The value of high-resolution nutrient monitoring: A case study of the River Frome, Dorset, UK

The River Frome was sampled at sub-daily sampling interval, with additional storm sampling, through an annual cycle. Samples were analysed for total phosphorus (TP), soluble reactive phosphorus (SRP), total oxidisable nitrogen (TON) and dissolved reactive silicon (Si). The resulting data set was artificially decimated to mimic sampling frequencies from 12 h to monthly time interval. Monthly sampling interval resulted in significant errors in the estimated annual TP and SRP load of up to 35% and 28% respectively, and the resulting data sets were insufficient to observe peaks in P concentration in response to storm events. Weekly sampling reduced the maximum percentage errors in annual load estimate to 15.4% and 6.5%. TON and silicon concentrations were less variable with changing river flow, and monthly sampling was sufficient to predict annual load estimates to within 10%. However, to investigate within-river nutrient dynamics and behaviour, it is suggested that a weekly sampling interval would be the minimum frequency required for TON and Si studies, and daily sampling would be a minimum requirement to adequately investigate phosphorus dynamics. The loss in nutrient-concentration signal due to reduced sampling interval is presented. Hysteresis in the nutrient concentration/flow relationships for all 32 storm events during the study period were modelled and seasonal patterns discussed to infer nutrient sources and behaviour. The high-resolution monitoring in this study identified, for the first time, major peaks in phosphorus concentration in winter that coincide with sudden falls in air temperature, and was associated with biofilm breakdown. This study has shown that to understand complex catchment nutrient processes, accurately quantify nutrient exports from catchments, and observe changes in water quality as a result of nutrient mitigation efforts over time, it is vital that the newly emerging field-based automated sampler/analyzer technologies begin to be deployed, to allow for routine high-resolution monitoring of our rivers in the future.     

Water‐quality response to a high‐elevation wildfire in the Colorado Front Range

Water quality of the Big Thompson River in the Front Range of Colorado was studied for 2 years following a high‐elevation wildfire that started in October 2012 and burned 15% of the watershed. A combination of fixed‐interval sampling and continuous water‐quality monitors was used to examine the timing and magnitude of water‐quality changes caused by the wildfire. Prefire water quality was well characterized because the site has been monitored at least monthly since the early 2000s. Major ions and nitrate showed the largest changes in concentrations; major ion increases were greatest in the first postfire snowmelt period, but nitrate increases were greatest in the second snowmelt period. The delay in nitrate release until the second snowmelt season likely reflected a combination of factors including fire timing, hydrologic regime, and rates of nitrogen transformations. Despite the small size of the fire, annual yields of dissolved constituents from the watershed increased 20–52% in the first 2 years following the fire. Turbidity data from the continuous sensor indicated high‐intensity summer rain storms had a much greater effect on sediment transport compared to snowmelt. High‐frequency sensor data also revealed that weekly sampling missed the concentration peak during snowmelt and short‐duration spikes during rain events, underscoring the challenge of characterizing postfire water‐quality response with fixed‐interval sampling. Copyright © 2015 John Wiley & Sons, Ltd.     

Temporal sampling strategies and uncertainty in calibrating a conceptual hydrological model for a small boreal catchment

How much data is needed for calibration of a hydrological catchment model? In this paper we address this question by evaluating the information contained in different subsets of discharge and groundwater time series for multi‐objective calibration of a conceptual hydrological model within the framework of an uncertainty analysis. The study site was a 5·6‐km² catchment within the Forsmark research site in central Sweden along the Baltic coast. Daily time series data were available for discharge and several groundwater wells within the catchment for a continuous 1065‐day period. The hydrological model was a site‐specific modification of the conceptual HBV model. The uncertainty analyses were based on a selective Monte Carlo procedure. Thirteen subsets of the complete time series data were investigated with the idea that these represent realistic intermittent sampling strategies. Data subsets included split‐samples and various combinations of weekly, monthly, and quarterly fixed interval subsets, as well as a 53‐day ‘informed observer’ subset that utilized once per month samples except during March and April—the months containing large and often dominant snow melt events—when sampling was once per week. Several of these subsets, including that of the informed observer, provided very similar constraints on model calibration and parameter identification as the full data record, in terms of credibility bands on simulated time series, posterior parameter distributions, and performance indices calculated to the full dataset. This result suggests that hydrological sampling designs can, at least in some cases, be optimized. Copyright © 2009 John Wiley & Sons, Ltd.     

Evaluation of remote sensing‐based evapotranspiration estimates using a water transfer numerical simulation under different vegetation conditions in an arid area

Daily actual evapotranspiration (AET) and seasonal AET values are of great practical importance in the management of regional water resources and hydrological modelling. Remotely sensed AET models and Landsat satellite images have been used widely in producing AET estimates at the field scale. However, the lack of validation at a high spatial frequency under different soil water conditions and vegetation coverages limits their operational applications. To assess the accuracies of remote sensing‐based AET in an oasis‐desert region, a total of 59 local‐scale daily AET time series, simulated using HYDRUS‐1D calibrated with soil moisture profiles, were used as ground truth values. Of 59 sampling sites, 31 sites were located in the oasis subarea and 28 sites were located in the desert subarea. Additionally, the locally validated mapping evapotranspiration at high resolution with internalized calibration surface energy balance model was employed to estimate instantaneous AET values in the area containing all 59 of the sampling sites using seven Landsat subimages acquired from June 5 to August 24 in 2011. Daily AET was obtained using extrapolation and interpolation methods with the instantaneous AET maps. Compared against HYDRUS‐1D, the remote sensing‐based method produced reasonably similar daily AET values for the oasis sites, while no correlation was observed for daily AET estimated using these two methods for the desert sites. Nevertheless, a reasonable monthly AET could be estimated. The correlation analysis between HYDRUS‐1D‐simulated and remote sensing‐estimated monthly AET values showed relative root‐mean‐square error values of 15.1%, 12.1%, and 12.3% for June, July, and August, respectively. The root mean square error of the summer AET was 10.0%. Overall, remotely sensed models can provide reasonable monthly and seasonal AET estimates based on periodic snapshots from Landsat images in this arid oasis‐desert region.     

Sampling Strategies for Estimation of Parameters Related to Ground Water Quality

Multiple theoretical sampling designs are studied to determine whether sampling designs can be identified that will provide for characterization of ground water quality in rural regions of developing nations. Sampling design in this work includes assessing sampling frequency, analytical methods, length of sampling period, and requirements of sampling personnel. The results answer a set of questions regarding whether using innovative sampling designs can allow hydrogeologists to take advantage of a range of characterization technologies, sampling strategies, and available personnel to develop high-value, water-quality data sets. Monte Carlo studies are used to assess different sampling strategies in the estimation of three parameters related to a hypothetical chemical observed in a ground water well: mean concentration (MeanC), maximum concentration (MaxC), and total mass load (TML). Five different scenarios are simulated. These scenarios are then subsampled using multiple simulated sampling instruments, time periods (ranging from 1 to 10 years), and sampling frequencies (ranging from weekly to semiannually to parameter dependent). Results are analyzed via the statistics of the resulting estimates, including mean square error, bias, bias squared, and precision. Results suggest that developing a sampling strategy based on what may be considered lower quality instruments can represent a powerful field research approach for estimating select parameters when applied at high frequency. This result suggests the potential utility of using a combination of lower quality instrument and local populations to obtain high frequency data sets in regions where regular monitoring by technicians is not practical.     

High‐frequency water quality monitoring in an urban catchment: hydrochemical dynamics,primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river‐system, The Cut in England, using in situ sub‐daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190 000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Although 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in‐stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic, and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. © 2015 The Authors. Hydrological Processes published by John Wiley & Sons Ltd.     

CHOICE OF SAMPLING STRATEGY AND ESTIMATION METHOD FOR CALCULATING NITROGEN AND PHOSPHORUS TRANSPORT IN SMALL LOWLAND STREAMS

As reliable estimates of stream nutrient transport are required for many purposes including trend analysis, mass balances and model development, the impact of sampling strategy and estimation method on the bias and precision of stream nitrogen (N) and phosphorus (P) transport calculations was evaluated. The study was undertaken in two catchments in eastern Denmark. Selection of the most accurate sampling strategy and estimation method, i.e. with the lowest root mean square error (RMSE) was based on random (Monte Carlo) runs for generating replicate data sets from an essentially complete record of the concentration of total N (TN), total P (TP), particulate P (PP) and dissolved P (DP) during a two-year period (June 1987 to June 1989). The evaluation comprised 13 different estimation methods and seven discrete sampling strategies involving three categories (regular, stratified and strata sampling). The regular sampling strategies were more accurate (lower RMSE) during high-flow periods than stratified sampling. The greatest improvement in RMSE for TN, TP, PP and DP transport was obtained when increasing the sampling frequency from 12 each year (monthly) to 18 (monthly in summer and fortnightly in winter) and 26 each year (fortnightly). The increase in accuracy (RMSE) was less when increasing the sampling frequency to 52 (weekly) or 104 (biweekly). Nearly all the methods evaluated underestimated the annual transport of TP and PP, whereas TN and DP were both under- and overestimated. The best method of estimating N and P transport when utilizing discrete sampling was both site- and time-dependent. The overall best and most reproducible (stream to stream, year to year) method for estimating annual transport of TN, TP, PP and DP was a linear interpolation method. When this method was used to derive estimates of annual TN and TP transport based on fortnightly sampling, the RMSE was 1.4–5.4 and 20.2–38.5%, respectively, in the Gelbæk stream and 1.1–4.9 and 10.5–15.0%, respectively, in the Gjern Å stream. Subdividing the hydrograph into two strata (low-flow and high-flow periods) and sampling these strata separately for calculating TP transport was superior to discrete sampling for the smaller of the two catchments. A combination of regular sampling (monthly) and pooled high-flow sampling (eight events out of a total of 43) reduced the RMSE of the annual TP load to 10.4%.     

Effects of temporal scales and space mismatches on the TRMM 3B42 v7 precipitation product in a remote mountainous area

The accurate measurement of precipitation is essential to understanding regional hydrological processes and hydrological cycling. Quantification of precipitation over remote regions such as the Tibetan Plateau is highly unreliable because of the scarcity of rain gauges. The objective of this study is to evaluate the performance of the satellite precipitation product of tropical rainfall measuring mission (TRMM) 3B42 v7 at daily, weekly, monthly, and seasonal scales. Comparison between TRMM grid precipitation and point‐based rain gauge precipitation was conducted using nearest neighbour and bilinear weighted interpolation methods. The results showed that the TRMM product could not capture daily precipitation well due to some rainfall events being missed at short time scales but provided reasonably good precipitation data at weekly, monthly, and seasonal scales. TRMM tended to underestimate the precipitation of small rainfall events (less than 1 mm/day), while it overestimated the precipitation of large rainfall events (greater than 20 mm/day). Consequently, TRMM showed better performance in the summer monsoon season than in the winter season. Through comparison, it was also found that the bilinear weighted interpolation method performs better than the nearest neighbour method in TRMM precipitation extraction.     

Subsurface Transport of Inorganic and Organic Solutes from Experimental Road Spreading of Oil-Field Brine

A study designed to evaluate ground water quality changes resulting from spreading oil-field brine on roads for ice and dust control was conducted using a gravel roadbed that received weekly applications of brine eight times during the winter phase and 11 times during the summer phase of the study. A network of 11 monitoring wells and five pressure-vacuum lysimeters was installed to obtain ground water and soil water samples. Thirteen sets of water- quality samples were collected and analyzed for major ions, trace metals, and volatile organic compounds. Two sets of samples were taken prior to brine spreading, four sets during winter-phase spreading, five sets during summer- phase spreading, and two sets during the interim between the winter and summer phases. A brine plume delineated by elevated specific-conductance values and elevated chloride concentrations developed downgradient of the roadbed during both the winter and summer phases. The brine plume caused chloride concentrations in ground water samples to exceed U.S. EPA public drinking-water standards by two-fold during the winter phase and five-fold during the summer phase. No other major ions, trace metals, or volatile organic compounds exceeded the standards during the winter or summer phases. More than 99 percent dilution of the solutes in the brine occurred between the roadbed surface and the local ground water flow system. Further attenuation of calcium, sodium, potassium, and strontium resulted from adsorption, whereas further attenuation of benzene resulted from volatilization and adsorption.     

Hydrograph separation using tracers and digital filters to quantify runoff components in a semi‐arid mesoscale catchment

Chemical hydrograph separation using electrical conductivity and digital filters is applied to quantify runoff components in the 1,640 km² semi‐arid Kaap River catchment and its subcatchments in South Africa. A rich data set of weekly to monthly water quality data ranging from 1978 to 2012 (450 to 940 samples per site) was analysed at 4 sampling locations in the catchment. The data were routinely collected by South Africa's national Department of Water and Sanitation, using standard sampling procedures. Chemical hydrograph separation using electrical conductivity (EC) as a tracer was used as reference and a recursive digital filter was then calibrated for the catchment. Results of the two‐component hydrograph separation indicate the dominance of baseflow in the low flow regime, with a contribution of about 90% of total flow; however, during the wet season, baseflow accounts for 50% of total flow. The digital filter parameters were very sensitive and required calibration, using chemical hydrograph separation as a reference. Calibrated baseflow estimates ranged from 40% of total flow at the catchment outlet to 70% in the tributaries. The study demonstrates that routinely monitored water quality data, especially EC, can be used as a meaningful tracer, which could also aid in the calibration of a digital filter method and reduce uncertainty of estimated flow components. This information enhances our understanding of how baseflow is generated and contributed to streamflow throughout the year, which can aid in quantification of environmental flows, as well as to better parameterize hydrological models used for water resources planning and management. Baseflow estimates can also be useful for groundwater and water quality management.     

Comparison of methods for calculating annual solute exports from six forested appalachian watersheds

Six methods were compared for calculating annual stream exports of sulfate, nitrate, calcium, magnesium and aluminum from six small Appalachian watersheds. Approximately 250–400 stream samples and concurrent stream flow measurements were collected during baseflows and storm flows for the 1989 water year at five Pennsylvania watersheds and during the 1989–1992 water years at a West Virginia watershed. Continuous stream flow records were also collected at each watershed. Solute exports were calculated from the complete data set using six different scenarios ranging from instantaneous monthly measurements of stream chemistry and stream flow, to intensive monitoring of storm flow events and multiple regression equations. The results for five of the methods were compared with the regression method because statistically significant models were developed and the regression equations allowed for prediction of solute concentrations during unsampled storm flows. Results indicated that continuous stream flow measurement was critical to producing exports within 10% of regression estimates. For solutes whose concentrations were not correlated strongly with stream flow, weekly grab samples combined with continuous records of stream flow were sufficient to produce export estimates within 10% of the regression method. For solutes whose concentrations were correlated strongly with stream flow, more intensive sampling during storm flows or the use of multiple regression equations were the most appropriate methods, especially for watersheds where stream flows changed most quickly. Concentration–stream flow relationships, stream hydrological response, available resources and required level of accuracy of chemical budgets should be considered when choosing a method for calculating solute exports. © 1997 John Wiley & Sons, Ltd.     

Compared performances of different algorithms for estimating annual nutrient loads discharged by the eutrophic River Loire

Good estimates of pollutant fluxes are required for Earth systems sciences and water quality management. The gradual accumulation of water quality data records over the past few decades has increased the value of these data for examining long‐term trends. On many major rivers, however, infrequent sampling of most pollutants makes flux estimates and their analysis difficult. This paper explores the performance of different methods for estimating nutrient fluxes. The objective is to assess the accuracy (bias) and precision (dispersion) of annual nutrient fluxes based on monthly sampling, which is the frequency with which 80% of French water quality surveys have been carried out since 1971. The study is based on a data set of nutrient concentrations surveyed at high frequency during a 5 year pilot study (1981–85) at the Orléans station in the middle reaches of the River Loire, France. The mean specific fluxes were 641 (nitrate‐N), 96 (total‐P) and 37 kg year⁻¹ km⁻² (orthophosphate‐P). For each year, the data set was then ‘resampled’ by randomly simulating 12 sampling dates. 100 simulated monthly samplings were generated, upon which seven estimation methods were tested. The evaluations indicate that, when concentrations of specific substances in large rivers exhibit seasonal variation, a simple method based on linear interpolation between samples taken at approximately monthly intervals is advocated. With the monthly sampling interval, the precision (confidence level of 95%) of annual nutrient fluxes obtained by the appropriate methods was 13% for nitrates, 20% for total‐P, 26% for orthophosphates, and 34% for particulate‐P. The frequency of water quality surveys required to obtain an annual nutrient flux with 10% precision was around 15 days for nitrate, 10 days for orthophosphate‐P and total‐P, and about 5 days in the case of particulate‐P. Copyright © 2004 John Wiley & Sons, Ltd.     

Trends in the chemistry of precipitation and surface water in a national network of small watersheds

Trends in precipitation and surface water chemistry at a network of 15 small watersheds (< 10 km²) in the USA were evaluated using a statistical test for monotonic trends (the seasonal Kendall test) and a graphical smoothing technique for the visual identification of trends. Composite precipitation samples were collected weekly and surface water samples were collected at least monthly. Concentrations were adjusted before trend analysis, by volume for precipitation samples and by flow for surface water samples. A relation between precipitation and surface water trends was not evident either for individual inorganic solutes or for solute combinations, such as ionic strength, at most sites. The only exception was chloride, for which there was a similar trend at 60% of the sites. The smoothing technique indicated that short-term patterns in precipitation chemistry were not reflected in surface waters. The magnitude of the short-term variations in surface water concentration was generally larger than the overall long-term trend, possibly because flow adjustment did not adequately correct for climatic variability. Detecting the relation between precipitation and surface water chemistry trends may be improved by using a more powerful sampling strategy and by developing better methods of concentration adjustment to remove the effects of natural variation in surface waters.     

Evaluation of the possibility for phytoplankton monitoring frequency reduction in the coastal waters of the Community of Valencia, in the scope of the Water Framework Directive

The Water Framework Directive, under the European Legislation, requires that all European waters, should reach a good ecological status by 2015. To achieve this goal, a phytoplankton monitoring network with monthly water samplings was established to evaluate the ecological quality, in the coastal waters of the Community of Valencia, and the collected data have allowed us to study the efficiency of the monthly campaigns of the monitoring network. With the results obtained in this research, we have designed a new monitoring strategy for the coastal waters of Valencia that for certain water bodies can mean lower sampling frequency. The new monitoring policy provides results as reliable as the previous strategy and allows a precise ecological classification of water bodies at a lower cost. The methodologies we have developed can be used in other monitoring networks and are not limited by geographic location or by the type of water body.     

Spatial–temporal variability in water quality and macro-invertebrate assemblages in the Upper Mara River basin,Kenya

Tropical rivers display profound temporal and spatial heterogeneity in terms of environmental conditions. This aspect needs to be considered when designing a monitoring program for water quality in rivers. Therefore, the physico-chemical composition and the nutrient loading of the Upper Mara River and its two main tributaries, the Amala and Nyangores were monitored. Initial daily, and later a weekly monitoring schedule for 4 months spanning through the wet and dry seasons was adopted. Benthic macro-invertebrates were also collected during the initial sampling to be used as indicators of water quality. The aim of the current study was to investigate the physico-chemical status and biological integrity of the Upper Mara River basin. This was achieved by examining trends in nutrient concentrations and analyzing the structure, diversity and abundance of benthic macro-invertebrates in relation to varying land use patterns. Sampling sites were selected based on catchment land use and the level of human disturbance, and using historical records of previous water quality studies. River water pH, dissolved oxygen, electrical conductivity (EC), temperature, and turbidity were determined in situ. All investigated parameters except iron and manganese had concentration values within allowable limits according to Kenyan and international standards for drinking water. The Amala tributary is more mineralized and also shows higher levels of pH and EC than water from the Nyangores tributary. The latter, however, has a higher variability in both the total phosphorus (TP) and total nitrogen (TN) concentrations. The variability in TP and TN concentrations increases downstream for both tributaries and is more pronounced for TN than for TP. Macro-invertebrate assemblages responded to the changes in land use and water quality in terms of community composition and diversity. The study recommends detailed continuous monitoring of the water quality at shorter time intervals and to identify key macro-invertebrate taxa that can be used to monitor changes of the water quality in rivers of the Mara basin as a result of anthropogenic changes.     

When to conduct an isotopic survey for lake water balance evaluation in highly seasonal climates

One‐time or short‐term lake water isotopic surveys are often employed to evaluate regional lake water balance. However, it can be difficult to determine the optimal time‐window for sampling to obtain a representative long‐term perspective of lake water balance in settings influenced by seasonal variations in precipitation, evaporative loss, glacial/snow meltwater, and larger seasonal shifts in isotopic composition of precipitation. This is especially true for areas of the Tibetan Plateau that are influenced by the summer Indian monsoon. Although high‐frequency sampling is always preferred as the most rigorous approach to characterize the water budget of lakes or watersheds, this may be impractical in remote regions and over large spatial scales. To assess the potential sensitivity of isotope balance characterization to seasonal variability, we used a weekly lake water isotope data set acquired over a period of 3 years on the Tibetan Plateau to evaluate the potential inaccuracies that might have arisen from using isotopic data collected during narrower time‐windows. For this assessment, we use weekly isotopic data collected during the study and assume that these sampling events were stand‐alone one‐time surveys. We then demonstrate the sensitivity of the isotope balance method in this setting, particularly for the rainy season that significantly underestimated the evaporation/inflow. In contrast, isotopic composition of the lake water was found to be more representative of long‐term conditions when sampled in October on the Tibetan Plateau. To broaden our evaluation of seasonality effects over a range of climatic zones, published high‐frequency isotopic data were also compiled, and a similar assessment was carried out for selected regions of the world. The synthesized data and model outputs, which confirm pronounced variations in lake water isotopic composition and evaporation/inflow across a range of seasonal climates, were used to determine optimal sampling windows for these specific regions.     

Pollution Source Investigation and Water Quality Management in the Carp Lake Watershed,Taiwan

In this study, a full survey of pollutant sources and water quality was conducted, followed by the application of a water quality model (Water Quality Analysis Simulation Program, WASP) to establish strategies of water quality control in Carp Lake, Taiwan. Results of the field investigation show that both point and non‐point source (NPS) pollutants were responsible for the poor water quality. The contributions of biochemical oxygen demand (BOD) from point source and NPS pollution were 45.9 and 55.1%, respectively. About 80% of total phosphorus (TP) were contributed by NPS. Additionally, point source and NPS pollution discharged 55.5 and 44.5% of NH₃–N load, respectively. The Carlson's Trophic State Index ranged from 61.9 to 69.2 showing serious eutrophic problems in Carp Lake. The calculated BOD, NH₃–N, and TP carrying capacity were approximately 2.8, 0.42, and 0.15 kg per day, respectively. However, the current pollutant loadings are approximately 3.0–5.5 times the calculated carrying capacity. With the help of the calibrated WASP model, remedial strategies for the lake water from short‐term to long‐term were developed. The completion of the small local sewer system to remove 80% of the point source pollution can serve as a short‐term goal while 40–60% of NPS removal by natural treatment systems may serve as a mid‐term goal. Furthermore, 80% of both source point and NPS pollution removal can be considered as a long‐term strategy. Results of heavy metal analysis show that the enriched sediment would be safe for agricultural applications.     

Effects of streamflow isotope sampling strategies on the calibration of a tracer-aided rainfall-runoff model

Isotopes are increasingly used in rainfall-runoff models to constrain conceptualisations of internal catchment functioning and reduce model uncertainty. However, there is little guidance on how much tracer data is required to adequately do this, and different studies use data from different sampling strategies. Here, we used a 7-year time series of daily stable water isotope samples of precipitation and streamflow to derive a range of typical stream sampling regimes and investigate how this impacts calibration of a semi-distributed tracer-aided model in terms of flow, deuterium and flux age simulations. Over the 7 years weekly sampling facilitated an almost identical model performance as daily, and there were only slight deteriorations in performance for fortnightly sampling. Monthly sampling resulted in poorer deuterium simulations and greater uncertainty in the derived parameter sets ability to accurately represent catchment functioning, evidenced by unrealistic reductions in the volumes of water available for mixing in the saturation area causing simulated water age decreases. Reducing sampling effort and restricting data collection to 3 years caused reductions in the accuracy of deuterium simulation, though the deterioration did not occur if sampling continued for 5 years. Analysis was also undertaken to consider the effects of reduced sampling effort over the driest and wettest hydrological years to evaluate effects of more extreme conditions. This showed that the model was particularly sensitive to changes in sampling during dry conditions, when the catchment hydrological response is most non-linear. Across all dataset durations, sampling in relation to flow conditions, rather than time, revealed that samples collected at flows >Q50 could provide calibration results comparable to daily sampling. Targeting only extreme high flows resulted in poor deuterium and low flow simulations. This study suggests sufficient characterization of catchment functioning can be obtained through reduced sampling effort over longer timescales and the targeting of flows >Q50.     

Observed Spatial and Temporal Distributions of CVOCs at Colorado and New York Vapor Intrusion Sites

The vapor intrusion impacts associated with the presence of chlorinated volatile organic contaminant plumes in the ground water beneath residential areas in Colorado and New York have been the subject of extensive site investigations and structure sampling efforts. Large data sets of ground water and indoor air monitoring data collected over a decade-long monitoring program at the Redfield, Colorado, site and monthly ground water and structure monitoring data collected over a 19-month period from structures in New York State are analyzed to illustrate the temporal and spatial distributions in the concentration of volatile organic compounds that one may encounter when evaluating the potential for exposures due to vapor intrusion. The analysis of these data demonstrates that although the areal extent of structures impacted by vapor intrusion mirrors the areal extent of chlorinated volatile organic compounds in the ground water, not all structures above the plume will be impacted. It also highlights the fact that measured concentrations of volatile organic compounds in the indoor air and subslab vapor can vary considerably from month to month and season to season. Sampling results from any one location at any given point in time cannot be expected to represent the range of conditions that may exist at neighboring locations or at other times. Recognition of this variability is important when designing sampling plans and risk management programs to address the vapor intrusion pathway.     

Nutrient loss and water quality under extensive grazing in the upper Burdekin river catchment, North Queensland

Increased sediment and nutrient losses resulting from unsustainable grazing management in the Burdekin River catchment are major threats to water quality in the Great Barrier Reef Lagoon. To test the effects of grazing management on soil and nutrient loss, five 1 ha mini-catchments were established in 1999 under different grazing strategies on a sedimentary landscape near Charters Towers. Reference samples were also collected from watercourses in the Burdekin catchment during major flow events. Soil and nutrient loss were relatively low across all grazing strategies due to a combination of good cover, low slope and low rainfall intensities. Total soil loss varied from 3 to 20 kg ha(-1) per event while losses of N and P ranged from 10 to 1900 g ha(-1) and from 1 to 71 g ha(-1) per event respectively. Water quality of runoff was considered moderate across all strategies with relatively low levels of total suspended sediment (range: 8-1409 mg l(-1)), total N (range: 101-4000 microg l(-1)) and total P (range: 14-609 microg l(-1)). However, treatment differences are likely to emerge with time as the impacts of the different grazing strategies on land condition become more apparent. Samples collected opportunistically from rivers and creeks during flow events displayed significantly higher levels of total suspended sediment (range: 10-6010 mg l(-1)), total N (range: 650-6350 microg l(-1)) and total P (range: 50-1500 microg l(-1)) than those collected at the grazing trial. These differences can largely be attributed to variation in slope, geology and cover between the grazing trial and different catchments. In particular, watercourses draining hillier, grano-diorite landscapes with low cover had markedly higher sediment and nutrient loads compared to those draining flatter, sedimentary landscapes. These preliminary data suggest that on relatively flat, sedimentary landscapes, extensive cattle grazing is compatible with achieving water quality targets, provided high levels of ground cover are maintained. In contrast, sediment and nutrient loss under grazing on more erodable land types is cause for serious concern. Long-term empirical research and monitoring will be essential to quantify the impacts of changed land management on water quality in the spatially and temporally variable Burdekin River catchment.