vorliegenden Arbeit steht damit aus bodenchemischer Sicht erstmals ein umfassendes Werkzeug für die Bewertung zukünftiger Entwicklungen in der Dübener Heide zur Verfügung. Die aufgestellten Prognosen lassen für die Auflagen der Dübener Heide die folgenden Aussagen zu: Die pH-Werte werden weiter fallen, so dass sich bereits in wenigen Jahrzehnten signifikante pH-Unterschiede zwischen den mittleren und fernen Standorten nicht mehr feststellen lassen werden. Die nahen Standorte werden sich zwar noch am längsten durch erhöhte pH-Werte auszeichnen, aber in etwa 150 Jahren wird in der gesamten Dübener Heide wieder der standorttypische pH-Wert von etwa 3,0 vorliegen. Verbunden mit der Abnahme der pH-Werte werden auch die Basensättigungen zurückgehen. Etwa 50 Jahre lang können die nahen Standorte noch als mindestens basenreich (> 50 % Basensättigung [AG-BODEN 2005]) angesehen werden. Gegen Ende des betrachteten Zeitraums von 150 Jahren ist dann mit einem einheitlichen Niveau der Basensättigung von ca. 20 % (Grenze zwischen mittelbasisch und basenarm [AG-BODEN 2005]) in den Auflagen der Dübener Heide zu rechnen. Die Vorräte von Calcium und Magnesium werden nach und nach ausgetragen, wobei die Hauptursache dafür bei Calcium die Auswaschung aufgrund der Wirkung saurer Niederschläge, bei Magnesium der Ernteentzug ist. Mindestens 50 Jahre kann aber an den nahen Standorten noch von einer überdurchschnittlich guten Calciumversorgung ausgegangen werden. Stellenweise kann aber trotz der hohen Vorräte bereits in 30 Jahren die Magnesiumversorgung zum wachstumsbegrenzenden Faktor werden, da nur ein relativ kleiner Teil des Magnesiums freisetzbar zu sein scheint. Bezüglich des Risikos nachteiliger Wirkungen aufgrund zu hoher verfügbarer Schwermetall-Gehalte sind nur Cadmium und Zink von Bedeutung. Die verfügbaren Gehalte dieser Schwermetalle werden im Zuge der Wiederversauerung ansteigen. Gleichzeitig erfolgt aber auch eine Auswaschung der Gehalte, die dem Anstieg der verfügbaren Gehalte und damit dem Überschreiten der Vorsorgewerte entgegenwirkt. Eine Gefährdung der Waldbestände ist demnach kaum zu erwarten. Die Toleranz der Bäume gegenüber Cadmium und Zink sollte aber trotzdem für langfristige waldbauliche Planungen berücksichtigt werden. / In this study the dynamics of nutrients and pollutants within fly ash-affected forest soils of the Dübener Heide, Germany, were examined concerning their current state and the future development to be expected. In the Dübener Heide large amounts of fly ash were deposited over decades, which had a crucial and lasting impact on the soil properties. Even 15 years after the abrupt end of the immissions this influence can still be proven. The ecosystem has adapted itself to the environmental conditions changed by the fly ash. However, after the loss of further immissions the system is subject to changes once again with yet unknown consequences for the forest. As a basis for sustainable forest planning and an adapted nature park management the current soil-chemical state of the Dübener Heide was examined and prognoses for the future development were derived within the ENFORCHANGE subproject of soil processes. For the determination of the current state 12 sites, that are representative for the typical soil types and stands of the Dübener Heide, were selected which have increasing distances to the coal-fired power plant Zschornewitz, regarded as the main emitter. Soil profiles, two meters in depth, were set up and sampled in depth stages. The soil samples were analyzed for different soil-chemical parameters by means of standard methods. The results were judged regarding the exceeding of mean, critical and limiting values as well as the occurrence of dependencies on depth or distance. By that means parameters which are definitely influenced by the fly ash as well as the most strongly affected depth stages were identified. These information were used afterwards in order to statistically divide the sites into groups of different grade of fly ash-affection. Furthermore current potentials and risks were estimated, and the previous development was judged by comparison with literature data. The results for the current soil-chemical state of the Dübener Heide can be summarized as follows: The pH value, the base saturation and the total contents of the metals aluminium, iron, calcium, magnesium, cadmium, cobalt, nickel and zinc were identified as definitely fly ash-affected. Decreasing values of these soil-chemical parameters are clearly observable with increasing distance from the main emitter. So on average, the pH values of the forest floor horizons close to the emitter are greater by about 1.5 pH units than that of sites far from the emitter. Thereby the forest floor horizons far from the emitter already have approximately the typical pH value while pH values are sill raised by the fly ash at the closed-by sites. Very high base saturations around 90 % and total metal contents, that are higher by approximately 20 400 % compared with more distant sites are present in the forest floor horizons of sites close to the emitter, too. In addition, the pH gradient is the cause for the fact that the available contents of metals with pH-dependent mobility exhibit very clearly formed distance gradients, with the available contents rising with the distance to the emitter contrary to the total contents of the metals. By means of the total contents it can be proven, that the influence of the fly ash mainly concerns the forest floor horizons. The transport of whole fly ash particles into the mineral soil is regarded as insignificant on the basis of the available results. However, a displacement of solved fly ash components with seepage water takes place. This leads to the fact, that a fly ash-induced influence on the pH value, the base saturation, and the available contents of the base cations is partly detectable as far as 30 cm in depth. However, in still deeper mineral horizons different location factors predominate. For the analysis of the fly ash influence the Oa-horizon is the most suitable. Here the clearest and strongest gradients of all affected soil-chemical parameters are present. The Oe-horizon is additionally marked in parts by the influence of the vegetation (base pump) According to the current values of the definitely fly ash-affected parameters the sites can be divided into three groups with different grade of fly ash-affection. The distance gradients are reflected in these groups, and that is why the groups were termed closed-by, intermediate and distant sites. However, the grouping found in the current study exhibits changes compared with the grouping of the Dübener Heide into the four smoke damage zones [LUX 1965b] according to the damage done to the stands by the smoke. Thus, today the formerly strongly affected site Ochsenkopf-BDF (RSZ 1) is no longer assigned to the closed-by but instead to the intermediate sites, while a part of the formerly moderately affected sites (RSZ 3) is now combined into one group together with formerly only slightly damaged site (RSZ 4). A comparison with existing literature data from the Dübener Heide shows, that the differences between the zones (e.g. in pH value) decrease more and more with time, and that nutrients (like calcium) are slowly washed out. Concerning the potentials and risks it can be indicated that apart from cadmium, which exhibits increased values over the entire Dübener Heide, the majority of the examined sites has averaged values and contents typical for the location. Only at the closed-by sites pH values, base saturations, total contents of calcium above the average and violations of limits of precaution of cadmium and zinc occur. But the high pH values at these sites lead to the fact, that the mobile heavy metal contents exhibit still low values at present, and that the positive effect of the improved nutrient situation predominates. The site Burgkemnitz takes a special position, since it has extremely high calcium contents and in connection with its very thick forest floor horizon also very high element stocks even in comparison with the likewise closed-by site Buchholz. Due to the already observable acidification and the decrease in calcium contents a degradation of the nutrient situation and an increasing mobilization of the heavy metals are to be expected particularly for the closed-by sites. Therefore, as a basis for the estimation of the effect of future changes on the forest ecosystem and the stands prognoses for the development of the relevant fly ash-affected parameters in the forest floor horizons of the Dübener Heide were derived. With the help of these prognoses both the extent of the change to be expected and its time frame should become better assessable. For the prognoses literature data, measured values of the current study and the results of a release experiment were used in order to be able to derive from it trends for the averaged development within the different groups of sites found for the current state. Additionally the influences of different factors not considered for the prognoses were discussed. So with this, for the first time there is available a comprehensive tool for the evaluation of future developments in the Dübener Heide from soil-chemical point of view. The set up prognoses allow the following statements for the forest floor horizons of the Dübener Heide: The pH values will continue to fall, so that already in a few decades significant pH differences between the intermediate and the distant sites will not be determinable any more. The longest time the closed-by sites will be characterised by increased pH values, but in approximately 150 years a location typical pH value of about 3.0 will be present over the entire Dübener Heide again. Connected with the reduction of the pH values the base saturation will decrease, too. About 50 more years the closed-by sites can still be regarded as at least base rich (> 50 % base saturation [AG-BODEN 2005]). But towards the end of the considered time of 150 years it has to be reckoned on a uniform level of the base saturation of approximately 20 % (threshold between medium-basic and base-poor [AG-BODEN 2005]) in the forest floor horizons of the Dübener Heide. The stocks of calcium and magnesium will be gradually decreased, for what the main cause is leaching due to the effect of acid precipitations for calcium and harvest removal for magnesium. At least for 50 more years it can be assumed that the closed-by sites will have a calcium supply good above average. In parts, however, despite the high stocks the magnesium supply can already become the growth-limiting factor in 30 years, since only a relative small part of magnesium seems to be available for leaching. Only cadmium and zinc are of importance concerning the risk of unfavourable effects caused by too high contents of mobile heavy metals. The available contents of these heavy metals will rise as the result of increasing acidification. But at the same time leaching of the metals takes place what counteracts the rise of the available contents and thus the violation of the limits of precaution. According to this an endangerment of the forest stands is hardly to be expected. However, for long-term forest-structural planning the tolerance of the trees with respect to cadmium and zinc should be considered nevertheless.

published_or_final_version / abstract / toc / Geography and Geology / Master / Master of Philosophy

Although silicon (Si) has not yet been recognized as an essential nutrient element, its application to sugarcane (Saccharum officinarum L.) has proved to be beneficial. Since optimum crop production depends on the maintenance of adequate plant nutrients in the soil, there is a need in the South African sugar industry for a reliable index for assessing the requirement for supplemental silicon (Si) in soils, particularly in reducing the risk of Eldana saccharina stalk borer infestation in cane. The objective of this study was to assess Si availability in soils, to select a suitable Si extraction method and a critical value for determining when a response is likely. For this purpose, five acid soils (representing. some of the most important agricultural soil groups used for sugarcane production in the sugar belt) were used in October 2004, in the lAKE WILSON glasshouse of the South African Sugarcane Research Institute (SASRI) based at Mount Edgecombe. Except for the Arcadia form soil with an initial Si content of 1.2 mmol kg- I as estimated using the O.OlM H2S04 + (NH4)zS04) extractant, soils representing the other five soil forms namely Cartref, Glenrosa, Longlands and Nomanci; exhibited a sub-optimal Si content of not more than 4.0 mmol kg-I. Sorghum was used as a plant crop and sugarcane as a ratoon crop because of their Si accumulator status. Three different Si sources: calmasil, slagment and wollastonite; with respectively 9.85, 15.20, and 5.25% Si content were applied at increasing rates of 0, 3 and 6 tons ha- 1 as Si fertilizers. Silicon (Si) was extracted from untreated and treated soils by utilizing six different extractants, (1) O.OlM H2S04 + (NH4)2S04; (2) Distilled water; (3) 0.025M H2S04; (4) 0.5M CH3COOH; (5) 0.5M CH3COONH4pH 4.8; and (6) O.OlM CaCh.2H20. The amount of soil Si extracted followed the order: 0.025M H2S04 > 0.5M CH3COOH > O.OlM H2S04 + (NH4)2S04 > O.OlM CaCh.2H20 > 0.5M CH3COON~ pH 4.8 > distilled water. Soil Si extracted by 0.025M H2S04 was significantly correlated with soil exchangeable cations,. CEC, clay content, cane biomass yield, cane Si uptake and increasing rates of applied Si. Averaged over all soil forms investigated, the increases in dry biomass yield and Si uptake ranged. from 18% to 154% for sorghum; and from 23% to 85% for cane respectively. Even though the highest increases (%) in cane biomass yield and Si uptake were obtained on a Nomanci form soil with initial poor fertility status, the highest means were obtained on an Arcadia form soil with the highest Si initial content. There was no difference between different Si sources in their ability to influence cane biomass yield and Si uptake, and therefore the supply to the soils. Even though the lower and higher Si source rates were not different from each other, they increased cane yield and Si uptake, indicating that Si was undoubtedly beneficial for sugarcane. The Si critical levels for different soils as estimated by 0.025M H2S04 were 6.0 mmol kg-1 (168 mg kg-I) for Arcadia; 2.6 mmol kg-I (64 mg kg-I) for Cartrel; 2.5 mmol kg-I (64 mg kg-I) for Glenrosa; 1.6 mmol kg-I (45 mg kg-I) for Longlands; and 2.4 mmol kg-I (67 mg kg-i) for Nomanci form soils. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2007.

Little is known regarding the effects of land use on soil organic matter and P status of South African soils. For that reason, the effects of the main agricultural land uses in the midlands region of KwaZulu-Natal [maize (Zea mays), sugarcane (Saccharum spp), annual ryegrass pasture (Lolium multiflorum), permanent kikuyu pasture (Pennisetum clandestnum), gum (Eucalyptus grandis) and pine (Pinus patula)] on soil organic matter content, microbial biomass C and P and inorganic and organic P pools derived from a modified Hedley P fractionation was investigated on two sites where the longterm history of land management was known. In comparison with undisturbed native grassland, permanent kikuyu pasture resulted in an increase in organic C, organic P and microbial biomass C and P. Maize and sugarcane production resulted in a decrease in organic C, organic P and microbial C and P. Under annual pasture, gum and pine forests, organic matter and microbial biomass concentrations remained similar to those under native grassland. Under native grassland, extractable organic P accounted for 50% or more of the total P content of soils but under agricultural management with regular applications of fertilizer P, there was an increase in the percentage of total P present as inorganic P. Agricultural management greatly affected the distribution of P among the various inorganic and organic P fractions. Resin-Pi and NaHC03-Pi (the potentially-available forms of Pi) showed similar trends with land use being greatly elevated under kikuyu pasture at both sites and sugarcane and maize at one site. This accumulated Pi was thought to have originated from recent fertilizer applications and possibly recently mineralized organic P. Trends for NaOH-Pi with land use differed greatly from those of the Resin- and NaHC03Pi fractions. Concentrations were notably high under maize and sugarcane production. Of the pools of soil organic P, the NaHC03-Po fraction was most greatly affected by land use, being elevated under kikuyu and decreased under maize and sugarcane. This supports the assertion that it is the NaHC03-Po fraction that is the most labile soil organic P pool. It was concluded that land use greatly affects soil organic C and P status, soil microbial biomass C and P contents, soil inorganic P concentrations and the distribution of P among the various P fractions. A short-term (8 weeks) laboratory incubation experiment was carried out to compare the effects of inorganic (KH2P04) and organic (cattle manure, poultry manure and maize crop residues) sources of P, applied at a rate equivalent to 30 kg P ha-1 , on soil inorganic and organic P fractions and the potential availability of soil P. Additional treatments consisted of lime [Ca(OHhl at 5 ton ha-1 and lime plus inorganic P. Applications of lime raised soil pH to a similar extent after 1, 4 and 8 weeks incubation. After 8 weeks, a small increase in soil pH was also noted for the cattle and poultry manure and maize residue treatments. For the inorganic P fractions, substantial treatment effects were observed only for the Resin-Pi fraction. The inorganic P source was more effective than the organic ones at increasing Resin-Pi after 1 and 4 weeks incubation and of the organic sources, cattle and poultry manure were more effective than maize residues. Resin-Pi concentrations generally increased between 1 and 4 weeks incubation but then declined rapidly between 4 and 8 weeks incubation. After 8 weeks incubation, treatment effects on Resin-Pi were small. Concentrations of NaHC03-Pi, dilute HCI-Pi and concentrated HCI-Pi all declined over the incubation period. There was no clear trend with incubation for NaOH-Pi although for the poultry manure and maize treatments, concentrations declined between 4 and 8 weeks incubation. In general, concentrations of NaHC03-Po were greater for organic than inorganic P sources after 8 weeks incubation suggesting microbial immobilization of P in these treatments. There were increases in NaHC03-Po and concentrated HCI-Po over the incubation period suggesting progressive immobilization of P from the Pi fractions that declined in concentration during the incubation. Concentrations of NaOH-Po were not greatly affected by incubation period. The lime treatments, however, had lower NaOH-Po concentrations than the others suggesting that liming may have stimulated microbial mineralization of Po. Residual-P concentrations increased over the incubation period. This was attributed to conversion of extractable Pi fractions into recalcitrant, non-extractable Pi forms and/or immobilization of Pinto intransigent organic forms. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2006.

Copies of author's previously published articles inserted. / Bibliography: leaves 195-230. / xx, 320 leaves : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / In this study the soil aqueous phase chemistry of Zn and Cu in alkaline sodic soils are investigated. The chemistry of trace metal ions at indigenous concentrations in alkaline sodic soils are reported. Metal ions at low concentrations are measured by the graphite furnace atomic absorption spectrometry (GFAAS) technique. / Thesis (Ph.D.)--University of Adelaide, Dept. of Soil Science, 1998

The major land use in New Zealand is pastoral farming of sheep and cattle. In intensively grazed dairy-pasture systems, animals graze on nitrogen (N)-rich legume-based pastures, but do not efficiently utilize the N they ingest. On average only 10.5% of the N in forage-based animal feed is converted into milk and the remainder is excreted in dung and urine. In the pastures, a cow urine patch can typically contain up to 1000 kg N ha-1. Nitrogen input, either in the form of cow urine or fertilizer, often exceeds immediate plant requirements and hence is susceptible to losses as ammonia (NH3) volatilisation and nitrous oxide (N2O) emissions and removal in drainage water through nitrate (NO3-) leaching. This loss of N from grazed pastures causes detrimental environmental impacts in the form of acidification and eutrophication of the soil and water bodies, global warming, destruction of stratospheric ozone, and NO3- toxicity. Various approaches have been attempted to mitigate the economic and environmental impacts of N losses. One such approach is the use of Urease (UIs) and Nitrification (NIs) inhibitors. There have been extensive studies on the value of UIs in arable farming and NIs in grazed pastures. However, only limited work on the impact of UI and NI alone and in combination in influencing the N dynamics, and thus mitigating N gaseous losses from pastures, has been conducted. This thesis examines the impact of UI (Agrotain; N-(n-butyl) thiophosphoric triamide) and NI (Dicyandiamide, commonly known as DCD), when applied alone or in combination to cow urine and urea fertiliser, on N losses through NH3 and N2O emissions and NO3- leaching, and on herbage production under glasshouse conditions and a field-plot study. The degradation rate of DCD, and its effect on nitrification and on N2O emissions from four soils varying in their physical and chemical properties was also examined under laboratory incubations. The results from the field-plot study were then used to predict the effect of DCD on N2O emissions reductions from urine by adapting the process-based NZ-DNDC model. Both NH3 and N2O emissions have common sources in agriculture. Therefore, chambers were adapted to measure their emissions simultaneously using active and passive gas sampling. Active sampling involved continuous air flow and the use of acid (0.05 M H2SO4 and 2% H3BO3) traps for NH3 measurements and passive sampling involved collecting three gas samples over a one-hour period from a static chamber used for N2O emissions. The first glasshouse experiment used UI with urine or urea to assess its effect on NH3 and N2O emissions, changes in soil mineral-N and N uptake by pasture plants. The UI treatments also involved two commercial products, Sustain Yellow (urea coated with Agrotain and elemental S) and Sustain Green (urea coated with Agrotain). The use of UI effectively decreased total NH3 emissions, as well as delaying the time of maximum NH3 emissions from both urea (600 kg N ha-1) and urine (476 kg N ha-1) by 27% and 22%, respectively. The UI-induced decrease in NH3 volatilization ranged from 42-48% when urea was applied @ 100 kg N ha-1. Urease inhibitor was also effective in decreasing N2O emissions significantly from urine and urea applied @ 100 kg N ha-1. The addition of UI increased dry matter yield by 13-19% as compared to the urea-alone treatment. In the second glasshouse study, NI (DCD) was added @ 25 kg ha-1 to urea (@ 25, 50 and 75 kg N ha-1) and urine (@ 144, 290 and 570 kg N ha-1) applied at different rates. Addition of DCD reduced N2O emissions from both urea and urine and NO3- leaching from urine. Dicyandiamide reduced N2O emissions by 34-93% from the added urea and 33-80% from the added urine. However, its use increased the amount of ammonium (NH4+) present in the soil by 3 to 13% both in the urea and urine treatments, and this NH4+ was susceptible to leaching and volatilisation losses. The addition of DCD, however, resulted in a 60-65% reduction in NO3- leaching from urine applied to pasture soil cores. It also caused a significant reduction in NO3- -induced cation leaching. Leaching of K+, Mg+2 and Ca+2 ions was reduced by 36-42%, 33-50% and 72%, respectively, with DCD applied to cattle urine (290 and 570 kg N ha-1). The combined use of UI and NI was more effective in controlling N gaseous losses than using them individually. The combination of UI and NI retarded NH3 emissions by 70% in the urea treatment and by 4% in the urine treatment (field-plot study). It also considerably reduced N2O emissions (50-51%) following the application of urea and urine (field-plot study) to pasture soil. With the combined inhibitors, there was a 14 and 38% increase in herbage yield from added urea and urine (field-plot study), respectively. A laboratory incubation experiment was undertaken to study the effect of soil types and the rate of DCD application on the degradation kinetics of DCD. The rate of degradation of DCD varied among the four soils studied. The degradation was slowest (half-life period of 6 to 11 days) in an allophanic soil with a high concentration of organic matter. The effectiveness of DCD in inhibiting nitrification also varied depending on the nature and amount of soil organic matter and clay content. The maximum inhibition was observed in a soil with low organic matter and high clay content. Finally, 'NZ-DNDC', a process-based model, was adapted and used to simulate the effect of DCD on emissions reduction using DCD inhibition values that vary according to different soil types. This model effectively simulated the effect of DCD on N2O emissions reductions in Tokomaru silt loam following urine application. However, more field data are required from a range of pasture soils with contrasting amount of soil organic matter and clay content under differing climatic conditions to further test this model modification to predict emission-reductions with DCD application in different soil types.

The soils used by the East Coast Organic Producers Trust (ECOPT; the grower group that this study is targeted towards) have exceptionally low soil Olsen P concentrations (ca. 6 mg/L). These and other limitations (e.g. poor weed and pest and disease control) result in many ECOPT growers being unable to produce economic yields on anything other than small scale gardens. Fertilisers and manures are seldom used by these growers, which exacerbates the problem. Thus, the object of this research was to provide information to ECOPT on which fertilisers and application strategies would provide the best returns on their phosphorus (P) fertiliser investment. The experimental work was carried out in two parts. A laboratory study tested a range of phosphate rock (PR) based fertilisers and application rates; Ben Guerir reactive phosphate rock (RPR; 67, 133, 267, 533 and 1,333 mg P/kg soil), BioPhos and BioSuper (267 and 1,333 mg P/kg soil) and a no fertiliser Control. Soil fertiliser mixtures were incubated for 155 days and periodic measurements of PR dissolution, soil pH and Bic-P (analogous to Olsen P but expressed in µg/g) were undertaken. The field study used fewer application rates and two application methods; banded and broadcast. Broadcast plots were applied at 678 mg P/kg soil (488 kg P/ha); banded RPR was applied at 236, 678 and 1475 mg P/kg soil (40, 115 and 250 kg P/ha respectively) and banded BioPhos and BioSuper at 678 mg P/kg soil (115 kg P/ha). A Control was also included. Fertilisers were applied in October 2004 and changes in soil pH and Bic-P were measured in the broadcast plots only over a 344 day period. Potato (Solanum tuberosum L. cv. Desiree) was the test crop. Regression analysis was used to generate exponential equations to describe the changes in Bic-P over time (∆Bic-P). Differences between fertilisers in the amount of P dissolved and pH fluxes were used to explain the differences in ∆Bic-P. BioSuper dissolved quicker and generated greater ∆Bic-P than RPR and BioPhos, which were similar. Higher application rates produced greater increases in Bic-P than lower rates but decreased the % of P applied that dissolved. The increase in Bic-P over time from fertiliser application was much slower in the field compared with the laboratory. This was put down to differences in experimental conditions; mainly soil pH and soil aggregate surface area. Potato tuber yield (mean = 35 t/ha) did not respond to any of the fertiliser treatments despite a significant increase in P concentration of the shoots mid-way through the season in all broadcast treatments (shoot P concentration was not analysed in the banded plots). Water and N availability were the main limiting factors in this season as the crop was not irrigated and soil N supply was insufficient to produce a full canopy. Phosphorus response curves generated using the fertiliser response model PARJIB (Reid, 2002), and an economic analysis, indicated that for RPR and BioPhos the optimum economic application rate was 200 kg P/ha and for BioSuper it was 100 kg P/ha (applied every third and second year respectively).

Sulphur is an important nutrient to plants, and reports of its deficiency have been increasing worldwide. Sulphur starvation causes losses in both yield and quality, and it reduces nitrogen use efficiency of plants. As the timing for fertilisation can be decisive for avoiding deleterious effects, improvements in the description of the sulphur balance in fields are a valuable contribution for assisting fertiliser management. Sulphate is the most important inorganic form of sulphur in soils. Being the mobile form, sulphate is readily available for plants, and also prone to be leached. Therefore the description of the movement of sulphate is the key component of the sulphur balance. Leaching of sulphate from the soil can be significantly delayed by its adsorption onto the soil particles. Soil type and pH are the main factors defining the sulphate adsorption capacity; although the presence of other ions in the soil solution can have a considerable effect. It has been reported that in some soils, typically volcanic and tropical soils with variable-charge characteristics, the co-presence of sulphate and calcium can substantially enhance their retention via ion-pair adsorption (IPA). To determine the influence of cations on the movement of sulphate, series of batch and miscible displacement experiments were conducted using two New Zealand soils, of contrasting ion adsorption capacities: the Taupo sandy and Egmont loam soils. These experiments demonstrated the occurrence of cooperative adsorption of sulphate and calcium in the Egmont soil, but not in the Taupo soil. Batch experiments were conducted to examine the IPA adsorption process in the Egmont soil in more detail. Based on the analyses of the results from these two series of experiments, plus the review of published data, three different mathematical approaches for evaluating the amount of solute adsorbed as ion-pairs are proposed. A computer program was built for solving an adsorption model using these three approaches, and was used to compare the model's predictions and the observed adsorption data. An extension of this program, coupling the adsorption model with a solute transport description, was used to simulate the movement of sulphate and calcium. Comparisons between the data from the miscible displacements and the results from this model are used to demonstrate the applicability of the proposed IPA description for modelling the transport of these ions in the soil. Finally, results from a pot trial with Egmont soil are used to examine the relevance of IPA for the movement of sulphate under non-equilibrium conditions, and with active plant growth. Although the results from this experiment regarding IPA were statistically non-significant, some insights could be obtained and are discussed. More studies involving IPA under non-equilibrium experiments are needed for a better understanding of the relevance of IPA in field conditions.