Richard A. Smith

Some of the characteristics that complicate the analysis of water quality time series are non‐normal distributions, seasonality, flow relatedness, missing values, values below the limit of detection, and serial correlation. Presented here are techniques that are suitable in the face of the complications listed above for the exploratory analysis of monthly water quality data for monotonie trends. The first procedure described is a nonparametric test for trend applicable to data sets with seasonality, missing values, or values reported as ‘less than’: the seasonal Kendall test. Under realistic stochastic processes (exhibiting seasonality, skewness, and serial correlation), it is robust in comparison to parametric alternatives, although neither the seasonal Kendall test nor the alternatives can be considered an exact test in the presence of serial correlation. The second procedure, the seasonal Kendall slope estimator, is an estimator of trend magnitude. It is an unbiased estimator of the slope of a linear trend and has considerably higher precision than a regression estimator where data are highly skewed but somewhat lower precision where the data are normal. The third procedure provides a means for testing for change over time in the relationship between constituent concentration and flow, thus avoiding the problem of identifying trends in water quality that are artifacts of the particular sequence of discharges observed (e.g., drought effects). In this method a flow‐adjusted concentration is defined as the residual (actual minus conditional expectation) based on a regression of concentration on some function of discharge. These flow‐adjusted concentrations, which may also be seasonal and non‐normal, can then be tested for trend by using the seasonal Kendall test.

Seasonal hypoxia in the northern Gulf of Mexico has been linked to increased nitrogen fluxes from the Mississippi and Atchafalaya River Basins, though recent evidence shows that phosphorus also influences productivity in the Gulf. We developed a spatially explicit and structurally detailed SPARROW water-quality model that reveals important differences in the sources and transport processes that control nitrogen (N) and phosphorus (P) delivery to the Gulf. Our model simulations indicate that agricultural sources in the watersheds contribute more than 70% of the delivered N and P. However, corn and soybean cultivation is the largest contributor of N (52%), followed by atmospheric deposition sources (16%); whereas P originates primarily from animal manure on pasture and rangelands (37%), followed by corn and soybeans (25%), other crops (18%), and urban sources (12%). The fraction of in-stream P and N load delivered to the Gulf increases with stream size, but reservoir trapping of P causes large local- and regional-scale differences in delivery. Our results indicate the diversity of management approaches required to achieve efficient control of nutrient loads to the Gulf. These include recognition of important differences in the agricultural sources of N and P, the role of atmospheric N, attention to P sources downstream from reservoirs, and better control of both N and P in close proximity to large rivers.

We describe a method for using spatially referenced regressions of contaminant transport on watershed attributes (SPARROW) in regional water‐quality assessment. The method is designed to reduce the problems of data interpretation caused by sparse sampling, network bias, and basin heterogeneity. The regression equation relates measured transport rates in streams to spatially referenced descriptors of pollution sources and land‐surface and stream‐channel characteristics. Regression models of total phosphorus (TP) and total nitrogen (TN) transport are constructed for a region defined as the nontidal conterminous United States. Observed TN and TP transport rates are derived from water‐quality records for 414 stations in the National Stream Quality Accounting Network. Nutrient sources identified in the equations include point sources, applied fertilizer, livestock waste, nonagricultural land, and atmospheric deposition (TN only). Surface characteristics found to be significant predictors of land‐water delivery include soil permeability, stream density, and temperature (TN only). Estimated instream decay coefficients for the two contaminants decrease monotonically with increasing stream size. TP transport is found to be significantly reduced by reservoir retention. Spatial referencing of basin attributes in relation to the stream channel network greatly increases their statistical significance and model accuracy. The method is used to estimate the proportion of watersheds in the conterminous United States (i.e., hydrologic cataloging units) with outflow TP concentrations less than the criterion of 0.1 mg/L, and to classify cataloging units according to local TN yield (kg/km 2 /yr).

Knowledge of headwater influences on the water-quality and flow conditions of downstream waters is essential to water-resource management at all governmental levels; this includes recent court decisions on the jurisdiction of the Federal Clean Water Act (CWA) over upland areas that contribute to larger downstream water bodies. We review current watershed research and use a water-quality model to investigate headwater influences on downstream receiving waters. Our evaluations demonstrate the intrinsic connections of headwaters to landscape processes and downstream waters through their influence on the supply, transport, and fate of water and solutes in watersheds. Hydrological processes in headwater catchments control the recharge of subsurface water stores, flow paths, and residence times of water throughout landscapes. The dynamic coupling of hydrological and biogeochemical processes in upland streams further controls the chemical form, timing, and longitudinal distances of solute transport to downstream waters. We apply the spatially explicit, mass-balance watershed model SPARROW to consider transport and transformations of water and nutrients throughout stream networks in the northeastern United States. We simulate fluxes of nitrogen, a primary nutrient that is a water-quality concern for acidification of streams and lakes and eutrophication of coastal waters, and refine the model structure to include literature observations of nitrogen removal in streams and lakes. We quantify nitrogen transport from headwaters to downstream navigable waters, where headwaters are defined within the model as first-order, perennial streams that include flow and nitrogen contributions from smaller, intermittent and ephemeral streams. We find that first-order headwaters contribute approximately 70% of the mean-annual water volume and 65% of the nitrogen flux in second-order streams. Their contributions to mean water volume and nitrogen flux decline only marginally to about 55% and 40% in fourth- and higher-order rivers that include navigable waters and their tributaries. These results underscore the profound influence that headwater areas have on shaping downstream water quantity and water quality. The results have relevance to water-resource management and regulatory decisions and potentially broaden understanding of the spatial extent of Federal CWA jurisdiction in U.S. waters.

One result of increased scientific and public interest in water quality over the past few decades has been the gradual accumulation of reliable long‐term water quality data records and an interest in examining these data for long‐term trends. This paper summarizes and examines some of the major issues and choices involved in detecting and estimating the magnitude of temporal trends in measures of stream water quality. The first issue is the type of trend hypothesis to examine: step trends versus monotonic trend. The second relates to the general category of statistical methods to employ: parametric versus nonparametric. The third issue relates to the kind of data to analyze: concentration data versus flux data. The fourth relates to issues of data manipulation to achieve the best results from the trend analysis. These issues include the use of mathematical transformations of the data and the removal of natural sources of variability in water quality due to seasonal and stream discharge variations. The final issue relates to the choice of a trend technique for the analysis of data records with censored or “less than” values. The authors' experiences during the past decade with the development of several trend detection techniques and application of these techniques to a large number of water quality records provide insight into the issues related to a choice of a statistical test for trend in water quality.