The South Burnett region of Queensland is Australia's most important rainfed peanut (Arachis hypogea L.) production area. It also produces a considerable amount of cereal and grain legume crops. The cropping soils of the region are red, acid to neutral, clay loams that are classified as Ferrosols (Australian Soil Classification). Over 50 years of cropping on these soils has resulted in severe depletion of nutrient reserves, particularly potassium (K). In addition, the remaining K is predominantly confined to the surface 10 or 15cm of the soil profile, a feature commonly refered to as nutrient stratification. Dry periods during the summer cropping season are common due to the highly variable, summer-dominant rainfall pattern of the South Burnett. As topsoil dries out, crops forage for moisture and nutrients from lower in the soil profile where K reserves are smaller. It is therefore suspected that the combination of dry periods and stratified K reserves have resulted in an increasing incidence of K deficiency symptoms in summer crops. To investigate these issues, K relations of Ferrosols of the South Burnett were studied using soils from two representative sites. The pools of soil K that are important to crop growth in Ferrosols, and their interaction was examined through fractionation of soil K pools, and determination of quantity/intensity relationships, charge characteristics and clay mineralogy, and a leaching column study. A rapid K uptake period was identified for peanut and the effect of profile distribution and soil moisture during this period on K accessibility was studied in a divided column experiment. Finally, on-farm trials were used to evaluate commercial-scale options for improving K distribution in field profiles. It was found that the immediately available exchangeable K pool in these soils was the most important source of soil K, and was poorly buffered by slowly available non-exchangeable K. However the leaching column study revealed that K was preferentially adsorbed onto soil cation exchange sites, displacing calcium (Ca) and magnesium (Mg) ions, and therefore was not susceptible to vertical movement within the soil profile. These observations helped to explain the development of stratified K profiles in these soil types. Peanut (cv. Streeton) was found to take up most of its K requirement between 25-70 days after planting. The divided column study showed that profile distribution, and topsoil iv moisture content during this rapid K uptake period, were able to affect the ability of peanut plants to access K. Plants that grew in low K soil, or where soil was dry at the site of K supply, had reduced access to K. However, improving access to K did not result in improved growth, but rather in a significant reduction in dry matter (DM) production, apparently due to interference in the availability of other nutrients, possibly phosphorus (P), magnesium (Mg) or boron (B). Field studies showed that application of K and profile inversion improved K uptake and DM production of various crop species. However, in most instances improved K uptake and DM production was not reflected in increased yield. It was suggested that a combination of agronomic factors, seasonal conditions and crop type prevented the expression of yield responses to improved K nutrition and these influences need to be understood. The findings of this project have important consequences for nutrition of crops grown on Ferrosols in the South Burnett region. Surface applied K cannot be expected to increase exchangeable K in the subsoil unless it is incorporated to depth. Similarly, band applied K will remain close to the site of application as a result of only limited vertical or lateral movement. This may affect the ability of roots to access band applied K. The ability of surface applied K to displace Ca and Mg from soil exchange sites may have negative implications for the Ca nutrition of developing peanut pods. On the other hand, it could present an opportunity for the movement of Ca into deeper soil layers to address the amelioration of acid subsoils. The unexplained negative responses to potassium chloride application and apparent effect on P, Mg or B nutrition need to be investigated.

The current silvicultural regimes of Pinus radiata plantations in New Zealand with wider initial tree spacings have created the potential for increased growth of understorey vegetation. A consequence of this is that the response of P. radiata to P fertiliser is expected to be more influenced by the interaction between the P fertiliser, the tree and the understorey vegetation than was the case in the past. The objectives of this study were to investigate the influence of different rates of a soluble and a sparingly-soluble P fertiliser (Triple superphosphate and Ben-Geurier phosphate rock) and weed control, and their interactions, on soil P chemistry and the growth and P uptake of 4-5-year-old second-rotation P. radiata on an Allophanic Soil (Kaweka forest) and a Pumice Soil (Kinleith forest). The results showed that the application of P fertilisers had no effect on P. radiata growth at both field trial sites two years after this treatment, although it increased radiata needle P concentration. However, at both sites, the understorey vegetation removal treatment increased tree diameter at breast height and basal area. At the highly P-deficient (Bray-2 P 4 µg g-1) Kaweka forest, the presence of understorey (bracken fern and some manuka) reduced resin-Pi and Olsen P concentrations, but at the moderate P fertility (Bray-2 P 13 µg g-1) Kinleith forest, the understorey (Himalayan honeysuckle, buddleia and some toetoe) increased Bray-2 P, resin-Pi, and Olsen P concentrations. A glasshouse study on P. radiata seedlings was conducted to test the hypothesis that when ryegrass (Lolium multiflorum) is grown with P. radiata, it increases radiata needle P concentration, while when broom (Cytisus scoparius L.) is grown with P. radiata, it has no effect. The acid phosphatase activity in the rhizosphere of P. radiata was higher when radiata was grown with broom than that when it was grown with ryegrass. This is consistent with the higher P concentration in needles of radiata grown with broom than that of radiata grown with ryegrass, in the absence of P fertiliser addition. However, when P fertiliser was added (50 and 100 µg P g-1 soil) the needle P concentration of radiata grown with broom was lower than that when radiata was grown with ryegrass.

Oil palm is the largest national crop produced in Papua New Guinea. It is grown on over 80,000 ha of young volcanic soils in five Provinces, employs over 12,000 workers and uses >12,000 tonnes of fertiliser to offset nitrogen deficiency which is the most limiting factor to production. Oil palms strip out 160 - 200 kg N ha-1 yr-1 from the soil. Nitrogen fertilisers account for 60-70 % of all variable production costs but 40-60 % of applied fertiliser cannot be accounted for. Few studies have investigated the amounts of nitrogen lost via leaching, denitrification, volatilisation or as surface runoff in tropical soils and none have been done in Papua New Guinea. Oil palm soils typically have extremely high infiltrabilities (80-8,500 mm hr-1) and receive high annual rainfall which throughfall makes spatially non-uniform. The objective of this study was to assess and quantify nitrogen losses and suggest strategies that might assist in reducing them and their impact on the environment. The modest facilities available at the two research sites, West New Britain (Dami) and Oro (Sangara) Provinces, meant that no analytical work could be done on-site, so simple but appropriate methods were used to evaluate losses, with samples collected, preserved and sent off-shore for analysis. Large four-palm plots were used to evaluate runoff; a gas trap was used to collect evolved nitrous oxide, and lysimeters, suction cups and finally an in situ destructive soil sampling procedure were all used to assess leaching losses and the rate of nitrification of ammonium fertiliser. Results suggest that under the extreme total annual rainfall at Dami (3,500-4,000 mm) and to a lesser extent at Sangara (2,500-3,000 mm), leaching is the dominant loss pathway, with the rate of loss depending, to some extent, on the rate of nitrate formation and the retentivity of the soil for ammonium, but mainly on the rate at which drainage water is generated. A leaching model was developed that indicated that the average residence time of nitrogen fertiliser in the root zone (0-50 cm) varied from 21 days in February, at Dami, to 190 days in May, at Sangara.

An abundance of waste products from the forestry industry (sawdust and paper pulp) lead to the concept of using them as growing media for high value crops on a field scale. However, management of subsequent weed growth posed a problem as the impact of these novel media on the performance and fate of herbicides was unknown. Three aspects of sawdust and paper pulp waste were examined and compared to two cropping soils, viz. their effect on herbicide behaviour with regard to crop selectivity, weed control efficacy and the environmental fate of selected chemicals. Cropping species such as lettuce and onions were more susceptible to alachlor and chlorpropham in sawdust than in paper pulp. The two cropping soils evaluated (Horotiu sandy loam and Mangateretere silt loam) tended to be intermediate although the former was often close to the sawdust and the latter to the paper pulp in terms of herbicide phytotoxicity to the crop plants. For the less water soluble herbicide pendimethalin, the differences in crop selectivity in the different media were not significant. The effect of the media on the efficacy of weed control was evaluated through plant species with a much lower tolerance to the herbicides evaluated in contrast to the above species. For these plants the efficacy of the herbicides was generally lower in both the sawdust and paper pulp than in the two soils. The effect was more pronounced with the more soluble alachlor, where efficacy was reduced by factors of 5 – 10, compared to pendimethalin where efficacy reduction was by factors of 0 – 3. The two high organic media had contrasting effects on the various environmental behaviour indices evaluated. Herbicide adsorption as quantified by distribution coefficient (Kd) was higher in the two novel media compared to both the Horotiu and Mangateretere soils. However, when the Kd was normalised to organic carbon (Koc), there was less variation amongst the media indicating that organic matter is an important factor in controlling sorption in these media. However, despite the high level of adsorption in the sawdust, herbicides were most prone to leaching in this medium. Conversely the paper pulp tended to be more retentive while the two soils were intermediate. The degradation as quantified by half-lives (t½) of the herbicides was generally slower in the two novel media, probably reflecting the higher sorption in these two media but also due to the lower level of microbial activity in the sawdust and paper pulp. The study shows that herbicide behaviour in these carbon based media differs significantly from that expected from soil organic matter, mainly due to the non-humified nature of the organic matter in the media and its poor biological activity.

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.

This study has provided fundamental information on the fate of urine nitrogen (N) when applied to pasture soils. In this work the three pasture soils used were a Bruntwood silt loam (BW), an old well-developed (lime and fertilizer incorporated and farmed for more than 20 years) peat soil (OP) and a young peat (YP) which was less developed (farmed for about 10 years). Initial soil chemical and physical measurements revealed that the peat soils were acidic, had higher cation exchange capacities, had greater carbon:nitrogen ratios and were better buffered against changes in soil pH than the BW soil. However, the BW soil was more fertile with a higher pH. The peat soils had lower bulk densities and higher porosities. Four experiments were performed. In the first experiment ¹⁵N-labelled urine was applied at 500 kg N ha⁻¹ to intact soil cores of the three soils. Treatments imposed were the presence and absence of a water table at two temperatures, 8°C or 23° C, over 11-14 weeks. ¹⁵N budgets were determined. This first experiment showed that the nitrification rate was faster in the BW soil and was retarded with a water table present. Significant leaching of nitrate occurred at 8°C in the BW soil without a water table. This was reduced when a water table was present. Leaching losses of urine-N were lower in the peat soils than in the BW soil. Apparent denitrification losses (i.e. calculated on a total-N recovery basis) ranged from 18 to 48 % of the ¹⁵N-applied with the greatest losses occurring in the peat soils. The second experiment examined denitrification losses, over 30 days, following the application of synthetic urine-N at 420 kg N ha⁻¹ to small soil cores situated in growth cabinets. The effects of temperature (8°C or 18°C) and synthetic urine (presence or absence) were measured on the BW and OP soils. Nitrous oxide (N₂0) measurements were taken from all soil cores and a sub-set of soil cores, at 18°C, had ¹⁵N-labelled synthetic urine-N applied so that ¹⁵N-labelled nitrogen gases could be monitored. This experiment showed that the application of synthetic urine and increased soil temperature enhanced denitrification losses from both soils. Denitrification losses, at 18°C, as ¹⁵N-labelled nitrogen gases accounted for 24 to 39 % of the nitrogen applied. Nitrous oxide comprised less than half of this denitrification loss. Losses of N₂0 in leachate samples from the soil cores accounted for less than 0.1 % of the nitrogen applied. A third experiment, using Iysimeters, was performed over a 150 day period in the field. The six treatments consisted of the 3 soils with applied synthetic urine, with or without a simulated water table; each replicated three times. Lysimeters were installed in the field at ground level and ¹⁵N-labelled synthetic urine-N was applied (500 kg N ha⁻¹) on June 4 1992 (day 1). Nitrification rates differed between the soils following the trend noticed in the first experiment. As in the first experiment, nitrate was only detected in the leachate from the BW soil and the inclusion of a water table reduced the concentration of nitrate. In the BW soil, the leachate nitrate concentrations exceeded the World Health Organisation's recommended limit (< 10 mg N L-1) regardless of water table treatment. No nitrate was detected in the leachates from the peat soils but there was some leaching of organic-N (< 5 % of N added) in all the peat soil treatments. Denitrification losses were monitored for the first 100 days of the experiment. In the BW soil without a water table, N₂0 production peaked at approximately day 20 and accounted for 3 % of the nitrogen applied. In the peat soils the measured denitrification losses accounted for less than 1 % of the nitrogen applied. Apparent denitrification losses in the peats were, however, calculated to be approximately 50 % of the ¹⁵N-labelled synthetic urine-N applied. It is postulated that the difference between apparent denitrification losses and those measured could have been due to; loss of dinitrogen in leachate, protracted production of dinitrogen below detectable limits, production of denitrification gases after measurements ceased (i.e. days 100 to 150) and entrapment of dinitrogen in soil cores. Due to the apparent denitrification losses being so high, further research into this nitrogen loss pathway was performed. The fourth and final experiment measured denitrification directly using highly enriched (50 atom %) ¹⁵N-labelled synthetic urine-N. It was performed in a growth cabinet held initially at 8°C. The ¹⁵N-labelled synthetic urine was applied at 500 kg N ha⁻¹ to small soil cores of each soil type. Fluxes of N₂0 and ¹⁵N-labelled gases were measured daily for 59 days. On day 42 the temperature of the growth cabinet was increased to 12°C in an attempt to simulate the mean soil temperature at the end of the field experiment. Up to this time, production of nitrogenous gases from the YP soil had been very low. Interpretation of gaseous nitrogen loss in the YP soil was difficult due to the possibility of chemodenitrification occurring. However, in the OP and BW soils, gaseous losses of nitrogen (determined as ¹⁵N-labelled gas) represented 16 and 7 % of the nitrogen applied respectively. Nitrous oxide comprised approximately half of this gaseous nitrogen loss, in both the OP and BW soils. This work implies that urine-N applied to the mineral soil (BW) could potentially threaten the quality of ground water due to nitrate contamination through leaching. In contrast, denitrification appears to be the major loss mechanism from the peat soils, with the production of nitrous oxide being the primary focus for any environmental concern. Future work should examine the fate of the nitrate leached from the BW soil and the potential for dilution, plant uptake or denitrification below a 30 cm soil depth. A better understanding of the denitrification mechanisms could help reduce denitrification and thereby improve the efficiency of nitrogen use and reduce the output of nitrous oxide.

The fate and behaviour of estrogens in the environment are of concern due to the compounds’ endocrine disruption potential. Estrogens, namely 17β-estradiol (E2), estrone (E1), and estrogen sulphates, i.e. 17β-estradiol-3-sulphate (E2-3S) and estrone-3-sulphate (E1-3S) excreted by livestock constitute a potential source for estrogen contamination in the environment. A method was developed to separate and quantify the hormones by high-performance-liquid-chromatography (HPLC) and ultraviolet detection (UV). A combination of dichloromethane (DCM) and dicyclohexylamine hydrochloride (DCH·HCl) gave recoveries from 97.3 to 107% for E1-3S extraction from aqueous solutions. The recoveries from soil samples ranged from 80.9 to 95.2% (E2-3S), and from 86.3 to 91.7% (E1-3S), respectively. Results of batch sorption studies showed that Freundlich isotherms were nonlinear (N ≠ 1) with Kf values ranging from 34.2 to 57.2, and from 3.42 to 4.18 mg¹-N LN kg⁻¹ for E1, and E1-3S, respectively, indicating the sorption affinity of E1-3S was about an order of magnitude lower than that of E1. The hydrophilic sulphate group of E1-3S possibly shielded the compound from hydrophobic interactions with the soil organic matter and allophanic clay minerals that were proposed as sorbents for E1. Contraction of clay minerals, “salting out” and competitive sorption of artificial urine constituents were likely to have been responsible for observed changes in Freundlich parameters when artificial urine was used as mediator matrix. Plotting the effective distribution coefficient as a function of hypothetical exposure concentrations facilitated the comparison of the sorption behaviour of both compounds as influenced by the mediator solution. The results emphasized that using the CaCl₂ matrix might result in false inferences for the sorption behaviour of these compounds in a dairying environment. The four hormones rapidly degraded in the agricultural soils under aerobic conditions, and the majority of the compounds degraded > 50% within the first 24 hrs. Soil arylsulphatase activities were directly correlated with degradation rate constants of the estrogen sulphates. Estrone was identified as a metabolite of E2 and E1-3S, and these three compounds were observed as metabolites of E2-3S. Single-first order (SFO) and double first-order in parallel (DFOP) kinetics were used to model the degradation and metabolite formation data. The results showed that the DFOP model was in most cases better able to predict the parent compound degradation than the SFO model, and also enabled to estimate accurate degradation endpoints. ER-CALUX® analysis revealed the formation of estrogenicity during E2-3S degradation, which could partly be explained by the formation of the metabolites E2 and E1. Transport studies with E1-3S and E1 showed that the transport and retention of both compounds were significantly influenced by the mediator matrix. While no breakthrough curves (BTCs) were recorded during hormone application in CaCl₂ (10 mM) both hormones were detected in the leachate when applied in artificial urine. Rate-limited sorption processes were proposed for the delayed arrival of the hormone BTCs compared with a conservative bromide tracer. Intense colouration of the leachate during the artificial urine experiments suggested the hormones were likely to be moved by colloid-facilitated transport. Furthermore, the detection of residue hormone and metabolite concentrations implied that degradation of E1-3S and E1 was hampered by urine constituents such as glycine and urea.

New Zealand’s 5.3 million strong dairy herd returns approximately 106 million litres of urine to pasture soils daily. The urea in that urine is rapidly hydrolysed to ammonium (NH₄⁺), which is then nitrified, with denitrification of nitrate (NO₃⁻) ensuing. Nitrous oxide (N₂O), a potent greenhouse gas (GHG), is produced via nitrification and denitrification, which are enzyme-catalysed processes mediated by soil microbes. Thus microbes are linked intrinsically to urine patch chemistry. However, few previous studies have investigated microbial dynamics in urine patches. Therefore the objective of these four experiments was to investigate the effects on soil microbial communities of cow urine deposition. Methods used included phospholipid fatty acid (PLFA) analyses of microbial community structure and microbial stress, dehydrogenase activity (DHA) assays measuring microbial activity, and headspace gas sampling of N₂O, ammonia (NH₃) and carbon dioxide (CO₂) fluxes. Experiment 1, a laboratory study, examined the influence of soil moisture and urinary salt content on the microbial community. Both urine application and high soil moisture increased microbial stress, as evidenced by significant changes in PLFA trans/cis and iso/anteiso ratios. Total PLFAs and DHA showed a short-term (< 1 week) stimulatory effect on microbes after urine application. Mean cumulative N₂O-N fluxes were 2.75% and 0.05% of the nitrogen (N) applied, from the wet (70% WFPS) and dry (35% WFPS) soils, respectively. Experiment 2, a field trial, investigated nutrient dynamics and microbial stress with plants present. Concentrations of the micronutrients, copper, iron and molybdenum, increased up to 20-fold after urine application, while soil phosphorus (P) concentrations decreased from 0.87 mg kg ⁻¹ to 0.48 mg kg⁻¹. Plant P was also lower in urine patches, but total PLFAs were higher, suggesting that microbes had utilised the available nutrients. Microbial stress again resulted from urine application but, in contrast to experiment 1, the fungal biomass recovered after its initial inhibition. Studies published during the course of this thesis reported that hippuric acid (HA) and its hydrolysis product benzoic acid (BA) significantly reduced N₂O-N emissions from synthetic cow urine, thus experiment 3 investigated this effect using real cow urine. Cumulative N₂O-N fluxes were 16.8, 5.9 and 4.7% of N applied for urine (U) alone, U+HA and U+BA, respectively. Since NH₃-N volatilisation remained unchanged, net gaseous N emissions were reduced. Trends in total PLFAs and microbial stress were comparable to experiment 1 results. Experiment 4 studied HA effects at different temperatures and found no inhibition of N₂O-N fluxes from HA-amended urine. However, mean cumulative N₂O-N fluxes were reduced from 7.6% of N applied at 15–20°C to 0.2% at 5–10°C. Total cumulative N emissions (N₂O-N + NH₃-N) were highest at 20°C (17.5% of N applied) and lowest at 10°C (9.8% of N applied). Microbial activity, measured as potential DHA, increased with increasing temperature. This work has clearly shown that the stimulation and inhibition of the soil microbial community by urine application are closely linked to soil chemistry and have significant impacts not only on soil nutrient dynamics but also on N₂O-N emissions and their possible mitigation.