Interspecific variation in the elemental and stable isotope content of seagrasses in South Florida

The elemental (C, N, and P) and isotope (δ13C, δ15N) content of leaves of the seagrasses Thalassia testudinum, Halodule wrightii, and Syringodium filiforme were measured across a 10 000 km2 survey of the seagrass communities of South Florida, USA, in 1999 and 2000. Trends at local and broad spatial scales were compared to examine interspecific variation in the seagrass characteristics often used as ecological indicators. The elemental and stable isotope contents of all species were variable and demonstrated marked interspecific variation. At broad spatial scales, mean N:P ratios were lowest for T. testudinum (36.5 ± 1.1) and S. filiforme (38.9 ± 1.3), and highest for H. wrightii (44.1 ± 1.8). Stable carbon isotope ratios (δ13C) were highest for S. filiforme (–6.2 ± 0.2‰), intermediate for T. testudinum (–8.6 ± 0.2‰), and lowest for H. wrightii (–10.6 ± 0.3‰). Stable nitrogen isotopes (δ15N) were heaviest for T. testudinum (2.0 ± 0.1‰), and lightest for H. wrightii (1.0 ± 0.3‰) and S. filiforme (1.6 ± 0.2‰). Site depth was negatively correlated to δ13C for all species, while δ15N was positively correlated to depth for H. wrightii and S. filiforme. Similar trends were observed in local comparisons, suggesting that taxon-specific physiological/ecological properties strongly control interspecific variation in elemental and stable isotope content. Temporal trends in δ13C were measured, and revealed that interspecific variation was displayed throughout the year. This work documents interspecific variation in the nutrient dynamics of 3 common seagrasses in South Florida, indicating that interpretation of elemental and stable isotope values needs to be species specific.

Seasonal and spatial variation in the stable isotopic composition (δ18O and δD) of precipitation in south Florida

Precipitation data collected from five sites in south Florida indicate a strong seasonal and spatial variation in δ18O and δD, despite the relatively limited geographic coverage and low-lying elevation of each of the collection sites. Based upon the weighted-mean stable isotope values, the sites were classified as coastal Atlantic, inland, and lower Florida Keys. The coastal Atlantic sites had weighted-mean values of δ18O and δD of −2.86‰ and −12.8‰, respectively, and exhibited a seasonal variation with lower δ18O and δD values in the summer wet-season precipitation (δ18O = −3.38‰, δD = −16.5‰) as compared to the winter-time precipitation (δ18O = −1.66‰, δD = −3.2‰). The inland site was characterized as having the highest d-excess value (+13.3‰), signifying a contribution of evaporated Everglades surface water to the local atmospheric moisture. In spite of its lower latitude, the lower Keys site located at Long Key had the lowest weighted-mean stable isotope values (δ18O = −3.64‰, δD = −20.2‰) as well as the lowest d-excess value of (+8.8‰). The lower δD and δ18O values observed at the Long Key site reflect the combined effects of oceanic vapor source, fractionation due to local precipitation, and slower equilibration of the larger raindrops nucleated by a maritime aerosol. Very low δ18O and δD values (δ18O < −6‰, δD < −40‰) were observed just prior to the passage of hurricanes from the Gulf of Mexico as well as during cold fronts from the north-west. These results suggest that an oceanic vapor source region to the west, may be responsible for the extremely low δD and δ18O values observed during some tropical storms and cold fronts.

Size-based variation in intertissue comparisons of stable carbon and nitrogen isotopic signatures of bull sharks (Carcharhinus leucas) and tiger sharks (Galeocerdo cuvier)

Stable isotopes are important tools for understanding the trophic roles of elasmobranchs. However, whether different tissues provide consistent stable isotope values within an individual are largely unknown. To address this, the relationships among carbon and nitrogen isotope values were quantified for blood, muscle, and fin from juvenile bull sharks (Carcharhinus leucas) and blood and fin from large tiger sharks (Galeocerdo cuvier) collected in two different ecosystems. We also investigated the relationship between shark size and the magnitude of differences in isotopic values between tissues. Isotope values were significantly positively correlated for all paired tissue comparisons, but R2 values were much higher for δ13C than for δ15N. Paired differences between isotopic values of tissues were relatively small but varied significantly with shark total length, suggesting that shark size can be an important factor influencing the magnitude of differences in isotope values of different tissues. For studies of juvenile sharks, care should be taken in using slow turnover tissues like muscle and fin, because they may retain a maternal signature for an extended time. Although correlations were relatively strong, results suggest that correction factors should be generated for the desired study species and may only allow coarse-scale comparisons between studies using different tissue types.

Miocene stable isotope record of benthic foraminifera from IODP Site 320-U1336

Stable carbon and oxygen isotopes (d13C and d18O) of foraminiferal tests are amongst the most important tools in paleoceanography but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here, we compare three middle Miocene (16-13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicate continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (<100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and d18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well resolved paleo-magnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global Geological Timescale.

Stable isotope ratios on planktonic foraminifer N. pachyderma of surface sediments from the Arctic Ocean (Table 1)

Planktic foraminifers Neogloboquadrina pachyderma (sin.) from 87 eastern and central Arctic Ocean surface sediment samples were analyzed for stable oxygen and carbon isotope composition. Additional results from 52 stations were taken from the literature. The lateral distribution of delta18O (18O/16O) values in the Arctic Ocean reveals a pattern of roughly parallel, W-E stretching zones in the Eurasian Basin, each ~0.5 per mil wide on the delta18O scale. The low horizontal and vertical temperature variability in the Arctic halocline waters (0-100 m) suggests only little influence of temperature on the oxygen isotope distribution of N. pachyderma (sin.). The zone of maximum delta18O values of up to 3.8 per mil is situated in the southern Nansen Basin and relates to the tongue of saline (> 33%.) Atlantic waters entering the Arctic Ocean through the Fram Strait. delta18O values decrease both to the Barents Shelf and to the North Pole, in accordance with the decreasing salinities of the halocline waters. In the Nansen Basin, a strong N-S delta18O gradient is in contrast with a relatively low salinity change and suggests contributions from different freshwater sources, i.e. salinity reduction from sea ice meltwater in the south and from light isotope waters (meteoric precipitation and river-runoff) in the northern part of the basin. North of the Gakkel Ridge, delta18O and salinity gradients are in good accordance and suggest less influence of sea ice melting processes. The delta13C (13C/12C) values of N. pachyderma (sin.) from Arctic Ocean surface sediment samples are generally high (0.75-0.95 per mil). Lower values in the southern Eurasian Basin appear to be related to the intrusion of Atlantic waters. The high delta13C values are evidence for well ventilated surface waters. Because the perennial Arctic sea ice cover largely prevents atmosphere-ocean gas exchange, ventilation on the seasonally open shelves must be of major importance. Lack of delta13C gradients along the main routes of the ice drift from the Siberian shelves to the Fram Strait suggests that primary production (i.e. CO2 consumption) does probably not change the CO2 budget of the Arctic Ocean significantly.

On the microstructure, growth pattern and original porosity of belemnite rostra: insights from calcitic Jurassic belemnites

Calcitic belemnite rostra are usually employed to perform paleoenvironmental studies based on geochemical data. However, several questions, such as their original porosity and microstructure, remain open, despite they are essential to make accurate interpretations based on geochemical analyses.This paper revisits and enlightens some of these questions. Petrographic data demonstrate that calcite crystals of the rostrum solidum of belemnites grow from spherulites that successively develop along the apical line, resulting in a “regular spherulithic prismatic” microstructure. Radially arranged calcite crystals emerge and diverge from the spherulites: towards the apex, crystals grow until a new spherulite is formed; towards the external walls of the rostrum, the crystals become progressively bigger and prismatic. Adjacent crystals slightly vary in their c-axis orientation, resulting in undulose extinction. Concentric growth layering develops at different scales and is superimposed and traversed by a radial pattern, which results in the micro-fibrous texture that is observed in the calcite crystals in the rostra.Petrographic data demonstrate that single calcite crystals in the rostra have a composite nature, which strongly suggests that the belemnite rostra were originally porous. Single crystals consistently comprise two distinct zones or sectors in optical continuity: 1) the inner zone is fluorescent, has relatively low optical relief under transmitted light (TL) microscopy, a dark-grey color under backscatter electron microscopy (BSEM), a commonly triangular shape, a “patchy” appearance and relatively high Mg and Na contents; 2) the outer sector is non-fluorescent, has relatively high optical relief under TL, a light-grey color under BSEM and low Mg and Na contents. The inner and fluorescent sectors are interpreted to have formed first as a product of biologically controlled mineralization during belemnite skeletal growth and the non-fluorescent outer sectors as overgrowths of the former, filling the intra- and inter-crystalline porosity. This question has important implications for making paleoenvironmental and/or paleoclimatic interpretations based on geochemical analyses of belemnite rostra.Finally, the petrographic features of composite calcite crystals in the rostra also suggest the non-classical crystallization of belemnite rostra, as previously suggested by other authors.

Combining histology, stable isotope analysis and ZooMS collagen fingerprinting to investigate the taphonomic history and dietary behaviour of extinct giant tortoises from the Mare aux Songes deposit on Mauritius

Taphonomic research of bones can provide additional insight into a site's formation and development, the burial environment and ongoing post-mortem processes. A total of 30 tortoise (Cylindraspis) femur bone samples from the Mare aux Songes site (Mauritius)were studied histologically, assessing parameters such as presence and type of microbial alteration, inclusions, staining/infiltrations, the degree of microcracking and birefringence. The absence of microbial attack in the 4200 year old Mare aux Songes bones suggests the animals rapidly entered the soil whole-bodied and were sealed anoxically, although they suffered frombiological and chemical degradation (i.e. pyrite formation/oxidation, mineral dissolution and staining) related to changes in the site's hydrology. Additionally, carbon and nitrogen stable isotopeswere analysed to obtain information on the animals' feeding behaviour. The results show narrowly distributed δ13C ratios, indicating a terrestrial C3 plant-based diet, combined with a wide range in δ15N ratios. This is most likely related to the tortoises' drought-adaptive ability to change their metabolic processes, which can affect the δ15N ratios. Furthermore, ZooMS collagen fingerprinting analysis successfully identified two tortoise species (C. triserrata and C. inepta) in the bone assemblage,which,when combined with stable isotope data, revealed significantly different δ15N ratios between the two tortoise species. As climatic changes around this period resulted in increased aridity in the Mascarene Islands, this could explain the extremely elevated δ15N ratio in our dataset. The endemic fauna was able to endure the climatic changes 4200 years ago, although human arrival in the 17th century changed the original habitat to such an extent that it resulted in the extinction of several species. Fortunately we are still able to study these extinct tortoises due to the beneficial conditions of their burial environment, resulting in excellent bone preservation.

The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1 ‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02 ‰ at 2 mg/L to +0.90 ‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43 ‰ in 1983 to 1.18 ‰ in 2010 and were offset by δ66Zn = 0.6 - 0.7 ‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03 ‰; 1SD, n=15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

Stable isotope ratios in bentho-demersal biota along a depth gradient in the bay of biscay: A multitrophic study

Although stable isotope ratios are increasingly used to investigate the trophic ecology of marine organisms, their spatial variations are still poorly understood in the coastal environment. In this study, we measured the stable isotope composition (δ13C, δ15N) of suspended particulate organic matter (SPOM) (primary producer), a suspension feeder, the great scallop Pecten maximus (primary consumer), megabenthic decapods and benthic fishes (secondary consumers) along a depth gradient (from 5m to 155m depth) across the continental shelf of the Bay of Biscay. Although the three trophic levels exhibited similar δ13C patterns along the gradient, the δ15N patterns varied between SPOM, scallops and carnivores. The δ15N difference between SPOM and scallops decreased with increasing depth, suggesting that non trophic factors may affect the stable isotope composition of scallops at deepest sampling stations. An opposed trend was found between scallops and carnivores, suggesting that the trophic level of these carnivores increased at higher depth, possibly as an adaptation to lower prey abundances. Although our results suggest that primary consumers are suitable to establish isotopic baselines in coastal environments, we stress the need for further studies aiming at characterizing the variability of stable isotopes in coastal biota, and the respective effects of baseline, trophic and metabolic factors in their isotopic composition.

When males are more inclined to stay at home :Insights into the partial migration of a pelagic seabird provided by geolocators and isotopes

Partial migration has never been studied in pelagic seabirds, but investigating old unresolved questions in new contexts can provide useful fresh insights. We used geolocators and stable isotopes to investigate this phenomenon in a migratory pelagic seabird, the Cory’s shearwater (Calonectris diomedea). Although most birds migrated to the southern hemisphere, 8.1% of studied birds (N = 172) remained close to the breeding colony (Selvagem Grande, Madeira, Portugal), foraging within the Canary current. Almost all resident birds were males, while age or body size did not predict migratory status. Despite displaying a high repeatability (R = 0.72) in the choice of wintering area, residency was not a fixed strategy and individuals could switch between migrating and staying in the Canary current in different years. The predictions resulting from the “body size” and the “social dominance” hypotheses, in which larger individuals or dominant individuals, respectively, remain closer to the breeding areas, were not supported by our data. Resident males were able to occupy the nesting burrows much earlier than migratory males and arrival time in this species is known to affect the probability of engaging in a reproductive attempt. The selective pressure to arrive early at the colony is therefore the most likely explanation for the maintenance of this partial migration system.

Assessing land–ocean connectivity via submarine groundwater discharge (SGD) in the Ria Formosa Lagoon (Portugal): combining radon measurements and stable isotope hydrology

Natural radioactive tracer-based assessments of basin-scale submarine groundwater discharge (SGD) are well developed. However, SGD takes place in different modes and the flow and discharge mechanisms involved occur over a wide range of spatial and temporal scales. Quantifying SGD while discriminating its source functions therefore remains a major challenge. However, correctly identifying both the fluid source and composition is critical. When multiple sources of the tracer of interest are present, failure to adequately discriminate between them leads to inaccurate attribution and the resulting uncertainties will affect the reliability of SGD solute loading estimates. This lack of reliability then extends to the closure of local biogeochemical budgets, confusing measures aiming to mitigate pollution. Here, we report a multi-tracer study to identify the sources of SGD, distinguish its component parts and elucidate the mechanisms of their dispersion throughout the Ria Formosa – a seasonally hypersaline lagoon in Portugal. We combine radon budgets that determine the total SGD (meteoric + recirculated seawater) in the system with stable isotopes in water (δ2H, δ18O), to specifically identify SGD source functions and characterize active hydrological pathways in the catchment. Using this approach, SGD in the Ria Formosa could be separated into two modes, a net meteoric water input and another involving no net water transfer, i.e., originating in lagoon water re-circulated through permeable sediments. The former SGD mode is present occasionally on a multi-annual timescale, while the latter is a dominant feature of the system. In the absence of meteoric SGD inputs, seawater recirculation through beach sediments occurs at a rate of  ∼  1.4  ×  106 m3 day−1. This implies that the entire tidal-averaged volume of the lagoon is filtered through local sandy sediments within 100 days ( ∼  3.5 times a year), driving an estimated nitrogen (N) load of  ∼  350 Ton N yr−1 into the system as NO3−. Land-borne SGD could add a further  ∼  61 Ton N yr−1 to the lagoon. The former source is autochthonous, continuous and responsible for a large fraction (59 %) of the estimated total N inputs into the system via non-point sources, while the latter is an occasional allochthonous source capable of driving new production in the system.

Assessment of flood-related recharge to alluvial aquifers of an irrigated catchment following extended drought conditions using 3D visualisation and environmental tracers, Lockyer Valley, southeast Queensland, Australia.

The Lockyer Valley in southeast Queensland, Australia, hosts an economically significant alluvial aquifer system which has been impacted by prolonged drought conditions (~1997 to ~ 2009). Throughout this time, the system was under continued groundwater extraction, resulting in severe aquifer depletion. By 2008, much of the aquifer was at <30% of storage but some relief occurred with rains in early 2009. However, between December 2010 and January 2011, most of southeast Queensland experienced unprecedented flooding, which generated significant aquifer recharge. In order to understand the spatial and temporal controls of groundwater recharge in the alluvium, a detailed 3D lithological property model of gravels, sands and clays was developed using GOCAD software. The spatial distribution of recharge throughout the catchment was assessed using hydrograph data from about 400 groundwater observation wells screened at the base of the alluvium. Water levels from these bores were integrated into a catchment-wide 3D geological model using the 3D geological modelling software GOCAD; the model highlights the complexity of recharge mechanisms. To support this analysis, groundwater tracers (e.g. major and minor ions, stable isotopes, 3H and 14C) were used as independent verification. The use of these complementary methods has allowed the identification of zones where alluvial recharge primarily occurs from stream water during episodic flood events. However, the study also demonstrates that in some sections of the alluvium, rainfall recharge and discharge from the underlying basement into the alluvium are the primary recharge mechanisms of the alluvium. This is indicated by the absence of any response to the flood, as well as the observed old radiocarbon ages and distinct basement water chemistry signatures at these locations. Within the 3D geological model, integration of water chemistry and time-series displays of water level surfaces before and after the flood suggests that the spatial variations of the flood response in the alluvium are primarily controlled by the valley morphology and lithological variations within the alluvium. The integration of time-series of groundwater level surfaces in the 3D geological model also enables the quantification of the volumetric change of groundwater stored in the unconfined sections of this alluvial aquifer during drought and following flood events. The 3D representation and analysis of hydraulic and recharge information has considerable advantages over the traditional 2D approach. For example, while many studies focus on singular aspects of catchment dynamics and groundwater-surface water interactions, the 3D approach is capable of integrating multiple types of information (topography, geological, hydraulic, water chemistry and spatial) into a single representation which provides valuable insights into the major factors controlling aquifer processes.

A catchment modelling approach integrating surface and groundwater processes, land use and distribution of nutrients : Elimbah Creek, southeast Queensland

As the world’s population is growing, so is the demand for agricultural products. However, natural nitrogen (N) fixation and phosphorus (P) availability cannot sustain the rising agricultural production, thus, the application of N and P fertilisers as additional nutrient sources is common. It is those anthropogenic activities that can contribute high amounts of organic and inorganic nutrients to both surface and groundwaters resulting in degradation of water quality and a possible reduction of aquatic life. In addition, runoff and sewage from urban and residential areas can contain high amounts of inorganic and organic nutrients which may also affect water quality. For example, blooms of the cyanobacterium Lyngbya majuscula along the coastline of southeast Queensland are an indicator of at least short term decreases of water quality. Although Australian catchments, including those with intensive forms of land use, show in general a low export of nutrients compared to North American and European catchments, certain land use practices may still have a detrimental effect on the coastal environment. Numerous studies are reported on nutrient cycling and associated processes on a catchment scale in the Northern Hemisphere. Comparable studies in Australia, in particular in subtropical regions are, however, limited and there is a paucity in the data, in particular for inorganic and organic forms of nitrogen and phosphorus; these nutrients are important limiting factors in surface waters to promote algal blooms. Therefore, the monitoring of N and P and understanding the sources and pathways of these nutrients within a catchment is important in coastal zone management. Although Australia is the driest continent, in subtropical regions such as southeast Queensland, rainfall patterns have a significant effect on runoff and thus the nutrient cycle at a catchment scale. Increasingly, these rainfall patterns are becoming variable. The monitoring of these climatic conditions and the hydrological response of agricultural catchments is therefore also important to reduce the anthropogenic effects on surface and groundwater quality. This study consists of an integrated hydrological–hydrochemical approach that assesses N and P in an environment with multiple land uses. The main aim is to determine the nutrient cycle within a representative coastal catchment in southeast Queensland, the Elimbah Creek catchment. In particular, the investigation confirms the influence associated with forestry and agriculture on N and P forms, sources, distribution and fate in the surface and groundwaters of this subtropical setting. In addition, the study determines whether N and P are subject to transport into the adjacent estuary and thus into the marine environment; also considered is the effect of local topography, soils and geology on N and P sources and distribution. The thesis is structured on four components individually reported. The first paper determines the controls of catchment settings and processes on stream water, riverbank sediment, and shallow groundwater N and P concentrations, in particular during the extended dry conditions that were encountered during the study. Temporal and spatial factors such as seasonal changes, soil character, land use and catchment morphology are considered as well as their effect on controls over distributions of N and P in surface waters and associated groundwater. A total number of 30 surface and 13 shallow groundwater sampling sites were established throughout the catchment to represent dominant soil types and the land use upstream of each sampling location. Sampling comprises five rounds and was conducted over one year between October 2008 and November 2009. Surface water and groundwater samples were analysed for all major dissolved inorganic forms of N and for total N. Phosphorus was determined in the form of dissolved reactive P (predominantly orthophosphate) and total P. In addition, extracts of stream bank sediments and soil grab samples were analysed for these N and P species. Findings show that major storm events, in particular after long periods of drought conditions, are the driving force of N cycling. This is expressed by higher inorganic N concentrations in the agricultural subcatchment compared to the forested subcatchment. Nitrate N is the dominant inorganic form of N in both the surface and groundwaters and values are significantly higher in the groundwaters. Concentrations in the surface water range from 0.03 to 0.34 mg N L..1; organic N concentrations are considerably higher (average range: 0.33 to 0.85 mg N L..1), in particular in the forested subcatchment. Average NO3-N in the groundwater has a range of 0.39 to 2.08 mg N L..1, and organic N averages between 0.07 and 0.3 mg N L..1. The stream bank sediments are dominated by organic N (range: 0.53 to 0.65 mg N L..1), and the dominant inorganic form of N is NH4-N with values ranging between 0.38 and 0.41 mg N L..1. Topography and soils, however, were not to have a significant effect on N and P concentrations in waters. Detectable phosphorus in the surface and groundwaters of the catchment is limited to several locations typically in the proximity of areas with intensive animal use; in soil and sediments, P is negligible. In the second paper, the stable isotopes of N (14N/15N) and H2O (16O/18O and 2H/H) in surface and groundwaters are used to identify sources of dissolved inorganic and organic N in these waters, and to determine their pathways within the catchment; specific emphasis is placed on the relation of forestry and agriculture. Forestry is predominantly concentrated in the northern subcatchment (Beerburrum Creek) while agriculture is mainly found in the southern subcatchment (Six Mile Creek). Results show that agriculture (horticulture, crops, grazing) is the main source of inorganic N in the surface waters of the agricultural subcatchment, and their isotopic signature shows a close link to evaporation processes that may occur during water storage in farm dams that are used for irrigation. Groundwaters are subject to denitrification processes that may result in reduced dissolved inorganic N concentrations. Soil organic matter delivers most of the inorganic N to the surface water in the forested subcatchment. Here, precipitation and subsequently runoff is the main source of the surface waters. Groundwater in this area is affected by agricultural processes. The findings also show that the catchment can attenuate the effects of anthropogenic land use on surface water quality. Riparian strips of natural remnant vegetation, commonly 50 to 100 m in width, act as buffer zones along the drainage lines in the catchment and remove inorganic N from the soil water before it enters the creek. These riparian buffer zones are common in most agricultural catchments of southeast Queensland and are indicated to reduce the impact of agriculture on stream water quality and subsequently on the estuary and marine environments. This reduction is expressed by a significant decrease in DIN concentrations from 1.6 mg N L..1 to 0.09 mg N L..1, and a decrease in the �15N signatures from upstream surface water locations downstream to the outlet of the agricultural subcatchment. Further testing is, however, necessary to confirm these processes. Most importantly, the amount of N that is transported to the adjacent estuary is shown to be negligible. The third and fourth components of the thesis use a hydrological catchment model approach to determine the water balance of the Elimbah Creek catchment. The model is then used to simulate the effects of land use on the water balance and nutrient loads of the study area. The tool that is used is the internationally widely applied Soil and Water Assessment Tool (SWAT). Knowledge about the water cycle of a catchment is imperative in nutrient studies as processes such as rainfall, surface runoff, soil infiltration and routing of water through the drainage system are the driving forces of the catchment nutrient cycle. Long-term information about discharge volumes of the creeks and rivers do, however, not exist for a number of agricultural catchments in southeast Queensland, and such information is necessary to calibrate and validate numerical models. Therefore, a two-step modelling approach was used to calibrate and validate parameters values from a near-by gauged reference catchment as starting values for the ungauged Elimbah Creek catchment. Transposing monthly calibrated and validated parameter values from the reference catchment to the ungauged catchment significantly improved model performance showing that the hydrological model of the catchment of interest is a strong predictor of the water water balance. The model efficiency coefficient EF shows that 94% of the simulated discharge matches the observed flow whereas only 54% of the observed streamflow was simulated by the SWAT model prior to using the validated values from the reference catchment. In addition, the hydrological model confirmed that total surface runoff contributes the majority of flow to the surface water in the catchment (65%). Only a small proportion of the water in the creek is contributed by total base-flow (35%). This finding supports the results of the stable isotopes 16O/18O and 2H/H, which show the main source of water in the creeks is either from local precipitation or irrigation waters delivered by surface runoff; a contribution from the groundwater (baseflow) to the creeks could not be identified using 16O/18O and 2H/H. In addition, the SWAT model calculated that around 68% of the rainfall occurring in the catchment is lost through evapotranspiration reflecting the prevailing long-term drought conditions that were observed prior and during the study. Stream discharge from the forested subcatchment was an order of magnitude lower than discharge from the agricultural Six Mile Creek subcatchment. A change in land use from forestry to agriculture did not significantly change the catchment water balance, however, nutrient loads increased considerably. Conversely, a simulated change from agriculture to forestry resulted in a significant decrease of nitrogen loads. The findings of the thesis and the approach used are shown to be of value to catchment water quality monitoring on a wider scale, in particular the implications of mixed land use on nutrient forms, distributions and concentrations. The study confirms that in the tropics and subtropics the water balance is affected by extended dry periods and seasonal rainfall with intensive storm events. In particular, the comprehensive data set of inorganic and organic N and P forms in the surface and groundwaters of this subtropical setting acquired during the one year sampling program may be used in similar catchment hydrological studies where these detailed information is missing. Also, the study concludes that riparian buffer zones along the catchment drainage system attenuate the transport of nitrogen from agricultural sources in the surface water. Concentrations of N decreased from upstream to downstream locations and were negligible at the outlet of the catchment.