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.

Land application of wastes has become increasingly popular, to promote nutrient recycling and environmental protection, with soil functioning as a partial barrier between wastes and groundwater. Dairy shed effluent (DSE), may contain a wide variety of pathogenic micro-organisms, including bacteria (e.g. Salmonella paratyphyi, Escherichia coli. and Campylobacter), protozoa and viruses. Groundwater pathogen contamination resulting from land-applied DSE is drawing more attention with the intensified development of the dairy farm industry in New Zealand. The purpose of this research was to investigate the fate and transport of bacterial indicator-faecal coliform (FC) from land-applied DSE under different irrigation practices via field lysimeter studies, using two water irrigation methods (flood and sprinkler) with contrasting application rates, through the 2005-2006 irrigation season. It was aimed at better understanding, quantifying and modelling of the processes that govern the removal of microbes in intact soil columns, bridging the gap between previous theoretical research and general farm practices, specifically for Templeton soil. This study involved different approaches (leaching experiments, infiltrometer measurements and a dye infiltration study) to understand the processes of transient water flow and bacterial transport; and to extrapolate the relationships between bacterial transport and soil properties (like soil structure, texture), and soil physical status (soil water potential ψ and volumetric water content θ). Factors controlling FC transport are discussed. A contaminant transport model, HYDRUS-1D, was applied to simulate microbial transport through soil on the basis of measured datasets. This study was carried out at Lincoln University’s Centre for Soil and Environmental Quality (CSEQ) lysimeter site. Six lysimeters were employed in two trials. Each trial involved application of DSE, followed by a water irrigation sequence applied in a flux-controlled method. The soil columns were taken from the site of the new Lincoln University Dairy Farm, Lincoln, Canterbury. The soil type is Templeton fine sandy loam (Udic-Ustochrept, coarse loamy, mixed, mesic). Vertical profiles (at four depths) of θ and ψ were measured during leaching experiments. The leaching experiments directly measured concentrations of chemical tracer (Br⁻ or Cl⁻) and FC in drainage. Results showed that bacteria could readily penetrate through 700 mm deep soil columns, when facilitated by water flow. In the first (summer) trial, FC in leachate as high as 1.4×10⁶ cfu 100 mL⁻¹ (similar to the DSE concentration), was detected in one lysimeter that had a higher clay content in the topsoil, immediately after DSE application, and before any water irrigation. This indicates that DSE flowed through preferential flow paths without significant treatment or reduction in concentrations. The highest post-irrigation concentration was 3.4×10³ cfu 100 mL⁻¹ under flood irrigation. Flood irrigation resulted in more bacteria and Br⁻ leaching than spray irrigation. In both trials (summer and autumn) results showed significant differences between irrigation treatments in lysimeters sharing similar drainage class (moderate or moderately rapid). Leaching bacterial concentration was positively correlated with both θ and ψ, and sometimes drainage rate. Greater bacterial leaching was found in the one lysimeter with rapid whole-column effective hydraulic conductivity, Keff, for both flood and spray treatments. Occasionally, the effect of Keff on water movement and bacterial transport overrode the effect of irrigation. The ‘seasonal condition’ of the soil (including variation in initial water content) also influenced bacterial leaching, with less risk of leaching in autumn than in summer. A tension infiltrometer experiment measured hydraulic conductivity of the lysimeters at zero and 40 mm suction. The results showed in most cases a significant correlation between the proportion of bacteria leached and the flow contribution of the macropores. The higher the Ksat, the greater the amount of drainage and bacterial leaching obtained. This research also found that this technique may exclude the activity of some continuous macropores (e.g., cracks) due to the difference of initial wetness which could substantially change the conductivity and result in more serious bacterial leaching in this Templeton soil. A dye infiltration study showed there was great variability in water flow patterns, and most of the flow reaching deeper than 50 cm resulted from macropores, mainly visible cracks. The transient water flow and transport of tracer (Br⁻) and FC were modelled using the HYDRUS-1D software package. The uniform flow van Genuchten model, and the dual-porosity model were used for water flow and the mobile-immobile (MIM) model was used for tracer and FC transport. The hydraulic and solute parameters were optimized during simulation, on the basis of measured datasets from the leaching experiments. There was evidence supporting the presence of macropores, based on the water flow in the post-DSE application stage. The optimised saturated water content (θs) decreased during the post-application process, which could be explained in terms of macropore flow enhanced by irrigation. Moreover, bacterial simulation showed discrepancies in all cases of uniform flow simulations at the very initial stage, indicating that non-equilibrium processes were dominant during those short periods, and suggesting that there were strong dynamic processes involving structure change and subsequently flow paths. It is recommended that management strategies to reduce FC contamination following application of DSE in these soils must aim to decrease preferential flow by adjusting irrigation schemes. Attention needs to be given to a) decreasing irrigation rates at the beginning of each irrigation; b) increasing the number of irrigations, by reducing at the same time the amount of water applied and the irrigation rate at each irrigation; c) applying spray irrigation rather than flood irrigation.

Irish agriculture is becoming increasingly regulated, with restrictions on fertiliser application rates and stocking rates to reduce nitrate (NO₀⁻) leaching losses. However these regulations have been, to date, based on minimal field research. The purpose of this study was to determine the actual leaching losses of nitrate from Irish dairy pasture at a range of stocking rates, and to investigate the effectiveness of the nitrification inhibitor DCD at reducing nitrate leaching losses where these are deemed excessive. In grazed pastures, a major source of leached nitrate is the urine patch, where a high rate of N is applied in one application. This trial recorded the losses from urine and non-urine areas of pasture separately. Nitrate leaching losses from three soils were recorded using lysimeters at Johnstown Castle, Co. Wexford, over two years. Total nitrate losses were higher from the freely drained Clonakilty and Elton soils than from the heavy Rathangan soil. Mean nitrate losses from urine patches ranged from 16 - 233 kg nitrate-N / ha⁻¹, and were reduced by up to 53% when DCD was applied. DCD also reduced peak and mean nitrate-N concentrations in many cases. In addition, DCD halved the nitrous oxide (N₂O) emission factor on the Rathangan soil, caused increases in pasture N content, and increased herbage yield in some treatments. The distribution of urine patches under dairy grazing was recorded using GPS at Kilworth, Co. Cork. Cows were also found to deposit 0.359 urine patches per grazing hour. A model was produced to predict field-scale nitrate leaching losses from dairy pasture at a range of stocking rates. At 2.94 cows per hectare, the highest stocking rate, annual field N loss was below 34 kg nitrate-N ha⁻¹, mean drainage N concentrations were below 5.65 mg nitrate-N L⁻¹ (the EU drinking water guideline value), and the worst-case-scenario autumn peak concentration did not exceed 21.55 mg nitrate-N L⁻¹ (above the EU Maximum Allowable Concentration (MAC) but below the World Health Organisation (WHO) drinking water limit). DCD reduced total annual field N loss by 21% (a conservative estimate), and also reduced mean and peak nitrate concentrations. Provided fertiliser application rates are at or below 291 kg N ha⁻¹, and based on current legislative values for drinking water quality, this trial does not support any blanket restrictions on the stocking rate of Irish dairy farms. However where particularly high water quality is required, DCD shows potential as a useful tool to achieve low nitrate concentrations.

Worldwide there is considerable concern over the effects of human activities on the quantity and quality of freshwater. Measurement of infiltration behaviour will be important for improving freshwater management. This study identifies that New Zealand has a sporadic history of measuring soil water movement attributes on a limited number of soil types, although the current practical demand should be large for management of irrigation, dairy farm effluent disposal, as well as municipal / domestic waste- and storm-water disposal. Previous research has demonstrated that infiltration behaviour is governed by the interplay between numerous mechanisms including hydrophobicity and preferential flow, the latter being an important mechanism of contaminant leaching for many NZ soils. Future characterisation will need to recognise the dynamic nature of these interactions, and be able to reliably characterise the key infiltration mechanisms. Since macropores are responsible for preferential flow, it is critical that infiltration studies use a representative sample of the macropore network. The aim of this project was to study the mechanisms governing the infiltration behaviour of a layered soil in large (50 x 70 cm) monolith lysimeters, where the connectivity of the macropore network remains undisturbed. Four lysimeters of the Gorge silt loam were collected, a structured soil with four distinct layers. On each lysimeter there were four separate infiltration experiments, with water applied under suctions of 0, 0.5, 1, and 1.5 kPa by a custom-built tension infiltrometer. Each lysimeter was instrumented with 30 tensiometers, located in arrays at the layer boundaries. There was also a field experiment using ponded dye infiltration to visually define preferential flowpaths. Analysis of dye patterns, temporal variability in soil matric potential (Ψm), and solute breakthrough curves all show that preferential flow is an important infiltration mechanism. Preferential flowpaths were activated when Ψm was above -1.5 kPa. During saturated infiltration, at least 97% of drainage was through the ‘mobile’ pore volume of the lysimeter (θm), estimated among the lysimeters at 5.4 – 8.7 % of the lysimeter volume. Early-time infiltration behaviour did not show the classical square-root of time behaviour, indicating sorptivity was not the governing mechanism. This was consistent across the four lysimeters, and during infiltration under different surface imposed suctions. The most likely mechanism restricting sorptivity is weak hydrophobicity, which appears to restrict infiltration for the first 5 – 10 mm of infiltration. Overall, the Gorge soil’s early-time infiltration behaviour is governed by the dynamic interaction between sorptivity, hydrophobicity, the network of air-filled pores, preferential flow and air encapsulation. Long-time infiltration behaviour was intimately linked to the temporal dynamics of Ψm, which was in turn controlled by preferential flow and soil layer interactions. Preferential flowpaths created strong inter-layer connectivity by allowing an irregular wetting front to reach lower layers within 2 – 15 mm of infiltration. Thereafter, layer interactions dominate infiltration for long-time periods, as Ψm in soil layers with different K(Ψm) relationships self-adjusts to try to maintain a constant Darcy velocity. An important finding was that Ψm rarely attained the value set by the tension infiltrometer during unsaturated infiltration. The results show that ‘true’ steady-state infiltration is unlikely to occur in layered soils. A quasi-steady state was identified once the whole column had fully wet and layer interactions had settled to where Ψm changes occurred in unison through each soil layer. Quasi-steady state was difficult to identify from just the cumulative infiltration curve, but more robustly identified as when infiltration matched drainage, and Ψm measurements showed each layer had a stable hydraulic gradient. I conclude that the in-situ hydraulic conductivity, K(Ψm), of individual soil layers can be accurately and meaningfully determined from lysimeter-scale infiltration experiments. My results show that K(Ψm) is different for each soil layer, and that differences are consistent among the four lysimeters. Under saturated flow the subsoil had the lowest conductivity, and was the restricting layer. Most interestingly this pattern reversed during unsaturated flow. As Ψm decreased below -0.5 to -1 kPa, the subsoil was markedly more conductive, and the topsoil layers became the restricting layers. All four soil layers demonstrate a sharp decline in K(Ψm) as Ψm decreases, with a break in slope at ~ -1 kPa indicating the dual-permeability nature of all layers.

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.

It is widely accepted that bioavailability, rather than total soil concentration, is preferred when assessing the risk associated with metal contamination. Despite this, debate continues on what constitutes a bioavailable pool and how to best predict bioavailability, especially in relation to crop plants. The overall aim of this thesis was to assess and validate measures of cadmium (Cd), copper (Cu), nickel (Ni) and zinc (Zn) bioavailability in a range of soils amended with metal salts and biosolids. Six potential measures of bioavailability were investigated and compared: total metal; 0.04 M EDTA extraction; 0.05 M Ca(NO₃)₂ extraction; soil solution extracted using rhizon probes; effective solution concentration (CE) determined using diffusive gradients in thin films (DGT); and modelled free ion activities (WHAM 6.0). These were compared to shoot metal concentrations obtained from plants grown in three soils with contrasting properties treated with biosolids and metal salts. The first study involved a wheat seedling (Triticum aestivum) assay carried out under controlled environmental conditions on incubated soils treated with metal salts and biosolids. Results showed that the presence of biosolids resulted in increases of DOC, salinity, Ca and Mg in soil solution as well as total concentrations of Cu and Zn, dry matter was also adversely affected by increased levels of salinity. The addition of biosolids did not significantly alter the extractability or solubility of Cd, Cu, Ni and Zn although concentrations of Cd in shoots were significantly lower in plants grown in biosolids amended soils compared with unamended soils. The second study involved a field experiment that used 20 cm diameter by 30 cm deep soil monoliths of the same three soils treated with metals and biosolids, and perennial ryegrass (Lolium perenne) was grown for 24 months. Results revealed the addition of biosolids significantly increased the amount of DOC, salinity, Ca and Mg in solution. The presence of biosolids also significantly altered the bioavailability of Cd, Cu, Ni and Zn, as measured by soil solution, CE and free ion activity. However, this change had little effect on plant metal uptake. The length of time following treatment application had the greatest effect on soil chemistry and metal availability, resulting in pH decreases and increases in DOC, soil solution salinity, Ca and Mg. The free ion activities of each metal increased with time, as did soil solution Cd and Zn and CE-Cu, with results for Zn indicative of migration through the soil profile with time. Plant uptake of Ni and Zn also changed with time. Nickel concentrations in shoots decreased, while concentrations of Zn in shoots increased. The findings from the two studies demonstrated that biosolids increased the amount of DOC, salinity, Ca and Mg present in soil solution. In the lysimeter study measures of metal availability were affected in soils amended with biosolids, but this did not effect shoot concentrations. The overall predictive strengths of the six potential measures of bioavailability was investigated using results from the previously described experiments and related studies carried out by ESR and Lincoln University using nine different soils amended with combinations of biosolids and metal salts. Of the four metals Ni provided the strongest correlations between metal bioavailability and shoot concentrations, with 0.05 M Ca(NO₃)₂ extraction giving the strongest relationship for Ni concentrations in shoots (r² = 0.73). This suggests that the solubility of Ni is highly indicative of shoot concentrations and that Ca(NO₃)₂ is a robust measure of Ni bioavailability. In addition Ca(NO₃)₂ provided the best estimate of Zn bioavailability (r² = 0.65), and CE-Cd provided the best measure of Cd bioavailability, although it could only describe 47 % of shoot Cd concentration. Results for Cu were typical of previously described studies as assays of Cu availability are almost always poorly correlated with shoot concentrations, with total Cu having the strongest relationship (r² = 0.34). Methods based on the extractability and solubility of Cu in soils were poor indicators of Cu concentration in shoots. Overall, the addition of biosolids did not alter the outcome of these bioavailability assays, and results indicated that total metal concentrations present in the soils and biosolids matrix, plus length of time since soil treatment, had a greater affect on metal bioavailability.

Changes brought about by chemical and physical weathering were investigated in a chronosequence of terrace soils near Reefton, New Zealand. The parent materials of the soil, which ranged in age from about 1000 to over 130,000 years were outwash gravels, sands and silts derived from granite (dominant) and indurated sandstone. Variations in pH, organic matter, particle size, cation exchange properties, total Mg, Al, Si, K, Ca, Fe and Ti, poorly-ordered and organic-complexed forms of Al and Fe, and mineralogy caused by increasing duration of weathering and by short range, short term variations in the intensity of the biotic factor were determined. It was concluded that the younger soils represented dynamic systems in which alternative weathering cycles could replace each other as the growth, death and eventual disappearance of individual red beech trees caused localised fluctuations in pH. It was further concluded that these processes would lead ultimately to the formation of gley podzols as are now found on the two oldest surfaces p and that podzolisation preceded gleying. Attempts were made to determine if minerals of the plumbogummite group were responsible for the high proportion of soil phosphate from these soils that, on fractionation, appeared in the residual P fraction. It was found that attempts to concentrate these minerals by prolonged digestion with HF resulted in their solution, and in precipitation of complex fluorides that yielded diffraction spacings that have been mistaken for minerals of the plumbogummite group.

It is widely accepted that bioavailability, rather than total soil concentration, is preferred when assessing the risk associated with metal contamination. Despite this, debate continues on what constitutes a bioavailable pool and how to best predict bioavailability, especially in relation to crop plants. The overall aim of this thesis was to assess and validate measures of cadmium (Cd), copper (Cu), nickel (Ni) and zinc (Zn) bioavailability in a range of soils amended with metal salts and biosolids. Six potential measures of bioavailability were investigated and compared: total metal; 0.04 M EDTA extraction; 0.05 M Ca(NO₃)₂ extraction; soil solution extracted using rhizon probes; effective solution concentration (CE) determined using diffusive gradients in thin films (DGT); and modelled free ion activities (WHAM 6.0). These were compared to shoot metal concentrations obtained from plants grown in three soils with contrasting properties treated with biosolids and metal salts. The first study involved a wheat seedling (Triticum aestivum) assay carried out under controlled environmental conditions on incubated soils treated with metal salts and biosolids. Results showed that the presence of biosolids resulted in increases of DOC, salinity, Ca and Mg in soil solution as well as total concentrations of Cu and Zn, dry matter was also adversely affected by increased levels of salinity. The addition of biosolids did not significantly alter the extractability or solubility of Cd, Cu, Ni and Zn although concentrations of Cd in shoots were significantly lower in plants grown in biosolids amended soils compared with unamended soils. The second study involved a field experiment that used 20 cm diameter by 30 cm deep soil monoliths of the same three soils treated with metals and biosolids, and perennial ryegrass (Lolium perenne) was grown for 24 months. Results revealed the addition of biosolids significantly increased the amount of DOC, salinity, Ca and Mg in solution. The presence of biosolids also significantly altered the bioavailability of Cd, Cu, Ni and Zn, as measured by soil solution, CE and free ion activity. However, this change had little effect on plant metal uptake. The length of time following treatment application had the greatest effect on soil chemistry and metal availability, resulting in pH decreases and increases in DOC, soil solution salinity, Ca and Mg. The free ion activities of each metal increased with time, as did soil solution Cd and Zn and CE-Cu, with results for Zn indicative of migration through the soil profile with time. Plant uptake of Ni and Zn also changed with time. Nickel concentrations in shoots decreased, while concentrations of Zn in shoots increased. The findings from the two studies demonstrated that biosolids increased the amount of DOC, salinity, Ca and Mg present in soil solution. In the lysimeter study measures of metal availability were affected in soils amended with biosolids, but this did not effect shoot concentrations. The overall predictive strengths of the six potential measures of bioavailability was investigated using results from the previously described experiments and related studies carried out by ESR and Lincoln University using nine different soils amended with combinations of biosolids and metal salts. Of the four metals Ni provided the strongest correlations between metal bioavailability and shoot concentrations, with 0.05 M Ca(NO₃)₂ extraction giving the strongest relationship for Ni concentrations in shoots (r² = 0.73). This suggests that the solubility of Ni is highly indicative of shoot concentrations and that Ca(NO₃)₂ is a robust measure of Ni bioavailability. In addition Ca(NO₃)₂ provided the best estimate of Zn bioavailability (r² = 0.65), and CE-Cd provided the best measure of Cd bioavailability, although it could only describe 47 % of shoot Cd concentration. Results for Cu were typical of previously described studies as assays of Cu availability are almost always poorly correlated with shoot concentrations, with total Cu having the strongest relationship (r² = 0.34). Methods based on the extractability and solubility of Cu in soils were poor indicators of Cu concentration in shoots. Overall, the addition of biosolids did not alter the outcome of these bioavailability assays, and results indicated that total metal concentrations present in the soils and biosolids matrix, plus length of time since soil treatment, had a greater affect on metal bioavailability.

Worldwide there is considerable concern over the effects of human activities on the quantity and quality of freshwater. Measurement of infiltration behaviour will be important for improving freshwater management. This study identifies that New Zealand has a sporadic history of measuring soil water movement attributes on a limited number of soil types, although the current practical demand should be large for management of irrigation, dairy farm effluent disposal, as well as municipal / domestic waste- and storm-water disposal. Previous research has demonstrated that infiltration behaviour is governed by the interplay between numerous mechanisms including hydrophobicity and preferential flow, the latter being an important mechanism of contaminant leaching for many NZ soils. Future characterisation will need to recognise the dynamic nature of these interactions, and be able to reliably characterise the key infiltration mechanisms. Since macropores are responsible for preferential flow, it is critical that infiltration studies use a representative sample of the macropore network. The aim of this project was to study the mechanisms governing the infiltration behaviour of a layered soil in large (50 x 70 cm) monolith lysimeters, where the connectivity of the macropore network remains undisturbed. Four lysimeters of the Gorge silt loam were collected, a structured soil with four distinct layers. On each lysimeter there were four separate infiltration experiments, with water applied under suctions of 0, 0.5, 1, and 1.5 kPa by a custom-built tension infiltrometer. Each lysimeter was instrumented with 30 tensiometers, located in arrays at the layer boundaries. There was also a field experiment using ponded dye infiltration to visually define preferential flowpaths. Analysis of dye patterns, temporal variability in soil matric potential (Ψm), and solute breakthrough curves all show that preferential flow is an important infiltration mechanism. Preferential flowpaths were activated when Ψm was above -1.5 kPa. During saturated infiltration, at least 97% of drainage was through the ‘mobile’ pore volume of the lysimeter (θm), estimated among the lysimeters at 5.4 – 8.7 % of the lysimeter volume. Early-time infiltration behaviour did not show the classical square-root of time behaviour, indicating sorptivity was not the governing mechanism. This was consistent across the four lysimeters, and during infiltration under different surface imposed suctions. The most likely mechanism restricting sorptivity is weak hydrophobicity, which appears to restrict infiltration for the first 5 – 10 mm of infiltration. Overall, the Gorge soil’s early-time infiltration behaviour is governed by the dynamic interaction between sorptivity, hydrophobicity, the network of air-filled pores, preferential flow and air encapsulation. Long-time infiltration behaviour was intimately linked to the temporal dynamics of Ψm, which was in turn controlled by preferential flow and soil layer interactions. Preferential flowpaths created strong inter-layer connectivity by allowing an irregular wetting front to reach lower layers within 2 – 15 mm of infiltration. Thereafter, layer interactions dominate infiltration for long-time periods, as Ψm in soil layers with different K(Ψm) relationships self-adjusts to try to maintain a constant Darcy velocity. An important finding was that Ψm rarely attained the value set by the tension infiltrometer during unsaturated infiltration. The results show that ‘true’ steady-state infiltration is unlikely to occur in layered soils. A quasi-steady state was identified once the whole column had fully wet and layer interactions had settled to where Ψm changes occurred in unison through each soil layer. Quasi-steady state was difficult to identify from just the cumulative infiltration curve, but more robustly identified as when infiltration matched drainage, and Ψm measurements showed each layer had a stable hydraulic gradient. I conclude that the in-situ hydraulic conductivity, K(Ψm), of individual soil layers can be accurately and meaningfully determined from lysimeter-scale infiltration experiments. My results show that K(Ψm) is different for each soil layer, and that differences are consistent among the four lysimeters. Under saturated flow the subsoil had the lowest conductivity, and was the restricting layer. Most interestingly this pattern reversed during unsaturated flow. As Ψm decreased below -0.5 to -1 kPa, the subsoil was markedly more conductive, and the topsoil layers became the restricting layers. All four soil layers demonstrate a sharp decline in K(Ψm) as Ψm decreases, with a break in slope at ~ -1 kPa indicating the dual-permeability nature of all layers.