INFLUENCE OF DIFFERENT TEMPORAL SAMPLING STRATEGIES ON ESTIMATING TOTAL PHOSPHORUS AND SUSPENDED SEDIMENT CONCENTRATION AND TRANSPORT IN SMALL STREAMS1

ABSTRACT: Various temporal sampling strategies are used to monitor water quality in small streams. To determine how various strategies influence the estimated water quality, frequently collected water quality data from eight small streams (14 to 110 km²) in Wisconsin were systematically subsampled to simulate typically used strategies. These subsets of data were then used to estimate mean, median, and maximum concentrations, and with continuous daily flows used to estimate annual loads (using the regression method) and volumetrically weighted mean concentrations. For each strategy, accuracy and precision in each summary statistic were evaluated by comparison with concentrations and loads of total phosphorus and suspended sediment estimated from all available data. The most effective sampling strategy depends on the statistic of interest and study duration. For mean and median concentrations, the most frequent fixed period sampling economically feasible is best. For maximum concentrations, any strategy with samples at or prior to peak flow is best. The best sampling strategy to estimate loads depends on the study duration. For one‐year studies, fixed period monthly sampling supplemented with storm chasing was best, even though loads were overestimated by 25 to 50 percent. For two to three‐year load studies and estimating volumetrically weighted mean concentrations, fixed period semimonthly sampling was best.     

STATISTICAL METHODS AND SAMPLING DESIGN FOR ESTIMATING STEP TRENDS IN SURFACE-WATER QUALITY1

ABSTRACT: This paper addresses two components of the problem of estimating the magnitude of step trends in surface water quality. The first is finding a robust estimator appropriate to the data characteristics expected in water-quality time series. The Hodges-Lehmann class of estimators is found to be robust in comparison to other nonparametric and moment-based estimators. A seasonal Hodges-Lehmann estimator is developed and shown to have desirable properties. Second, the effectiveness of various sampling strategies are examined using Monte Carlo simulation coupled with application of this estimator. The simulation is based on a large set of total phosphorus data from the Potomac River. To assure that the simulated records have realistic properties, the data are modeled in a multiplicative fashion incorporating flow, hysteresis, seasonal, and noise components. The results demonstrate the importance of balancing the length of the two sampling periods and balancing the number of data values between the two periods. The inefficiency of sampling at frequencies much in excess of 12 samples per year is demonstrated. Rotational sampling designs are discussed, and efficient designs, at least for this river and constituent, are shown to involve more than one year of active sampling at frequencies of about 12 per year.     

REGRESSION MODELS FOR ESTIMATING HERBICIDE CONCENTRATIONS IN U.S. STREAMS FROM WATERSHED CHARACTERISTICS1

ABSTRACT: Regression models were developed for estimating stream concentrations of the herbicides alachlor, atrazine, cyanazine, metolachior, and trilluralin from use‐intensity data and watershed characteristics. Concentrations were determined from samples collected from 45 streams throughout the United States during 1993 to 1995 as part of the U.S. Geological Survey's National Water‐Quality Assessment (NAWQA). Separate regression models were developed for each of six percentiles (10th, 25th, 50th, 75th, 90th, 95th) of the annual distribution of stream concentrations and for the annual time‐weighted mean concentration. Estimates for the individual percentiles can be combined to provide an estimate of the annual distribution of concentrations for a given stream. Agricultural use of the herbicide in the watershed was a significant predictor in nearly all of the models. Several hydrologic and soil parameters also were useful in explaining the variability in concentrations of herbicides among the streams. Most of the regression models developed for estimation of concentration percentiles and annual mean concentrations accounted for 50 percent to 90 percent of the variability among streams. Predicted concentrations were nearly always within an order of magnitude of the measured concentrations for the model‐development streams, and predicted concentration distributions reasonably matched the actual distributions in most cases. Results from application of the models to streams not included in the model development data set are encouraging, but further validation of the regression approach described in this paper is needed.     

MODEL FOR PREDICTING TRANSPORT OF PESTICIDES AND THEIR METABOLITES IN THE UNSATURATED ZONE1

ABSTRACT: A finite element model based on Galerkin's upstream weighted residual technique was developed to predict the simultaneous convective-dispersion transport and transformations of pesticides and their metabolites in the unsaturated zone. Transformations of the parent compound and its metabolites were assumed to be first-order reactions for oxidation and hydrolysis, while adsorption of the pesticide species (parent compound and metabolites) to the soil components was assumed to be represented by a linear equilibrium (Freundlich type) isotherm. Volatilization and plant root uptake of pesticides in the solution phase were neglected in the analysis. The proposed model was used to simulate the transport and transformation of aldicarb and its metabolites, aldicarb sulfoxide and aldicarb sulfone, in the soil profile. Several examples are used to demonstrate the accuracy, validity, and applicability of the proposed model. Simulated results indicate that the proposed model can potentially be used to estimate the mass flux of water, and pesticide and pesticide metabolite concentrations in the subsurface environment. However, further verification of the model against actual field data is needed to fully demonstrate the model's potential.     

ECONOMICS OF SCREENING FOR PESTICIDES IN GROUND WATER1

ABSTRACT: In the United States, millions of dollars are currently spent to monitor water quality for a whole suite of organic compounds. However, results of several surveys conducted in the past decade indicate that only a few pesticides occur in a small proportion of wells. Screening methods based on historical evidence of contamination patterns and knowledge of the locales will have significant potential to reduce these costs and effectively identify contamination problems. In this paper, the economics of utilizing two screening methods, sequential analysis and sample compositing, in the design of monitoring strategies is captured In the form of mathematical models and illustrated for a state-level monitoring program. When the two methods are adopted, the total analytical cost to conclusively identify contaminated wells in a network of 4,000 wells is shown to range from $12,500 to $1,575,000 depending on the extent of contamination. In contrast, the total analytical cost of a conventional program where all the wells in the network are sampled and tested for a standard suite of pesticides at a cost of $250/sample is one million dollars. Given such wide range in costs, it is prudent to incorporate the screening concepts presented in this paper in the development of cost-effective monitoring programs.     

OCCURRENCE OF PESTICIDES IN GROUND WATER OF THE OZARK PLATEAUS PROVINCE1

ABSTRACT: Pesticides were detected in ground-water samples collected from 20 springs and nine wells in the Ozark Plateaus Province of Arkansas, Kansas, Missouri, and Oklahoma. From April through September 1993, water samples were collected from 50 shallow domestic wells and 50 springs in the Springfield Plateau and Ozark aquifers and analyzed for 47 pesticides and metabolites. Pesticides were detected in 17 water samples from the Springfield Plateau aquifer and 12 water samples from the Ozark aquifer. Fourteen pesticides were detected, with a maximum of four pesticides detected in any one sample. The most commonly detected pesticides were atrazine (14 detections), prometon (11 detections), and tebuthiuron (seven detections). P, P' DDE, a metabolite of DDT, was detected in water samples from three wells and one spring. The remaining pesticides were detected in three or less samples. The occurrence and distribution of pesticides probably are related to the local land use near a sampling site. Pesticide detections were significantly related to aquifer, site type, and discharge of springs.     

REGIONAL PATTERNS OF PESTICIDE CONCENTRATIONS IN SURFACE WATERS OF NEW YORK IN 19971

ABSTRACT: The predominant mixtures of pesticides found in New York surface waters consist of five principal components. First, herbicides commonly used on corn (atrazine, metolachlor, alachlor, cyanazine) and a herbicide degradate (deethylatrazine) were positively correlated to a corn‐herbicide component, and watersheds with the highest corn‐herbicide component scores were those in which large amounts of row crops are grown. Second, two insecticides (diazinon and carbaryl) and one herbicide (prometon) widely used in urban and residential settings were positively correlated to an urban/residential component. Watersheds with the highest urban/residential component scores were those with large amounts of urban and residential land use. A third component was related to two herbicides (EPTC and cyanazine) used on dry beans and corn, the fourth to an herbicide (simazine) and an insecticide (carbaryl) commonly used in orchards and vineyards, and the fifth to an herbicide (DCPA). Results of this study indicate that this approach can be used to: (1) identify common mixtures of pesticides in surface waters, (2) relate these mixtures to land use and pesticide applications, and (3) indicate regions where these mixtures of pesticides are commonly found.     

MASS LOAD ESTIMATION ERRORS UTILIZING GRAB SAMPLING STRATEGIES IN A KARST WATERSHED1

ABSTRACT: Developing a mass load estimation method appropriate for a given stream and constituent is difficult due to inconsistencies in hydrologic and constituent characteristics. The difficulty may be increased in flashy flow conditions such as karst. Many projects undertaken are constrained by budget and manpower and do not have the luxury of sophisticated sampling strategies. The objectives of this study were to: (1) examine two grab sampling strategies with varying sampling intervals and determine the error in mass load estimates, and (2) determine the error that can be expected when a grab sample is collected at a time of day when the diurnal variation is most divergent from the daily mean. Results show grab sampling with continuous flow to be a viable data collection method for estimating mass load in the study watershed. Comparing weekly, biweekly, and monthly grab sampling, monthly sampling produces the best results with this method. However, the time of day the sample is collected is important. Failure to account for diurnal variability when collecting a grab sample may produce unacceptable error in mass load estimates. The best time to collect a sample is when the diurnal cycle is nearest the daily mean.     

DISTRIBUTION OF NITRATE AND ORTHOPHOSPHATE IN SELECTED STREAMS IN CENTRAL NEBRASKA1

ABSTRACT: The Central Nebraska Basins is one of 60 study units in the National Water-Quality Assessment Program of the U.S. Geological Survey. The study unit includes the Platte River and two major tributaries, the Loup and Elkhorn Rivers. Agriculture is the predominant land use in the study unit, with only eight urbanized communities exceeding a population of 10,000. Water samples were collected from selected streams in the study unit during 1993–1995. The data were used to assess the distribution of nitrogen compounds and phosphorus in the streams and to relate the concentrations of these constituents to environmental settings. This article focuses on dissolved nitrate and orthophosphate. Dissolved nitrate concentrations were highest (90th percentiles were less than 7.0 milligrams per liter as nitrogen) in areas with extensive cropland and pasture, where chemical fertilizers are intensively applied. Synoptic measurements conducted in March and August 1994 indicate that relatively little residual fertilizer, as nitrate, applied during a single crop-growing season enters streams. Dissolved nitrate concentrations showed a seasonal pattern, being highest during winter months and lowest during the late spring and summer. Dissolved orthophosphate concentrations tended to be low across the study unit, 90 percent of all analyses did not exceed 1.7 milligrams per liter as phosphorus.     

COMPARISON OF METHODS FOR ESTIMATING FLOOD MAGNITUDES ON SMALL STREAMS IN GEORGIA1

ABSTRACT: The U.S. Geological Survey has collected flood data for small, natural streams at many sites throughout Georgia during the past 20 years. Flood-frequency relations were developed for these data using four methods: (1) observed (log-Pearson Type HI analysis) data, (2) rainfall-runoff model, (3) regional regression equations, and (4) map-model combination. The results of the latter three methods were compared to the analyses of the observed data in order to quantify the differences in the methods and determine if the differences are statistically significant. Comparison of regression-estimates with observed discharges for sites having 20 years (1966 to 1985) and 10 years (1976 to 1985) of record at different sites of annual peak record indicate that the regression-estimates are not significantly different from the observed data. Comparison of rainfall-runoff-model simulated estimates with observed discharges for sites having 10 years and 20 years of annual peak record indicated that the model-simulated estimates are significantly and not significantly different, respectively. The biasedness probably is due to a “loss of variance” in the averaging procedures used within the model and the short length of record as indicated in the 10 and 20 years of record. The comparison of map-model simulated estimates with observed discharges for sites having 20 years of annual-peak runoff indicate that the simulated estimates are not significantly different. Comparison of “improved” map-model simulated estimates with observed discharges for sites having 20 years of annual-peak runoff data indicate that the simulated estimates are different. The average adjustment factor suggested by Lichty and Liscum to calculate the “improved” map-model overestimates in Georgia by an average of 20 percent for three recurrence intervals analyzed.     

ATRAZINE AND METOLACHLOR OCCURRENCE IN SHALLOW GROUND WATER OF THE UNITED STATES, 1993 TO 1995: RELATIONS TO EXPLANATORY FACTORS1

ABSTRACT: Since 1991, the U.S. Geological Survey has been conducting the National Water Quality Assessment (NAWQA) Program to determine the quality of the Nation's water resources. In an effort to obtain a better understanding of why pesticides are found in shallow ground water on a national scale, a set of factors likely to affect the fate and transport of two herbicides in the subsurface were examined. Atrazine and metolachlor were selected for this discussion because they were among the most frequently detected pesticides in ground water during the first phase of the NAWQA Program (1993 to 1995), and each was the most frequently detected compound in its chemical class (triazines and acetanilides, respectively). The factors that most strongly correlated with the frequencies of atrazine detection in shallow ground‐water networks were those that provided either: (1) an indication of the potential susceptibility of ground water to atrazine contamination, or (2) an indication of relative ground‐water age. The factors most closely related to the frequencies of metolachlor detection in ground water, however, were those that estimated or indicated the intensity of the agricultural use of metolachlor. This difference is probably the result of detailed use estimates for these compounds being available only for agricultural settings. While atrazine use is relatively extensive in nonagricultural settings, in addition to its widespread agricultural use, metolachlor is used almost exclusively for agricultural purposes. As a result, estimates of agricultural applications provide a less reliable indication of total chemical use for atrazine than for metolachlor. A multivariate analysis demonstrated that the factors of interest explained about 50 percent of the variance in atrazine and metolachlor detection frequencies among the NAWQA land‐use studies examined. The inclusion of other factors related to pesticide fate and transport in ground water, or improvements in the quality and accuracy of the data employed for the factors examined, may help explain more of the remaining variance in the frequencies of atrazine and metolachlor detection.     

MODELING CONCENTRATION VARIATIONS IN HIGH-CAPACITY WELLS: IMPLICATIONS FOR GROUNDWATER SAMPLING1

ABSTRACT: High-capacity wells are used as a convenient and economical means of sampling groundwater quality. Although the inherent limitations of using these wells are generally recognized, little has been done to investigate how these wells actually sample groundwater. A semi-analytical particle tracking model is used to illustrate the influence of variable vertical contaminant distributions and aquifer heterogeneity on the composition of water samples from these wells during short pumping periods. The hypothetical pumping well used in the simulations is located in an unconfined, alluvial aquifer with a shallow water table and concentration gradients of nitrate-nitrogen contamination. This is a typical setting for many irrigated areas in the United States. The main conclusions are: (1) high-capacity wells underestimate the average amount of contamination within an aquifer; (2) shapes of concentration-time curves for high-capacity wells appear to be governed by the distribution of the contaminant and travel times to the well; (3) variables such as well construction, pumping rate, and hydrogeologic properties contribute to the magnitude of the concentration-time curves at individual high-capacity wells; and (4) a sampling strategy using concentration-time curves based on the behavioral characteristics of the well rather than individual samples will provide a much better framework for interpreting spatial contaminant distributions.     

EVALUATION OF SELECTED PESTICIDES IN NORTH CAROLINA SURFACE WATER SUPPLIES: INTAKE STUDY1

ABSTRACT: Studies were conducted to analyze the presence of 11 selected pesticides in 12 surface water supply intakes in the Piedmont and coastal plain regions of North Carolina. Samples were assayed using enzyme linked immunosorbent assays (ELISAs). Samples with pesticide detection of 1 μg/L or greater were extracted and confirmed using gas chromatography/mass spectrometry (GC/MS). Detection limits of the immunosorbent assays for pesticide residues were generally an order of magnitude higher than GC/MS. Atrazine was detected in approximately 45 percent of the samples, and on two occasions was at or above the lifetime Maximum Contaminant Level of 3.0 μg/L set by the Environmental Protection Agency for an annual average in finished drinking water. Metolachlor was detected in 58 percent of the samples. Of the remaining nine pesticides, including carbaryl, aldicarb, 2,4‐D, chiorpyrifos, acetochlor, methomyl, carbofuran, alachlor, and chlorothalonil, only aldicarb, 2,4‐D, and chlorpyrifos were detected in less than 9 percent of the samples for each pesticide.     

PROBABILISTIC METHODS IN STREAM QUALITY MANAGEMENT1

ABSTRACT. Recent advances in water quality modelling have pointed out the need for stochastic models to simulate the probabilistic nature of water quality. However, often all that is needed is an estimate of the uncertainty in predicting water quality variables. First order analysis is a simple method of providing an estimate in the uncertainty in a deterministic model due to uncertain parameters. The method is applied to the simplified Streeter-Phelps equations for DO and BOD; a more complete Monte Carlo simulation is used to check the accuracy of the results. The first order analysis is found to give accurate estimates of means and variances of DO and BOD up to travel times exceeding the critical time. Uncertainty in travel time and the BOD decay constant are found to be most important for small travel times; uncertainty in the reaeration coefficient dominates near the critical time. Uncertainty in temperature was found to be a negligible source of uncertainty in DO for all travel times.     

TRANSPORT CHARACTERISTICS OF PHOSPHORUS IN CHANNELIZED AND MEANDERING STREAMS1

ABSTRACT: Comparisons were made between rates of movement of orthophosphate in a canal and a meandering stream. The meander system had greater algal and macrophyte phosphate uptake rates, and lower plankton and sediment release rates compared to the canal. Chemical precipitation and direct rainfall influences on orthophosphate movement were insignificant relative to other terms. The major source of phosphorus to both systems was from upland runoff. The impact of this source was greater on the meandering system due to the smaller channel volume. When secondary effects of meandering were considered such as marsh inundation, the net orthophosphate movement within the meandering channel was less than that for the canal; due to the lower concentrations of phosphorus in marsh effluent waters. Field experiments were conducted to compare the longitudinal dispersion coefficient between a canal and meandering river system; the meandering stream had a dispersion coefficient over 17 times that measured for the canal. Rates of orthophosphate movement were combined into a single mass transport equation, and a numerical solution was obtained. Internal river and canal channel processes were overshadowed by external point source loadings.     

INFLUENCE OF WELL WATER QUALITY VARIABILITY ON SAMPLING DECISIONS AND MONITORING1

ABSTRACT: Local governmental agencies responsible for decisions in ground water quality management need not only data on ground water quality but they also must understand the relationship of accuracies and risks associated with this data as related to the number of wells to sample. In this report we address this problem by using the philosophical doctrines of probabilism and relativism with simple statistical procedures. This requires a reasonable estimate of the population variance in a quality parameter for a given management-unit area, and requires that the decisionmaker formulate constraints with an acceptable standard error of the sample mean and be willing to accept some level of probability of being Wrong. This technique is illustrated using a 21-year data base of well water chemical data in a 653 km² ground water quality study area in the San Joaquin Valley of California.     

FREQUENCY-DURATION ANALYSIS OF DISSOLVED-OXYGEN CONCENTRATIONS IN TWO SOUTHWESTERN WISCONSIN STREAMS1

ABSTRACT: Historically, dissolved-oxygen (DO) data have been collected in the same manner as other water-quality constituents, typically at infrequent intervals as a grab sample or an instantaneous meter reading. Recent years have seen an increase in continuous water-quality monitoring with electronic dataloggers. This new technique requires new approaches in the statistical analysis of the continuous record. This paper presents an application of frequency-duration analysis to the continuous DO records of a cold and a warm water stream in rural southwestern Wisconsin. This method offers a quick, concise way to summarize large time-series data bases in an easily interpretable manner. Even though the two streams had similar mean DO concentrations, frequency-duration analyses showed distinct differences in their DO-concentration regime. This type of analysis also may be useful in relating DO concentrations to biological effects and in predicting low DO occurrences.     

FACTORS AFFECTING PESTICIDE OCCURRENCE AND TRANSPORT IN A LARGE MIDWESTERN RIVER BASIN1

ABSTRACT: Several factors affect the occurrence and transport of pesticides in surface waters of the 29,400 km² White River Basin in Indiana. A relationship was found between pesticide use and the average annual concentration of that pesticide in the White River, although this relationship varies for different classes of pesticides. About one percent of the mass applied of each of the commonly used agricultural herbicides was transported from the basin via the White River. Peak pesticide concentrations were typically highest in late spring or early summer and were associated with periods of runoff following application. Concentrations of diazinon were higher in an urban basin than in two agricultural basins, corresponding to the common use of this insecticide on lawns and gardens in urban areas. Concentrations of atrazine, a corn herbicide widely used in the White River Basin, were higher in an agricultural basin with permeable, well‐drained soils, than in an agricultural basin with less permeable, more poorly drained soils. Although use of butylate and cyanazine was comparable in the White River Basin between 1992 and 1994, concentrations in the White River of butylate, which is incorporated into soil, were substantially less than for cyanazine, which is typically applied to the soil surface.     

NITROGEN AND PHOSPHORUS CONCENTRATIONS IN FOREST STREAMS OF THE UNITED STATES1

ABSTRACT: Seventy to eighty percent of the water flowing in rivers in the United States originates as precipitation in forests. This project developed a synoptic picture of the patterns in water chemistry for over 300 streams in small, forested watersheds across the United States. Nitrate (NO₃^?) concentrations averaged 0.31 mg N/L, with some streams averaging ten times this level. Nitrate concentrations tended to be higher in the northeastern United States in watersheds dominated by hardwood forests (especially hardwoods other than oaks) and in recently harvested watersheds. Concentrations of dissolved organic N (mean 0.32 mg N/L) were similar to those of NO₃～, whereas ammonium (NH₄⁺) concentrations were much lower (mean 0.05 mg N/L). Nitrate dominated the N loads of streams draining hardwood forests, whereas dissolved organic N dominated the streams in coniferous forests. Concentrations of inorganic phosphate were typically much lower (mean 12 mg P/L) than dissolved organic phosphate (mean 84 mg P/L). The frequencies of chemical concentrations in streams in small, forested watersheds showed more streams with higher NO₃^? concentrations than the streams used in national monitoring programs of larger, mostly forested watersheds. At a local scale, no trend in nitrate concentration with stream order or basin size was consistent across studies.