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R. J. Gilliom

Publications and source records attributed to R. J. Gilliom.

14 recordsLinked to original sources

Modeling variability and trends in pesticide concentrations in streams

A parametric regression model was developed for assessing the variability and long-term trends in pesticide concentrations in streams. The dependent variable is the logarithm of pesticide concentration and the explanatory variables are a seasonal wave, which represents the seasonal variability of concentration in response to seasonal application rates; a streamflow anomaly, which is the deviation of concurrent daily streamflow from average conditions for the previous 30 days; and a trend, which represents long-term (inter-annual) changes in concentration. Application of the model to selected herbicides and insecticides in four diverse streams indicated the model is robust with respect to pesticide type, stream location, and the degree of censoring (proportion of nondetections). An automatic model fitting and selection procedure for the seasonal wave and trend components was found to perform well for the datasets analyzed. Artificial censoring scenarios were used in a Monte Carlo simulation analysis to show that the fitted trends were unbiased and the approximate p-values were accurate for as few as 10 uncensored concentrations during a three-year period, assuming a sampling frequency of 15 samples per year. Trend estimates for the full model were compared with a model without the streamflow anomaly and a model in which the seasonality was modeled using standard trigonometric functions, rather than seasonal application rates. Exclusion of the streamflow anomaly resulted in substantial increases in the mean-squared error and decreases in power for detecting trends. Incorrectly modeling the seasonal structure of the concentration data resulted in substantial estimation bias and moderate increases in mean-squared error and decreases in power. ?? 2008 American Water Resources Association.

Journal of the American Water Resources Associatio

Regression models for estimating herbicide concentrations in U.S. streams from watershed characteristics

Regression models were developed for estimating stream concentrations of the herbicides alachlor, atrazine, cyanazine, metolachlor, and trifluralin 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.

Journal of the American Water Resources Associatio

Atrazine and metolachlor occurrence in shallow ground water of the United States, 1993 to 1995: Relations to explanatory factors

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.

Journal of the American Water Resources Associatio

Pesticides in the hydrologic system - What do we know and what's next?

Even though the occurrence and behaviour of pesticides in the environment have been studied for decades, water-quality managers and the public still demand more complete and consistent information, and there are many unanswered questions for environmental scientists. In many respects, the greatest potential for unintended adverse effects of pesticides is through contamination of the hydrologic system, which supports aquatic life and related food chains and is used for recreation, drinking water, and many other purposes. The movement of water is one of the primary mechanisms by which pesticides are transported from targeted application areas to other parts of the environment; thus, there is potential for movement into and through all components of the hydrologic system. Extensive reviews of existing information on pesticides in the hydrologic system, including the atmosphere (Majewski and Capel, 1995), ground water (Barbash and Resek, 1996), surface water (Larson et al., 1997), and fluvial sediments and aquatic biota (Nowell et al., 1999), uncovered volumes of useful information, but also noted critical information gaps. For example: (a) relatively few pesticides have been thoroughly studied, particularly transformation products; (b) most data have been collected for small-scale site and field studies in agricultural areas; (c) urban areas have received little attention for monitoring or research; (d) the geographic and temporal distributions of data collection have been highly uneven; and (e) comparing and synthesizing results from most studies is difficult because of inconsistent approaches to data collection and chemical analysis.

Hydrological Processes

Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry

Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deuterated 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (7lt; 0.05 μg/L) to 3.77μg/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

International Journal of Environmental Analytical

Streamflow, dissolved solids, suspended sediment, and trace elements, San Joaquin River, California, June 1985-September 1988

The 1985-88 study period included hydrologic extremes throughout most of central California. Except for an 11-month period during and after the 1986 flood, San Joaquin River streamflows during 1985-88 were generally less than median for 1975-88. The Merced Tuolumne, and Stanislaus Rivers together comprised 56 to 69 percent of the annual San Joaquin River flow, Salt and Mud Sloughs together comprised 6 to 19 percent, the upper San Joaquin River comprised 2 to 25 percent, and unmeasured sources from agricultural discharges and ground water accounted for 13 to 20 percent. Salt and Mud Sloughs and the unmeasured sources contribute most of the dissolved-solids load. The Merced, Tuolumne, and Stanislaus Rivers greatly dilute dissolved-solids concentrations. Suspended-sediment concentration peaked sharply at more than 600 milligrams per liter during the flood of February 1986. Concentrations and loads varied seasonally during low-flow conditions, with concentrations highest during the early summer irrigation season. Trace elements present primarily in dissolved phases are arsenic, boron, lithium, molybdenum, and selenium. Boron concentrations exceeded the irrigation water-quality criterion of 750 micrograms per liter more than 75 percent of the time in Salt and Mud Sloughs and more than 50 percent of the time at three sites on the San Joaquin River. Selenium concentrations exceeded the aquatic-life criterion of 5 micrograms per liter more than 75 percent of the time in Salt Slough and more than 50 percent of the time in Mud Slough and in the San Joaquin River from Salt Slough to the Merced River confluence. Concentrations of dissolved solids, boron, and selenium usually are highest during late winter to early spring, lower in early summer, higher again in mid-to-late summer, and the lowest in autumn, and generally correspond to seasonal inflows of subsurface tile-drain water to Salt and Mud Sloughs. Trace elements present primarily in particulate phases are aluminum, chromium, copper, iron, manganese, nickel, and zinc, none of which cause significant water-quality problems in the river.

California

Trace elements in bed sediments of the San Joaquin River and its tributary streams, California, 1985

Bed sediments were sampled at 24 sites on the San Joaquin River, California and its tributaries in October 1985 to assess the distribution of trace elements and factors affecting their concentrations. The proportion of less than 62-micrometer sediment was significantly (alpha=0.05) correlated with organic-carbon concentrations. Bed sediments from tributaries originating in the Sierra Nevada were much coarser than sediments in streams draining the Coast Range and western valley. Selenium concentrations in water have been measured. Interrelations among trace elements were examined using principal component analysis. 57% of the variance was accounted for in the first two principal components, which together show a distinct separation between sites dominated by Coast Range sediments and sites dominated by Sierra Nevada sediments. The third and fourth components accounted for 21% of the variance and distinguished the mixed-source sediments of the intermittent upper San Joaquin River from other parts of the river system. Generally, elements in bed sediments of the San Joaquin River and its tributaries were similar in concentration to elements in San Joaquin Valley soils, and concentrations were far below hazardous waste criteria. Concentrations were lower than in sediments from some polluted urban rivers and water more comparable to other rural agricultural rivers. (USGS)

Water-Resources Investigations Report

Sources and concentrations of dissolved solids and selenium in the San Joaquin River and its tributaries, California, October 1985 to March 1987

Sources and concentrations of dissolved solids and selenium in the San Joaquin River and its tributaries, California, were assessed by a mass-balance approach to determine the effects of tile-drain water and irrigation-return flows on the river. The study included low-flow periods from October 1985 to mid-February 1986 and mid-May 1986 through March 1987, and a high-flow period from mid-February to mid-May 1985. During the combined low-flow period, the dissolved-solids load from eastside tributaries and the upper San Joaquin River accounted for only 18% of the total load at Vernalis, located farthest downstream, even though they accounted for 71% of the streamflow. Salt and Mud Sloughs contributed 40% of the dissolved-solids load but only 9% of streamflow. Unmeasured sources of dissolved solids contributed about 42% of the total load during low flow. In contrast, Salt and Mud Sloughs, which receive most of the tile-drain water that enters the river, contributed almost 80% of the total selenium load to the river, and loading of selenium concentrations were highest in Salt and Mud Sloughs and decreased downstream in the San Joaquin River with dilution from eastside tributaries. A State standard for dissolved solids of 500 mg/L was exceeded 11% of the time in the San Joaquin River at Vernalis. The U.S. Environmental Protection Agency 's 4-day average aquatic-life criterion of 5 micrograms/L of selenium was exceeded in more than 60% of the samples from the sloughs and in about 20% of the samples from the San Joaquin River, just downstream of the Merced River. (USGS)

Water-Resources Investigations Report

Organochlorine pesticide residues in bed sediments of the San Joaquin River and its tributary streams, California

The distribution and concentrations of organochlorine pesticide residues in bed sediments were assessed from samples collected at 24 sites in the San Joaquin River and its tributaries in the San Joaquin Valley, California. Sampling was designed to collect the finest grained bed sediments present in the vicinity of each site. One or more of the 14 pesticides analyzed were detected at every site. Pesticides detected at one or more sites were chlordane, DDD, DDE, DDT, dieldrin, endosulfan, mirex, and toxaphene. Pesticides not detected were endrin, heptachlor, heptachlor epoxide, lindane, methoxychlor, and perthane. The most frequently detected pesticides were DDD (83% of sites), DDE (all sites), DDT (33% of sites), and dieldrin (58% of sites). Maximum concentrations of these pesticides, which were correlated with each other and with the amount of organic carbon in the sample, were DDD, 260 micrograms/kg; DDE, 430 micrograms/kg; DDT, 420 micrograms/kg; and dieldrin, 8.9 micrograms/kg. Six small tributary streams that drain agricultural areas west of the San Joaquin River had the highest concentrations. Water concentrations and loads were estimated for each pesticide from its concentration in bed sediments, the concentration of suspended sediment, and streamflow. Estimated loadings of DDD, DDE, DDT, and dieldrin from tributaries to the San Joaquin River indicate that most of the loading to the river at the time of the study was probably from the westside tributaries. Estimated water concentrations exceeded the aquatic life criterion for the sum of DDD, DDE, and DDt of 0.001 microgram/L at nine of the 24 sites sampled. Five of the nine sites are westside tributaries and one is the San Joaquin River near Vernalis. (Author 's abstract)

California

Selected water-quality data for the San Joaquin River and its tributaries, California, June to September 1985

Streamflow, specific conductance, and concentrations of dissolved solids, boron, molybdenum, and selenium were measured at 11 sites on the San Joaquin River and its tributaries approximately twice per month during June to September 1985. Streamflows were lowest in the San Joaquin River near Stevinson (median 43 cu ft sq /sec) and in Mud Slough (median 74.7 cu ft sq). The flow of the San Joaquin River increased downstream to Vernalis (median 2,460 cu ft sq); most flows are from the Merced (median 221.5 cu ft sq), Tuolumne (median 201 cu ft sq), and Stanislaus (median 1,390 cu ft sq) Rivers, which enter the San Joaquin River from the east. The Stanislaus River had the lowest median concentrations of dissolved solids (59 milligrams per liter), dissolved boron (10 micrograms per liter), and dissolved molybdenum (less than 1 microgram per liter). Dissolved selenium was lowest in the Stanislaus, Tuolumne, and Merced Rivers, and the San Joaquin River near Stevinson, all of which had concentrations that were not detectable at the level of 1 microgram per liter, except for one detection of dissolved selenium of 1 microgram per liter in the Tuolumne River. Mud Slough had the highest median concentrations of dissolved solids (1,425 milligrams per liter), dissolved boron (2,850 micrograms per liter), and dissolved selenium (21 micrograms per liter). The highest dissolved molybdenum concentrations were in Mud Slough (8 micrograms per liter) and the San Joaquin River at Freemont Ford (8 micrograms per liter). (USGS)

Open-File Report