Use of continuous monitoring to assess stream nitrate flux and transformation patterns

Delivery of nitrogen from farmed fields to the stream network is an ongoing water quality issue in central North America and other parts of the world. Although fertilization and other farming practices have been refined to produce environmental improvements, stemming loss of nitrogen, especially in the soluble nitrate form, is a problem that has seemingly defied solution. The Iowa Nutrient Reduction Strategy is a policy initiative designed to implement conservation and other farm management practices to produce reductions in nitrate loading. The strategy does not focus on how the streams themselves may or may not be processing nitrogen and reducing downstream loading. We used continuous high-frequency nitrate and discharge monitoring over 3 years at two sites separated by 18 km in a low-order, agricultural stream in eastern Iowa to estimate how nitrogen is processed, and whether or not these processes are reducing downstream loading. We conclude that the upstream to downstream nitrate concentration decline between the two sites was not driven by denitrification. These data also show that nitrate concentrations are closely coupled to discharge during periods of adequate moisture, but decoupling of concentration from discharge occurs during dry periods. This decoupling is a possible indicator of in-stream nitrate processing. Finally, nitrate concentrations are likely diluted by water sourced from non-row crop land covers in the lower reaches of the watershed.     

The importance of small urbanized watersheds to pollutant loading in a large oligotrophic subalpine lake of the western USA

Urban land use has been implicated as a major contributor of nonpoint source pollution in aquatic systems. Through increased nonpoint delivery of pollutants, including constituents found in stormwater, Lake Tahoe is undergoing a marked decline in its transparency, primarily due to increasing production of algae from enhanced nutrient loading and delivery of fine particles to the lake from the watershed. In response to these findings, a regional restoration effort is underway to improve basin watersheds and the water quality in Lake Tahoe. In this study, stormwater autosamplers were used to collect flow-weighted composite samples that characterized event mean concentrations for event and nonevent conditions within a small, urbanized watershed in the Tahoe basin. An event-specified constant-concentration water quality model was then applied to the event mean concentration and continuous streamflow data to estimate pollutant loads for nitrate, nitrite, ammonia, orthophosphate, and suspended sediment. These data were compared with previously reported load estimates from 10 primary monitored streams in larger watersheds of the Tahoe basin. Results from a linear regression analysis demonstrate strong and significant relationships between watershed impervious area and pollutant loadings from Lake Tahoe watersheds. These small, urbanized watersheds and intervening zones, which only comprise 10 % of the total Lake Tahoe drainage area, include a significant portion of the total Lake Tahoe impervious area. The findings of this study suggest that small, urbanized watersheds and intervening zones are disproportionately important contributors of nonpoint source pollution, including nutrients and suspended particles.     

Trends in nutrient and sediment retention in Great Plains reservoirs (USA)

Reservoirs are artificial ecosystems with physical, chemical, and biological transitional characteristics between rivers and lakes. Greater water retention time in reservoirs provides conditions for cycling materials inputs from upstream waters through sedimentation, biological assimilation and other biogeochemical processes. We investigated the effects of reservoirs on the water quantity and quality in the Great Plains (Kansas, USA), an area where little is known about these dominant hydrologic features. We analyzed a 30-year time-series of discharge, total phosphorus (TP), nitrate (NO₃ ^?), and total suspended solids (TSS) from six reservoirs and estimated overall removal efficiencies from upstream to downstream, testing correlations among retention, discharge, and time. In general, mean removal of TP (42–74 %), TSS (0–93 %), and NO₃ ^? (11–56 %) from upstream to downstream did not change over 30 years. TP retention was associated with TSS removal, suggesting that nutrient substantial portion of P was adsorbed to solids. Our results indicated that reservoirs had the effect of lowering variance in the water quality parameters and that these reservoirs are not getting more or less nutrient-rich over time. We found no evidence of temporal changes in the yearly mean upstream and downstream discharges. The ratio upstream/downstream discharge was analyzed because it allowed us to assess how much contribution of additional unsampled tributaries may have biased our ability to calculate retention. Nutrient and sediment removal was less affected by hydraulic residence time than expected. Our study demonstrates that reservoirs can play a role in the removal and processing of nutrient and sediments, which has repercussions when valuing their ecological services and designing watershed management plans.     

Assessing possible visitor-use impacts on water quality in Yosemite National Park, California

There is concern that visitor-use associated activities, such as bathing, dish washing, wastewater production, and stock animal use near lakes and streams, could cause degradation of water quality in Yosemite National Park. A study was conducted during 2004-2007 to assess patterns in nutrient and Escherichia coli (E. coli) concentrations in the Merced and Tuolumne Rivers and characterize natural background concentrations of nutrients in the park. Results indicated that nutrient and E. coli concentrations were low, even compared to other undeveloped sites in the United States. A multiple linear regression approach was used to model natural background concentrations of nutrients, with basin characteristics as explanatory variables. Modeled nitrogen concentrations increased with elevation, and modeled phosphorus concentrations increased with basin size. Observed concentrations (±uncertainty) were compared to modeled concentrations (±uncertainty) to identify sites that might be impacted by point sources of nutrients, as indicated by large model residuals. Statistically significant differences in observed and modeled concentrations were observed at only a few locations, indicating that most sites were representative of natural background conditions. The empirical modeling approach used in this study can be used to estimate natural background conditions at any point along a study reach in areas minimally impacted by development, and may be useful for setting water-quality standards in many national parks.     

Atmospheric influences on water quality: a simulation of nutrient loading for the Pearl River Basin, USA

Knowledge of water quality conditions is essential in assessing the health of riverine ecosystems. The goal of this study is to determine the degree to which water quality variables are related to precipitation and air temperature conditions for a segment of the Pearl River Basin near Bogalusa, LA, USA. The AQUATOX ecological fate simulation model is used to estimate daily total nitrogen, total phosphorus, and dissolved oxygen concentrations over a 2-year period. Daily modeled output for each variable was calibrated against reliably measured data to assess the accuracy. Observed data were plotted against simulated data for controlled and perturbed models for validation, and stepwise multiple regression analysis was used to quantify the relationships between the water quality and meteorological variables. Results suggest that daily dissolved oxygen is significantly negatively correlated to concurrent daily mean air temperature with a total explained variance of 0.679 (p?<?0.01), and monthly dissolved oxygen is significantly negatively correlated to monthly mean air temperature with a total explained variance of 0.567 (p?<?0.01). Total mean monthly phosphorus concentration is significantly positively related to the previous month's precipitation with a total explained variance of 0.302 (p?<?0.01). These relationships suggest that atmospheric conditions have a strong influence on water quality in the Pearl Basin. Therefore, environmental planners should expect that future climatic changes are likely to alter water quality.     

Mercury proxies and mercury dynamics in a forested watershed of the US Northeast

Although many studies focus on mercury (Hg) and methylmercury (MeHg) dynamics in streams, challenges remain in identifying the relative importance of land cover and seasonality at regulating Hg and MeHg dynamics at the watershed scale. Developing robust proxies for Hg and/or MeHg determination also remains a challenge. Our study used Hg, MeHg, and dissolved organic carbon (DOC) concentration measurements and various DOC fluorescence indices to characterize Hg and DOC dynamics in a forested watershed of the US Northeast. Principal component analysis indicated that land cover/landscape position (i.e., headwater vs. wetland-influenced area vs. lake-influenced area) explained 44 % of the variance in Hg, MeHg, DOC concentrations, and DOC quality during the snow-free season, while seasonality (i.e., air temperature and discharge) explained only 21 % of the variance in the results. Furthermore, finding a good proxy for Hg that is valid across a range of landscape positions remains a challenge; however, regression analysis indicated that the fluorescence peak Humic C (excitation?=?350 nm; emission?=?max (420–480)), which corresponds to the presence of melanoidins in water, explained 21 % of the variability in MeHg concentrations across both space and time (p?=?0.001), and thus appears to be a possible proxy for MeHg determination in our study watershed. From a management perspective, land cover modifications (lake, reservoir, and wetland) are likely to play more important roles at regulating Hg, MeHg, and DOC exports at the watershed scale than long-term changes in the climate of this region.     

Probability-based nitrate contamination map of groundwater in Kinmen

Groundwater supplies over 50 % of drinking water in Kinmen. Approximately 16.8 % of groundwater samples in Kinmen exceed the drinking water quality standard (DWQS) of NO₃ ^?-N (10 mg/L). The residents drinking high nitrate-polluted groundwater pose a potential risk to health. To formulate effective water quality management plan and assure a safe drinking water in Kinmen, the detailed spatial distribution of nitrate–N in groundwater is a prerequisite. The aim of this study is to develop an efficient scheme for evaluating spatial distribution of nitrate–N in residential well water using logistic regression (LR) model. A probability-based nitrate–N contamination map in Kinmen is constructed. The LR model predicted the binary occurrence probability of groundwater nitrate–N concentrations exceeding DWQS by simple measurement variables as independent variables, including sampling season, soil type, water table depth, pH, EC, DO, and Eh. The analyzed results reveal that three statistically significant explanatory variables, soil type, pH, and EC, are selected for the forward stepwise LR analysis. The total ratio of correct classification reaches 92.7 %. The highest probability of nitrate–N contamination map presents in the central zone, indicating that groundwater in the central zone should not be used for drinking purposes. Furthermore, a handy EC–pH-probability curve of nitrate–N exceeding the threshold of DWQS was developed. This curve can be used for preliminary screening of nitrate–N contamination in Kinmen groundwater. This study recommended that the local agency should implement the best management practice strategies to control nonpoint nitrogen sources and carry out a systematic monitoring of groundwater quality in residential wells of the high nitrate–N contamination zones.     

A geographical approach to tracking Escherichia coli and other water quality constituents in a Texas coastal plains watershed

Diffuse sources of surface water pathogens and nutrients can be difficult to isolate in larger river basins. This study used a geographical or nested approach to isolate diffuse sources of Escherichia coli and other water quality constituents in a 145.7-km² river basin in south central Texas, USA. Average numbers of E. coli ranged from 49 to 64,000 colony forming units (CFU) per 100 mL depending upon season and stream flow over the 1-year sampling period. Nitrate-N concentrations ranged from 48 to 14,041 μg?L^?1 and orthophosphate-P from 27 to 2,721 μg?L^?1. High concentrations of nitrate-N, dissolved organic nitrogen, and orthophosphate-P were observed downstream of waste water treatment plants but E. coli values were higher in a watershed draining an older part of the city. Total urban land use explained between 56 and 72 % of the variance in mean annual E. coli values (p?<?0.05) in nine hydrologically disconnected creeks. Of the types of urban land use, commercial land use explained most of the variance in E. coli values in the fall and winter. Surface water sodium, alkalinity, and potassium concentrations in surface water were best described by the proportion of commercial land use in the watershed. Based on our nested approach in examining surface water, city officials are able to direct funding to specific areas of the basin in order to mitigate high surface water E. coli numbers and nutrient concentrations.     

Characterization and statistical modeling of bacterial (Escherichia coli) outflows from watersheds that discharge into southern Lake Michigan

Two watersheds in northwestern Indiana were selected for detailed monitoring of bacterially contaminated discharges (Escherichia coli) into Lake Michigan. A large watershed that drains an urbanized area with treatment plants that release raw sewage during storms discharges into Lake Michigan at the outlet of Burns Ditch. A small watershed drains part of the Great Marsh, a wetland complex that has been disrupted by ditching and limited residential development, at the outlet of Derby Ditch. Monitoring at the outlet of Burns Ditch in 1999 and 2000 indicated that E. coli concentrations vary over two orders of magnitude during storms. During one storm, sewage overflows caused concentrations to increase to more than 10,000 cfu/100 mL for several hours. Monitoring at Derby Ditch from 1997 to 2000 also indicated that E. coli concentrations increase during storms with the highest concentrations generally occurring during rising streamflow. Multiple regression analysis indicated that 60% of the variability in measured outflows of E. coli from Derby Ditch (n = 88) could be accounted for by a model that utilizes continuously measured rainfall, stream discharge, soil temperature and depth to water table in the Great Marsh. A similar analysis indicated that 90% of the variability in measured E. coli concentrations at the outlet of Burns Ditch (n = 43) during storms could be accounted for by a combination of continuously measured water-quality variables including nitrate and ammonium. These models, which utilize data that can be collected on a real-time basis, could form part of an Early Warning System for predicting beach closures.     

Influence of different nitrate–N monitoring strategies on load estimation as a base for model calibration and evaluation

Model-based predictions of the impact of land management practices on nutrient loading require measured nutrient flux data for model calibration and evaluation. Consequently, uncertainties in the monitoring data resulting from sample collection and load estimation methods influence the calibration, and thus, the parameter settings that affect the modeling results. To investigate this influence, we compared three different time-based sampling strategies and four different load estimation methods for model calibration and compared the results. For our study, we used the river basin model Soil and Water Assessment Tool on the intensively managed loess-dominated Parthe watershed (315 km²) in Central Germany. The results show that nitrate–N load estimations differ considerably depending on sampling strategy, load estimation method, and period of interest. Within our study period, the annual nitrate–N load estimation values for the daily composite data set have the lowest ranges (between 9.8% and 15.7% maximum deviations related to the mean value of all applied methods). By contrast, annual estimation results for the submonthly and the monthly data set vary in greater ranges (between 24.9% and 67.7%). To show differences between the sampling strategies, we calculated the percentage deviation of mean load estimations of submonthly and monthly data sets as related to the mean estimation value of the composite data set. For nitrate–N, the maximum deviation is 64.5% for the submonthly data set in the year 2000. We used average monthly nitrate–N loads of the daily composite data set to calibrate the model to achieve satisfactory simulation results [Nash–Sutcliffe efficiency (NSE) 0.52]. Using the same parameter settings with submonthly and monthly data set, the NSE dropped to 0.42 and 0.31, respectively. Considering the different results from the monitoring strategy and the load estimation method, we recommend both the implementation of optimized monitoring programs and the use of multiple load estimation methods to improve water quality characterization and provide appropriate model calibration and evaluation data.     

Impacts of intensive agricultural irrigation and livestock farming on a semi-arid Mediterranean catchment

Irrigation return flows (IRF) are a major contributor of non-point source pollution to surface and groundwater. We evaluated the effects of irrigation on stream hydrochemistry in a Mediterranean semi-arid catchment (Flumen River, NE Spain). The Flumen River was separated into two zones based on the intensity of irrigation activities in the watershed. General linear models were used to compare the two zones. Relevant covariables (urban sewage, pig farming, and gypsum deposits in the basin) were quantified with the help of geographic information system techniques, accompanied by ground-truthing. High variability of the water quality parameters and temporal dynamics caused by irrigation were used to distinguish the two river reaches. Urban activity and livestock farming had a significant effect on water chemistry. An increase in the concentration of salts (240–541 μS·cm^???1 more in winter) and nitrate (average concentrations increased from 8.5 to 20.8 mg·l^???1 during irrigation months) was associated with a higher level of IRF. Those river reaches more strongly influenced by urban areas tended to have higher phosphorus (0.19–0.42 mg·l^???1 more in winter) concentrations. These results support earlier research about the significant consequences to water quality of both urban expansion and intensive agricultural production in arid and semi-arid regions. Data also indicate that salinization of soils, subsoils, surface water, and groundwater can be an unwelcome result of the application of pig manure for fertilization (increase in sodium concentration in 77.9 to 138.6 mg·l^???1).     

Effects of climate and landcover change on stream discharge in the Ozark Highlands,USA

Stream discharge of a watershed is affected and altered by climate and landcover changes. These effects vary depending on the magnitude and interaction of the changes, and need to be understood so that local water resource availability can be evaluated and socioeconomic development within a watershed be pursued and managed in a way sustainable with the local water resources. In this study, the landcover and climate change effects on stream discharge from the Jacks Fork River basin in the Ozark Highlands of the south-central United States were examined in three phases: site observation and data collection, model calibration and simulation, and model experiment and analysis. Major results of the study show that climate fluctuations between wet and dry extremes resulted in the same change of the basin discharge regardless of the landcover condition in the basin. On the other hand, under a specified climate condition landcover change from a grassland basin to a fully forested basin only resulted in about one half of the discharge change caused by the climate variation. Furthermore, when landcover change occurred simultaneously with climate variation, the basin discharge change amplified significantly and became larger than the combined discharge changes caused by the climate and landcover change alone, a result indicating a synergistic effect of landcover and climate change on basin discharge variability. Agricultural Research Division, University of Nebraska-Lincoln, Contribution Number 13437.Qi Hu: Corresponding author: Dr. Qi Hu, Climate and Bio-Atmospheric Sciences Group, School of Natural Resource Sciences, 237 L.W. Chase Hall, University of Nebraska-Lincoln, Lincoln, NE 68583-0728, USA. E-mail: qhu2@unl.edu.     

Evaluation of the impacts of mine drainage from a coal waste pile on the surrounding environment at Smolnica, southern Poland

Mine drainage impacts from a coal waste pile at Smolnica, Poland have been monitored. Groundwater in an unconfined aquifer downgradient from the pile has near-neutral pH, but high concentrations of sulfate (up to 3,827 mg/l), chloride (up to 903 mg/l), and sodium (up to 2,606 mg/l). Concentrations of iron and manganese are elevated only locally, and concentrations of other metals are low. The behavior of sulfate seems to be conservative in the downgradient aquifer, and gypsum may only be precipitating locally. Concentrations of iron and manganese seem to be controlled by the precipitation of ferric oxide and hydroxides and rhodochrosite, respectively. Complete neutralization of mine drainage by carbonates is consistent with high concentrations of calcium (up to 470 mg/l) and magnesium (up to 563 mg/l) and also with high strontium concentrations of up to 3.08 mg/l, observed in groundwater downgradient from the pile. Hydraulic head profiles at two sites within the river bottom sediments indicate upward flow toward the river with large local differences in groundwater recharge. Water chemistry profiles in the river bottom sediments and geochemical modeling suggest conservative behavior of Na, Cl, and SO₄ and precipitation of Fe and Mn at the groundwater/river water interface. Mine drainage enters the Bierawka River and causes increasing sulfate concentrations. In contrast, concentrations of sodium and chloride in the Bierawka River decrease downgradient from the pile because water in the river upgradient from the pile is already highly contaminated by these species from the discharge of mining waters. Concentrations of Fe and Mn in the river water are low, as a consequence of the precipitation of Fe and Mn oxide and hydroxides. Direct geochemical modeling was able to reproduce measured concentrations of conservative species (e.g., Na, Cl, and SO₄), but errors for metals and Ba were relatively large. In addition, calculated P_CO2 values in the river water are very high, suggesting that equilibrium with atmospheric P_CO2 and P_O2 has not been reached, and at least some reactions should be modeled as kinetic processes. High concentrations of Na, Cl, and SO₄ contribute to the contamination of the Odra River, which is joined by the Bierawka River farther downgradient, thus limiting the use of river water for recreation and other purposes.     

Spatial and temporal patterns of dissolved nitrogen and phosphorus in surface waters of a multi-land use basin

Research on relationships between dissolved nutrients and land-use at the watershed scale is a high priority for protecting surface water quality. We measured dissolved nitrogen (DN) and ortho-phosphorus (P) along 130 km of the Calapooia River (Oregon, USA) and 44 of its sub-basins for 3 years to test for associations with land-use. Nutrient concentrations were analyzed for spatial and seasonal patterns and for relationships with land-use and stream discharge. Ortho-P and DN were higher in lower-elevation sub-basins dominated by poorly drained soils and agricultural production compared with higher-elevation sub-basins dominated by well-drained soils and forests. Eight lower basins had at least one sample period with nitrate-N?>?10 mg L^?1. The Calapooia River had lower concentrations of dissolved nutrients compared with lower sub-basins, often by an order of magnitude. Dissolved organic N represented a greater proportion of DN in the upper forested sub-basins. Seasonal nutrient concentrations had strong positive correlations to the percent of a sub-basin that was managed for agriculture in all seasons (p?values?≤?0.019) except summer. Results suggest that agricultural lands are contributing to stream nutrient concentrations. However, poorly drained soils in agricultural areas may also contribute to the strong relationships that we found between dissolved nutrients and agriculture.     

Assessment of land cover changes & water quality changes in the Zayandehroud River Basin between 1997–2008

Water quality of rivers is strongly influenced by landscape characteristics of their watershed, including land use /cover types, and their spatial configuration. This research evaluates the effects of land cover changes on the water quality of the Zayandehroud River, which is the most important river in the center of Iran. The main goal of this study was to quantify the change in rangelands, forests, and bare lands in the Zayandehroud river basin, which suffered intense human interference, in a period of 11 years (1997–2008), and to evaluate how landscape patterns (including the number of patches, edge density, percentage of rangelands, forests, and bare lands) influence on the 14 water quality indices (including BOD5, EC, NO3, P, and TDS) measured in 10 stations along the river. Results showed that from 1997 to 2008, bare lands increased from 5.8 to 20 %, while rangelands decreased from 70 to 55 % in the whole basin. The results indicated that water quality was significantly correlated with both the proportions and configuration of rangeland and bare land areas. The total edge (TE) of rangeland area had positive effects on water quality, especially on BOD5 and EC. Percentage of landscape (PLAND) and largest patch index (LPI) metrics of rangeland had positive effect on decreasing nutrient (NO₃, PO₄). The results showed that water quality was more likely degraded when there was high edge density (ED) of bare lands. Results of this study also revealed that degradation of rangeland lead to the degradation of water quality. Finding of this study highlights the importance of rangeland conservation in water quality management at landscape scale.     

Exploring the Relationship Between Hydrologic Parameters and Nutrient Loads Using Digital Elevation Model and GIS – A Case Study from Sugarcreek Headwaters, Ohio, U.S.A.

Ohio is typical among the Midwestern and Eastern United States with high levels of water pollutants, the main sources being from agriculture. In this study, we used a digital elevation model in conjunction with hydrological indices to determine the role of landscape complexity affecting the spatial and temporal variation in pollutant levels, in one of the most impaired headwater streams in Ohio. More than eighty five percent of the study area is dominated by agriculture. Spatial distribution of slope (S), altitude and wetness index along with other watershed parameters such as flow direction, flow accumulation, stream networks, flow stream orders and erosion index were used within a Geographic Information Systems framework to quantify variation in nitrate and phosphate loads to headwater streams. Stream monitoring data for nutrient loads were used to correlate the observed spatial and temporal patterns with hydrological parameters using multiple linear regressions. Results from the wetness index calculated from a digital elevation model suggested a range of 0.10–16.39, with more than 35% having values less than 4.0. A Revised Universal Soil Loss Equation (RUSLE) predicted soil loss in the range of 0.01–4.0 t/ha/yr. Nitrate nitrogen levels in the study area paralleled precipitation patterns over time, with higher nitrate levels corresponding to high precipitation. Atmospheric deposition through precipitation could explain approximately 35% of total nitrate levels observed in streams. Among the different topographic variables and hydrological indices, results from the step-wise multiple regression suggested the following best predictors, (1) elevation range and upstream flow length for nitrate, (2) flow direction and upstream flow length for ammonia-nitrogen and slope, and (3) elevation range for phosphate levels. Differences in the landscape models observed for nitrate, phosphate and ammonia-nitrogen in the surface waters were attributed partly to differences in the chemical activity and source strengths of the different forms of these nutrients through agricultural management practices. The results identify geomorphologic and landscape characteristics that influence pollutant levels in the study area.     

Nitrogen mineralization in O horizon soils during 27 years of nitrogen enrichment at the Bear Brook Watershed in Maine,USA

Chronic elevated nitrogen (N) deposition has altered the N status of temperate forests, with significant implications for ecosystem function. The Bear Brook Watershed in Maine (BBWM) is a whole paired watershed manipulation experiment established to study the effects of N and sulfur (S) deposition on ecosystem function. N was added bimonthly as (NH₄)₂SO₄ to one watershed from 1989 to 2016, and research at the site has studied the evolution of ecosystem response to the treatment through time. Here, we synthesize results from 27 years of research at the site and describe the temporal trend of N availability and N mineralization at BBWM in response to chronic N deposition. Our findings suggest that there was a delayed response in soil N dynamics, since labile soil N concentrations did not show increases in the treated watershed (West Bear, WB) compared to the reference watershed (East Bear, EB) until after the first 4 years of treatment. Labile N became increasingly available in WB through time, and after 25 years of manipulations, treated soils had 10× more extractable ammonium than EB soils. The WB soils had 200× more extractable nitrate than EB soils, driven by both, high nitrate concentrations in WB and low nitrate concentrations in EB. Nitrification rates increased in WB soils and accounted for ~?50% of net N mineralization, compared to ~?5% in EB soils. The study provides evidence of the decadal evolution in soil function at BBWM and illustrates the importance of long-term data to capture ecosystem response to chronic disturbance.     

Visual techniques for the detection of water quality trends: Double-mass curves and cusum functions

There is a great need for quantitative techniques to assess changes in water quality related to progressive watershed land-use developments, water-related impoundments or to evaluate the impact of recent sanitation programs. In choosing a physically representative variate for the water quality of the run-off, both concentrations and fluxes of pollutants must be taken into account. The importance of the climatic seasonal and hydrological factors associated with unstable event-related contributions of point and non-point pollution sources of the pollutants has lead us to simultaneously study water-discharge and pollutant flux time-series. The mass-discharge time-series are, in practice, far from being ideal for the application of classical trend analysis: they are relatively short and inaccurate: their distribution, orginating from mixed parent populations is very often highly skewed; they show a high level of serial dependence and the seasonal effects represent a large percentage of the variance, concealing possible long-term trends. Faced with the poor structure of these series which prohibits the use of statistical tests, experiments have been carried out with progressive-regressive inertial techniques, which imply the stationarity of water discharges. The double-mass technique was developed originally as a visual technique, to assess the homogeneity of precipitation records and was extended to study variations in sediment transport in modified watersheds. More recently confidence ‘rails’ and slope change detection have rendered its use more quantitative. Based on the same inertial principles, the Cumulative Sum (CUSUM) functions allow simultaneous evaluation of the covariability of the two series. An example involving weekly sampled nitrate concentrations and continuously monitored water discharges is developed.     

High-frequency nutrient monitoring to infer seasonal patterns in catchment source availability, mobilisation and delivery

To explore the value of high-frequency monitoring to characterise and explain riverine nutrient concentration dynamics, total phosphorus (TP), reactive phosphorus (RP), ammonium (NH₄-N) and nitrate (NO₃-N) concentrations were measured hourly over a 2-year period in the Duck River, in north-western Tasmania, Australia, draining a 369-km² mixed land use catchment area. River discharge was observed at the same location and frequency, spanning a wide range of hydrological conditions. Nutrient concentrations changed rapidly and were higher than previously observed. Maximum nutrient concentrations were 2,577 μg L^?1 TP, 1,572 μg L^?1 RP, 972 μg L^?1 NH₄-N and 1,983 μg L^?1 NO₃-N, respectively. Different nutrient response patterns were evident at seasonal, individual event and diurnal time scales—patterns that had gone largely undetected in previous less frequent water quality sampling. Interpretation of these patterns in terms of nutrient source availability, mobilisation and delivery to the stream allowed the development of a conceptual model of catchment nutrient dynamics. Functional stages of nutrient release were identified for the Duck River catchment and were supported by a cluster analysis which confirmed the similarities and differences in nutrient responses caused by the sequence of hydrologic events: (1) a build-up of nutrients during periods with low hydrologic activity, (2) flushing of readily available nutrient sources at the onset of the high flow period, followed by (3) a switch from transport to supply limitation, (4) the accessibility of new nutrient sources with increasing catchment wetness and hydrologic connectivity and (5) high nutrient spikes occurring when new sources become available that are easily mobilised with quickly re-established hydrologic connectivity. Diurnal variations that could be influenced by riverine processes and/or localised point sources were also identified as part of stage (1) and during late recession of some of the winter high flow events. Illustrated by examples from the Duck River study, we demonstrate that the use of high-frequency monitoring to identify and characterise functional stages of catchment nutrient release is a constructive approach for informing and supporting catchment management and future nutrient monitoring strategies.     

Soil disturbance/restoration effects on stream sediment loading in the Tahoe Basin—detection monitoring

Quantifying the relative impacts of soil restoration or disturbance on watershed daily sediment and nutrients loads is essential towards assessing the actual costs/benefits of the land management. Such quantification requires stream monitoring programs capable of detecting changes in land-use or soil functional and erosive area “connectivity” conditions across the watershed. Previously, use of a local-scale, field-data based runoff and erosion model for three Lake Tahoe west-shore watersheds as a detection monitoring “proof of concept” suggested that analyses of midrange average daily flows can reveal sediment load reductions of relatively small watershed fractional areas (～5 %) of restored soil function within a few years of treatment. Developing such an effective stream monitoring program is considered for tributaries on the west shore of the Lake Tahoe Basin using continuous (15-min) stream monitoring information from Ward (2,521 ha), Blackwood (2,886 ha), and the Homewood (260 ha, HMR) Creek watersheds. The continuous total suspended sediment (TSS) and discharge monitoring confirmed the hysteretic TSS concentration—flowrate relationship associated with the daily and seasonal spring snowmelt hydrographs at all three creeks. Using the complete dataset, daily loads estimated from 1-h sampling periods during the day indicated that the optimal sampling hours were in the afternoon during the rising limb of the spring snowmelt hydrograph, an observation likely to apply across the Sierra Nevada and other snowmelt driven watersheds. Measured rising limb sediment loads were used to determine if soils restoration efforts (e.g., dirt road removal, ski run rehabilitation) at the HMR creek watershed reduced sediment loads between 2010 and 2011. A nearly 1.5-fold decrease in sediment yields (kg/ha per m³/s flow) was found suggesting that this focused monitoring approach may be useful towards development of TMDL “crediting” tools. Further monitoring is needed to verify these observations and confirm the value of this approach.