Spatial and temporal information on catchment sediment sources and sinks can provide an improved understanding of catchment response to human-induced disturbances. This is essential for the implementation of well-targeted catchment-management decisions. This thesis investigates the nature and timing of catchment response to human activities by examining changes in sediment sources and sinks in a dry-tropical subcatchment of the Great Barrier Reef (GBR) catchment area, in northeastern Australia. Changes in catchment sediment sources, both in terms of spatial provenance and erosion type, are determined using sediment tracing techniques. Results indicate that changes in sediment source contributions over the last 250 years can be linked directly to changes in catchment land use. Sheetwash and rill erosion from cultivated land (40-60%) and channel erosion from grazed areas (30-80%) currently contribute most sediment to the river system. Channel erosion, on a basin-wide scale, appears to be more important than previously considered in this region of Australia. Optically stimulated luminescence and 137Cs dating are used to determine pre-and post- European settlement (ca. 1850) alluvial sedimentation rates. The limitations of using 137Cs as a floodplain sediment dating tool in a low fallout environment, dominated by sediment derived from channel and cultivation sources, are identified. Low magnitude increases in post-disturbance floodplain sedimentation rates (3 to 4 times) are attributed to the naturally high sediment loads in the dry-tropics. These low increases suggest that previous predictions which reflect order of magnitude increases in post-disturbance sediment yields are likely to be overestimates. In-channel bench deposits, formed since European settlement, are common features that appear to be important stores of recently eroded material. The spatially distributed erosion/sediment yield model SedNet is applied, both with generic input parameters and locally-derived data. Outputs are evaluated against available empirically-derived data. The results suggest that previous model estimates using generic input parameters overestimate post-disturbance and underestimate predisturbance sediment yields, exaggerating the impact of European catchment disturbance. This is likely to have important implications for both local-scale and catchment-wide management scenarios in the GBR region. Suggestions for future study and the collection of important empirical data to enable more accurate model performance are made.

Devido à intensificação das atividades industriais e agrícolas, aliada ao grande crescimento urbano e ao aumento exponencial da população no último século, a pressão sobre os recursos hídricos se intensificaram drasticamente. Sendo assim, existe a necessidade de se buscar novas fontes de abastecimento público de água. A captação de água pluvial remonta a milhares de anos, no entanto, por se tratar de uma área onde os estudos são recentes, muitas dúvidas permeiam sobre o método a ser adotado para a implantação de sistemas de captação pluvial, de forma que garanta a saúde de seus usuários. Desta forma, procurando acrescentar cientificamente e analisar novas possibilidades para sistemas de aproveitamento de água pluvial, este projeto objetivou analisar e caracterizar a qualidade da água em diversos pontos em um sistema de captação, armazenamento e utilização de água pluvial, instalado no Laboratório de Ecologia Isotópica do CENA/USP no município de Piracicaba, SP. Foi construído um sistema em escala real contendo cinco recipientes de 100 L para o descarte de primeiras águas, totalizando aproximadamente 3,3 mm de água descartada, com duas cisternas de 5 mil litros cada para armazenar a água captada. Foram coletadas amostras de água em sete pontos do sistema totalizando 36 análises por evento pluviométrico. Os parâmetros analisados foram pH, condutividade elétrica (CE), nitrogênio total (NT), carbono inorgânico dissolvido (DIC), carbono orgânico dissolvido (DOC) e oxigênio dissolvido (OD). As análises de OD foram descontinuadas após a constatação de que o OD, nas diferentes etapas do sistema, não apresentavam diferenças estatísticas devido ao esquema utilizado na montagem do sistema. O pH coletado sempre apresentou valores mais altos que os valores da precipitação, tendendo a diminuir conforme a água captada era descartada atingindo uma média de pH de 6,1 quando a água encontrava-se nas cisternas. A CE e o NT apresentaram valores mais altos que os valores encontrados na precipitação com um decaimento significativo para cada etapa de descarte, assim como apresentaram correlação com a intensidade pluviométrica e o intervalo de estiagem entre eventos pluviométricos. O desvio padrão de CE tendeu a diminuir a cada etapa de descarte, demonstrando que o sistema de descarte atuava como um homogeneizador da água coletada, independente das características pluviométricas. Os parâmetros de DIC também apresentaram valores maiores que os encontrados na água de chuva, assim como apresentaram queda significativa conforme a quantidade de água descartada. Os parâmetros de DOC não apresentaram qualquer correlação com a quantidade de água descartada ou com os parâmetros pluviométricos. Concluiu-se que o sistema de descarte de primeiras águas tem um papel fundamental na qualidade final da água captada. Assim como, que a recomendação da ABNT, de descartar os primeiros 2 mm de chuva, condiz exatamente com o ponto onde se obtêm a melhor qualidade de água com o mínimo de perda. Foi possível constatar que o intervalo de estiagem e a intensidade pluviométrica influenciaram diretamente na qualidade da água que será coletada. / Due to increasing industrial and agricultural activities, coupled with the extensive urban growth and the exponential increase in population in the last century, the pressure on water resources has intensified dramatically. Thus, there is a need to seek new sources of public water supply. The collection of rainwater goes back thousands of years, however, because it is an area where the studies are recent, many questions permeate on the method to be adopted for the implementation of rainwater harvesting systems, as well as ensure health of its users. Thus, seeking to add scientifically and analyze new possibilities for harnessing rainwater systems, this project aims to analyze and characterize water quality at various points in a system of capture, store and use rainwater, at the Laboratory of Isotope Ecology CENA / USP in Piracicaba, SP. A system has been built in real scale with five drums of 100 L for discarding of first waters, totaling approximately 3.3 mm discarted water, with two cisterns of 5000 liters each to store the collected water. Were seven sampling points totaling 36 analyzes per rainfall event. Parameters of pH, electrical conductivity (CE), total nitrogen (TN), dissolved inorganic carbon (DIC), dissolved organic carbon (DOC) and dissolved oxygen (OD) were analyzed. Analyses of OD were discontinued after the realization that the OD, in the different stages of the system, showed no statistical differences due to the layout of the system. The analyzed pH always showed a higher values than the precipitation and has tended to decrease as the collected water was discarded. Showing an average pH of 6.1 when the water reaches the cistern. The values of EC and NT were higher than the values found in precipitation and tended to decrease gradually in each stage of disposal system of the first water, as also showed a correlated pattern with the rainfall intensity and with the interval between rainfall events. The CE standard deviation tend to decrease at each step of the disposal system of the first water, demonstrating that the disposal system of the first water serves as a homogenizer of water captured, regardless of the rainfall characteristics. The parameters of DIC also showed higher values than those found in rain water, and showed a gradual decrease in each stage of disposal system of the first water. The parameters of DOC showed no correlation with the amount of discarted water or with the rainfall parameters. It was concluded that the disposal system of the first waters has a key role in the final quality of water abstracted. As well as the recommendation of ABNT, of discarding the first 2 mm of rain, matches exactly the point where you can get the best quality water with minimal loss. It was found that the drought period and the rainfall intensity directly influence the quality of water that will be collected.

Lakes play a major role in the global carbon (C) cycle, despite making up a small area of earth’s surface. Lakes receive, transport and process sizable amounts of C, emitting a substantial amount of the greenhouse gases, carbon dioxide (CO2) and methane (CH4), into the atmosphere. Ice-covered lakes are particularly sensitive to climate change, as future reductions to the duration of lake ice cover will have profound effects on the biogeochemical cycling of C in lakes. It is still largely unknown how reduced ice cover duration will affect CO2 and CH4 emissions from ice-covered lakes. Thus, the primary aim of this thesis was to fill this knowledge gap by monitoring the spatial and temporal dynamics of CO2 and CH4 in ice-covered lakes. The results of this thesis demonstrate that below ice CO2 and CH4 were spatially and temporally variable. Nutrients were strongly linked to below ice CO2 and CH4 oxidation variations across lakes. In addition, below ice CO2 was generally highest in small shallow lakes, and in bottom waters. Whilst below ice CH4 was elevated in surface waters near where bubbles from anoxic lake sediment were trapped. During the ice-cover period, CO2 accumulation below ice was not linear, and at ice-melt incomplete mixing of lake waters resulted in a continued CO2 storage in bottom waters. Further, CO2 transported from the catchment and bottom waters contributed to high CO2 emissions. The collective findings of this thesis indicate that CO2 and CH4 emissions from ice-covered lakes will likely increase in the future. The strong relationship between nutrients and C processes below ice, imply that future changes to nutrient fluxes within lakes will influence the biogeochemical cycling of C in lakes. Since catchment and lake sediment C fluxes play a considerable role in below ice CO2 and CH4 dynamics, changes to hydrology and thermal stability of lakes will undoubtedly alter CO2 and CH4 emissions. Nevertheless, ice-covered lakes constitute a significant component of the global C cycle, and as such, should be carefully monitored and accounted for when addressing the impacts of global climate change.

Diffuse transfers of pesticides from agricultural land to ground and surface waters can lead to significant drinking water quality issues. This thesis describes the development and application of a parameter-efficient, numerical model to predict pesticide concentrations in raw water sources within an integrated hydrological framework. As such, it fills an unoccupied niche that exists in pesticide fate modelling for a computationally undemanding model that contains enough process complexity to be applicable in a wide range of catchments and hydrogeological settings in the UK and beyond. The model represents the key processes involved in pesticide fate (linear sorption and first-order degradation) and transport (surface runoff, lateral throughflow, drain flow, percolation to the unsaturated zone, calculated using a soil water balance) in the soil at a daily time step. Soil properties are derived from the national soil database for England and Wales and are used to define the boundary conditions at the interface between the subsoil and the unsaturated zone. This is the basis of the integrated hydrological framework which enables the application of the model to both surface water catchments and groundwater resources. The unsaturated zone model accounts for solute transport through two flow domains (accounting for fracture flow and intergranular matrix flow) in three hydrogeological settings (considering the presence and permeability of superficial deposits). The model was first applied to a small headwater sub-catchment in the upper Cherwell. Performance was good for drainflow predictions (Nash Sutcliffe Efficiency > 0.61) and performed better than the MACRO model and as well as the modified MACRO model. Surface water model performance was evaluated for eight pesticides in five different catchments. Performance was generally good for flow prediction (Nash Sutcliffe Efficiency > 0.59 and percentage bias below 10 %, in the validation period for all but two catchments). The 90th percentile measured concentration was captured by the model in 62 % of catchment-pesticide combinations. In theremaining cases predictions were within, at most, a factor of four of measured 90th percentile concentrations. The rank order of the frequency of pesticides detected over 0.1 μg L-1 was also predicted reasonably well (Spearman’s rank coefficient > 0.75; p < 0.05 in three catchments). Pesticide transport in the unsaturated zone model was explored at the point scale in three aquifers (chalk, limestone and sandstone). The results demonstrate that representing the unsaturated zone processes can have a major effect on the timing and magnitude of pesticide transfers to the water table. In comparison with the other catchment scale pesticide fate models that predict pesticide exposure at a daily time-step, the model developed stands out requiring only a small number of parameters for calibration and quick simulation times. The benefit of this is that the model can be used to predict pesticide exposure in multiple surface and groundwater resources relatively quickly which makes it a useful tool for water company risk assessment. The broad-scale approach to pesticide fate and transport modelling presented here can help to identify and prioritise pesticide monitoring strategies, to compare catchments in order to target catchment management and to highlight potential problems that could arise under different future scenarios.

Mine abandonment and the discharge of contaminated mine water is recognised globally as a major source of surface water and groundwater pollution. Contamination generally arises from the oxidation of sulphide minerals, principally pyrite, by the mining process, and the subsequent chemical reactions can lead to the discharge of mineralised, often acidic, iron, and sulphate rich waters. In many historically mined river catchments, mine water discharge is the main cause of poor water quality. Within the UK, managing the legacy of abandoned mines is one of the principal challenges presented by modern environmental legislation, particularly the EU Water Framework Directive, a challenge that is exacerbated by the diverse and widespread nature of historical mining. The impact and hazard associated with abandoned mining in one of the UK’s most intensively mined regions, the Almond River Catchment, Scotland, was examined via: 1) a detailed GIS mapping and investigation of historical mining processes in the catchment, 2) mine site discharge sampling, 3) detailed site investigations, 4) geochemical modelling of four mine waste sites and 5) analysis of temporal and spatial river water quality in the catchment. The results are then brought together to produce a catchment scale mine water hazard map. Mapping has identified over 300 mine sites in the catchment including coal, oil shale and ironstone mine wastes and flooded coal and oil shale mines. The historical development of oil shale retort methods has been shown to have an impact on potential hazard. Sampling of discharge waters from the different mining activities, in conjunction with detailed mineralogical analysis and geochemical modelling at the four mine waste sites has characterised the main hazards. Ironstone and pyrite bearing coal mine wastes discharge waters with highly elevated Fe and sulphate concentrations, up to 160mgl-1 and 1900mgl-1 respectively, due to extensive pyrite oxidation and acid generating salt dissolution (principally jarosite). Coal mine wastes show variable mineralogy, due to the diverse nature of coal bearing strata, and discharge waters with variable chemistry. Oil Shale mine wastes are generally depleted in pyrite due to historic processing and discharge low sulphate waters with moderately elevated Fe concentrations, up to 5mgl-1. Flooded coal mines discharge sulphate dominant alkaline waters, due to the availability of carbonate minerals in the mine complex, with elevated Fe concentrations, up to 50mgl-1, while flooded oil shale mines discharge waters with moderately elevated Fe concentrations, up to 4mgl-1, due to lower pyrite content in mine strata and reduced availability of oxygen related to mine abandonment age. Once in the surface water environment iron and sulphate display significant concentration-flow dependence: iron increases at high flows due to the re-suspension of river bed iron precipitates (Fe(OH)3); sulphate concentrations decrease with increased flow as a result of dilution. Further examination of iron and sulphate loading at low flows indicates a close correlation of iron and sulphate with mined areas; cumulative low flow load calculations indicate that coal and oil shale mining regions contribute 0.21 and 0.31 g/s of iron, respectively, to the main Almond tributary. Decreases in iron loading on river sections demonstrate the deposition and diffuse storage of iron within the river channel. This river bed iron is re-suspended with increased flow resulting in significant transport of diffuse iron downstream with load values of up to 50 g/s iron. Based on this hazard classification, a catchment scale mine water hazard map has been developed. The map allows the prioritisation of actions for future mine water management.

Water-induced soil erosion and shallow landslides interact with each other and need to be studied in an integrated approach to understand hillslope sediment yields. The principal aim of this thesis was to study and model soil erosion and shallow landslides in an integrated way. The thesis presents results from laboratory and catchment-scale studies and modelling. A laboratory flume under a rainfall simulator was used for shallow landslide and soil erosion experiments using sandy and silty loess soils. In the experiments, landslide initiation, retrogressions and slip surface depths were measured and monitored directly or by using video camera recordings. Sediment and runoff were collected from the flume outlet every minute during landslides and every 10 minutes before and after landslides. Changes in the soil slope, after landslides, were recorded. Initially, six experiments including two repetitions were conducted using sandy soils at a 30º and 10º compound slope configuration, but with different soil profile depths. The experimental results showed that total and landslide-driven sediment yields were affected by the original soil profile depth; the greater the depth, the higher the sediment yield. Later, twelve other experiments were conducted on different slopes using silty loess soils. The experimental observations were used to validate an integrated modelling approach which includes WEPP for runoff and soil erosion modelling, a slope stability model for simulating shallow landslides, and a simple soil redistribution model for runout distance prediction. The model predictions were in good alignment with the observations. In all (sandy and silty loess) experiments, peak sediment discharges were related to the landslide events, proximity to the outlet and landslide volume. The post-failure soil erosion rate decreased as a function of changes in the slope profile. The GeoWEPP-SLIP modelling approach was proposed for catchment-scale modelling. The approach simulates soil erosion using the Hillslope and Flowpath methods in WEPP, predicts shallow landslides using a slope stability model coupled with the WEPP’s hillslope hydrology and finally uses a simple rule-based soil redistribution model to predict runout distance and post-failure topography. A case study application of the model to the Bowenvale research catchment (300 ha) showed that the model predictions were in good agreement with the observed values. However, the Hillslope method over-predicted the outlet sediment yield due to the computational weighting involved in the method. The Hillslope method predicted consistent values of sediment yield and soil erosion regardless to the changes in topography and land-cover in the post-failure scenarios. The Flowpath method, on the other hand, predicted higher values of sediment yield in the post-failure vegetation removal scenario. The effects of DEM resolution on the approach were evaluated using four different resolutions. Statistical analyses for all methods and resolutions were performed by comparing the predicted versus measured runoff and sediment yield from the catchment outlet and the spatial distribution of shallow landslides. Results showed that changes in resolution did not significantly alter the sediment yield and runoff between the pre- and post-failure scenarios at the catchment outlet using the Hillslope method. However, the Flowpath method predicted higher hillslope sediment yields at a coarser resolution level. Similarly, larger landslide areas and volumes were predicted for coarser resolutions whereas deposition volume decreased with the increase in grid-cell size due to changes in slope and flowpath distributions. The research conducted in the laboratory and catchment presented in this thesis helped understand the interactions between shallow landslides and soil erosion in an integrated approach.

Chemical weathering reactions are important for the physical, chemical, and biological development of the critical zone. We present findings from aqueous phase chemical analyses of surface and soil pore waters during a 15 month study in a small semi-arid mountain catchment of the Santa Catalina Mountain Critical Zone Observatory. Stream water geochemical solutes are sourced to two distinct locations - fractured bedrock baseflow stores and soil quickflow stores. Solid phase observations of albite, anorthite, and K-feldspar transformation to Ca-montmorillonite and kaolinite are supported by stream water saturation states calculated via a PHREEQC geochemical model. While differences in mineral assemblages, soil depths, and horizonation suggest greater weathering in schist versus granite lithologies and in hillslope divergent versus convergent zones, soil pore water solute ratio analysis does not readily distinguish these differences. However, preliminary investigation of aqueous rare earth elements suggests detectable lithologic and landscape positional differences warranting focus for future research efforts.

Groundwater response to climate variability and land cover change is important for sustainable management of water resources in the Southwest US. Global Climate Models (GCM) project that the region will dry in the 21st century and the transition to a more arid climate may be under way. In semiarid Basin and Range systems, this impact is likely to be most pronounced in Mountain System Recharge (MSR), a process which constitutes a significant component of recharge in these basins. Despite the importance of MSR the physical processes that control MSR, and hence the climate change impacts, have not been fully investigated because of the complexity of recharge processes in mountainous catchments and limited observations. In this study, methodologies were developed to provide process-based understanding of MSR based on empirical and data-driven approaches. For the empirical approach, a hydrologically-based seasonal ratio the Normalized Seasonal Wetness Index (NSWI) was developed. It incorporates seasonal precipitation variability and temperature regimes to seasonal MSR estimation using existing empirical equations. Stable isotopic data was used to verify recharge partitioning. Using the NSWI and statistically downscaled monthly GCM precipitation and temperature data, climate change impacts on seasonal MSR are evaluated. Second, a novel data-based approach was developed to quantify mountain block recharge based on the catchment storage-discharge (S-Q) relationships and informed by isotopic data. Development of S-Q relationships across the Sabino Creek catchment, Arizona, allowed understanding of MBR dynamics across scale.Two ArcGIS desktop applications were developed for ArcGIS 9.2 to enhance recharge and evapotranspiration (ET) estimation: Arc-Recharge and RIPGIS-NET. Arc-Recharge was developed to quantify and distribute recharge along MODFLOW cells using spatially explicit precipitation data and a digital elevation model. RIPGIS-NET was developed to provide parameters for the RIP-ET package and to visualize MODFLOW results. RIP-ET is an improved MODFLOW ET module for simulating ET. RIPGIS-NET improves alluvial recharge estimation by providing spatially explicit riparian ET estimates. Using such tools and the above methods improves recharge and ET estimation in groundwater models by incorporating temporally and spatially explicit data and hence the assessment of climate variability and land cover change on groundwater resources can be improved.

Hydrologic catchment response varies in time. The goal of this dissertation is to investigate how and why it varies and what controls these variations. In order to tackle these questions the first step is to develop a method that permits the capturing of the temporal variation of transit time distributions (TTDs). To this end, the established transfer function-convolution approach using time series of stable water isotopes was modified so that it is now able to determine variable mean transit times (mTTs). The type and the shape parameter of the transfer function also vary in time. We found that antecedent moisture content, saturated hydraulic conductivity, soil depth and subsequent precipitation intensity are all potential controls. We propose a dimensionless number that integrates these controls and relates available storage to incoming and outgoing water fluxes in combination with information on antecedent moisture conditions to predict TTD type and shape. The individual TTDs for every time step produced by this model can be superimposed, summed and normalized to create a classification tool for catchments that is based on its general response behavior to precipitation events: the master transit time distribution. With this model in hand the hydrologic response for three consecutive monsoon seasons in ten nested subcatchments was examined. It was found that the major response controls were changing between the years in accordance with three hydrologic response modes. The mTT correlated most strongly with soil depth in the first year, with hydraulic conductivity in the second year and with curvature in the third year. These variations were produced by differences in precipitation patterns that led to differences in soil saturation and consequently to different dominant flow processes: in the first year most of the water left the catchment via fast flow paths (macropore flow, overland flow), in the second year shallow subsurface flow in the soil matrix was more dominant and in the third year most outflowing water derived from slow base flow. To better predict hydrologic catchment response we propose to apply a dimensionless number to determine the catchment response mode for every time step before selecting the appropriate response control.

Abandoned metal mines in the Tamar catchment, south west England, represent a significant threat to surface water quality via generation of acid mine waters. Currently the River Tamar fails environmental quality standards (EQS) established under the Water Framework Directive (2000/60/EC) for dissolved Cu (x ̅ = 0.19 ± 0.05 μmol L-1) and Zn (x ̅ = 0.19 ± 0.06 μmol L-1, both 1997-2007) downstream of historic mining area of Gunnislake. The aim of this study was to quantify the risk to surface water quality by diffuse drainage generated by mine waste tips. For the first time, a GIS model was compiled and used to generate a priority list of known areas of mine waste, based on physical and environmental factors. The methodology was consistent with European guidance documentation published to meet the requirements of the Mining Waste Directive (2001/21/EC) and has since been applied, in a modified form, to other catchments in south west England. Two study sites, with contrasting mineralogy and hydrology, scored highly in the model and were the subject of field investigations from 2007-2009. These were Devon Great Consols (DGC), an abandoned Cu-As mine near Gunnislake and Wheal Betsy (WB), an abandoned Pb-Ag mine, near Mary Tavy. At each site, surface waters and shallow groundwaters were sampled and analysed for dissolved metals (including Al, Cu, Zn, Mn, Pb, Ni, and Cd), metalloids (As, Sb), major ions and anions. Samples of four selected mine waste tips were also gathered and subjected to a range of laboratory leaching experiments including the novel application of a dynamic upflow percolation test, based on an existing European method (CEN TS 14405). Leachates generated by the waste tips in the field were highly variable and elevated with respect to EQS for Al (up to 1850 μmol L-1), Cu (570 μmol L-1), Zn (34 μmol L-1), Ni (3.8 μmol L-1), Cd (0.17 μmol L-1), Mn (216 μmol L-1), Fe(537 μmol L-1) , As (380 μmol L-1) and Sb (5.4 μmol L-1). Estimated annual fluxes of dissolved metals were predicted using average rainfall data and catchment areas calculated in ArcHydro9 to estimate the annual discharge of waters from the tip. These calculations showed annual contaminant flux from the tips to exceed, or be of the same order of magnitude to, major adit discharges in the catchment (e.g. Cu 50900-66900 mol y-1 at DGC and 470 mol y-1 Cd at WB) and represented a significant contributor to metal flux in the Tamar catchment. Primary sulphide minerals in the waste were generally highly altered and metals (Pb, Cu, Zn, and Mn) and As were found to be strongly associated with secondary iron minerals, precipitated under oxic conditions. In finer wastes, sorption to clay minerals was also found to be very important for the retention of dissolved metals, particularly Pb. Concentrations of contaminants in column field leachates were similar for most metals (Cu, Zn, Mn, Ni and Cd) and may provide a useful tool for prediction of leachate composition. However, sorption and release of metals and As to the secondary phases and clays were highly sensitive to pH change and where laboratory experiments did not replicate field pH, discrepancies between in situ and laboratory results were observed up to two orders of magnitude in scale (particularly for As and Pb).