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Joseph L. Domagalski

Publications and source records attributed to Joseph L. Domagalski.

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Occurrence and distribution of dissolved pesticides in the San Joaquin River basin, California

The effects of pesticide application, hydrology, and chemical and physical properties on the occurrence of pesticides in surface water in the San Joaquin River Basin, California, were examined. The study of pesticide occurrence in the highly agricultural San Joaquin?Tulare Basins is part of the National Water-Quality Assessment Program of the U.S. Geological Survey. One hundred forty-three water samples were collected throughout 1993 from sites on the San Joaquin River and three of its tributaries: Orestimba Creek, Salt Slough, and the Merced River. Of the 83 pesticides selected for analysis in this study, 49 different compounds were detected in samples from the four sites and ranged in concentration from less than the detection limit to 20 micrograms per liter. All but one sample contained at least one pesticide, and more than 50 percent of the samples contained seven or more pesticides. Six compounds were detected in more than 50 percent of the samples: four herbicides (dacthal, EPTC, metolachlor, and simazine) and two insecticides (chlorpyrifos and diazinon). None of the measured concentrations exceeded U.S. Environmental Protection Agency drinking water criteria, and many of the measured concentrations were very low. The concentrations of seven pesticides exceeded criteria for the protection of freshwater aquatic life: azinphos-methyl, carbaryl, chlorpyrifos, diazinon, diuron, malathion, and trifluralin. Overall, some criteria for protection of aquatic life were exceeded in a total of 97 samples. Factors affecting the spatial patterns of occurrence of the pesticides in the different subbasins included the pattern of application and hydrology. Seventy percent of pesticides with known application were detected. Overall, 40 different pesticides were detected in Orestimba Creek, 33 in Salt Slough, and 26 in the Merced River. Samples from the Merced River had a relatively low number of detections, despite the high number (35) of pesticides applied, owing to the generally low percentage of irrigation return flow and contribution of pesticide-free streamflow from reservoir releases. Irrigation return flows in the Orestimba Creek and Salt Slough subbasins generally contained more pesticides at higher concentrations. In addition, the distribution of seven pesticides (alachlor, cyanazine, dacthal, fonofos, molinate, napropamide, and trifluralin) in the subbasins showed a direct spatial correspondence between occurrence and application rates. Temporal patterns of occurrence also were affected by patterns of application and hydrology. Most pesticides showed a clear correspondence between the times of their application and their occurrence. Fourteen pesticides had maximum application and concentrations during the summer irrigation season. However, several pesticides exhibited maximum concentrations during winter storms, although maximum application occurred at some other time of year?the result of differences in precipitation and streamflow between seasons. In some subbasins, precipitation runoff was more effective than irrigation return flows at transporting pesticides from the site of application to the stream. Also, during autumn, when there was neither precipitation nor irrigation, the transport of pesticides to streams was limited. The effect of chemical and physical properties on the occurrence of pesticides was examined for the San Joaquin River Basin as a whole. The runoff potential of each pesticide, calculated from the solubility, water-soil organic carbon partition coefficient Koc, and hydrolysis half-life, is generally consistent with the frequency of detection of pesticides in surface water in relation to the amount applied. These three properties each were generally, and weakly, correlated with the relative load of the pesticides in surface water. Pesticide occurrence and concentrations at the mouth of the basin (the San Joaquin River near Vernalis) was compared with pesticide occurrence and concentration in the three

Water-Resources Investigations Report

Results of a prototype surface water network design for pesticides developed for the San Joaquin River Basin, California

A nested surface water monitoring network was designed and tested to measure variability in pesticide concentrations in the San Joaquin River and selected tributaries during the irrigation season. The network design an d sampling frequency necessary for determining the variability and distribution in pesticide concentrations were tested in a prototype study. The San Joaquin River Basin, California, was sampled from April to August 1992, a period during the irrigation season where there was no rainfall. Orestimba Creek, which drains a part of the western San Joaquin Valley, was sampled three times per week for 6 weeks, followed by a once per week sampling for 6 weeks, and the three times per week sampling for 6 weeks. A site on the San Joaquin River near the mouth of the basin, and an irrigation drain of the eastern San Joaquin Valley, were sampled weekly during the entire sampling period. Pesticides were most often detected in samples collected from Orestimba Creek. This suggests that the western valley was the principal source of pesticides to the San Joaquin River during the irrigation season. Irrigation drainage water was the source of pesticides to Orestimba Creek. Pesticide concentrations of Orestimba Creek showed greater temporal variability when sampled three times per week than when sampled once a week, due to variations in field management and irrigation. The implication for the San Joaquin River basin (an irrigation-dominated agricultural setting) is that frequent sampling of tributary sites is necessary to describe the variability in pesticides transported to the San Joaquin River.

Journal of Hydrology

Pesticides in surface and ground water of the San Joaquin-Tulare basins, California: Analysis of available data, 1966 Through 1992

Available pesticide data (1966-92) for surface and ground water were analyzed for the San Joaquin-Tulare Basins, California, one of 60 large hydrologic systems being studied as part of the National Water-Quality Assessment Program of the U.S. Geological Survey. Most of the pesticide data were for the San Joaquin Valley, one of the most intensively farmed and irrigated areas of the United States. Data were obtained from the Storage and Retrieval data base of the U.S. Environmental Protection Agency, the water-quality data base of the U.S. Geological Survey, and from data files of State agencies. Pesticides detected in surface water include organochlorine pesticides, organophosphate pesticides, carbamate pesticides, and triazine herbicides. Pesticides detected in ground water include triazine and other organonitrogen herbicides and soil fumi gants. Surface-water data indicate seasonal patterns for the detection of organophosphate and carbamate pesticides, which are attributed to their use on almond orchards and alfafa fields. Organochlorine pesticides were detected primarily in river-bed sediments. Concentrations detected in bed sediments of the San Joaquin River near Vernalis are among the highest of any major river system in the United States. Patterns and timing of pesticide use indicate that pesticides might be present in surface-water systems during most months of a year. The most commonly detected pesticide in ground water is the soil fumigant, dibromochloropropane. Dibromochloropropane, used primarily on vineyards and orchards, was detected in ground water near the city of Fresno. Triazine and other organonitrogen herbicides were detected near vineyards and orchards in the same general locations as the detections of dibromochloropropane. Pesticides were detected in ground water of the east side of the valley floor, where the soils are sandy or coarsegrained, and water-soluble pesticides with long environmental half-lives were used. In contrast, fewer pesticides were detected in ground water of the west side of the valley, where soils generally are finer grained.

California

Occurrence and accumulation of pesticides and organic contaminants in river sediment, water and clam tissues from the San Joaquin River and tributaries, California

A study was conducted in 1992 to assess the effects of anthropogenic activities and land use on the water quality of the San Joaquin River and its major tributaries. This study focused on pesticides and organic contaminants, looking at distributions of contaminants in water, bed and suspended sediment, and the bivalve Corbicula fluminea. Results indicated that this river system is affected by agricultural practices and urban runoff. Sediments from Dry Creek contained elevated concentrations of polycyclic aromatic hydrocarbons (PAHs), possibly derived from urban runoff from the city of Modesto; suspended sediments contained elevated amounts of chlordane. Trace levels of triazine herbicides atrazine and simazine were present in water at most sites. Sediments, water, and bivalves from Orestimba Creek, a westside tributary draining agricultural areas, contained the greatest levels of DDT (1,1,1-trichloro-2-2-bis[p-chlorophenyl]ethane), and its degradates DDD (1,1-dichloro-2,2-bis[p-chlorophenyl]ethane), and DDE (1,1-dichloro-2,2- bis[p-chlorophenyl]ethylene). Sediment adsorption co efficients (K(oc)), and bioconcentration factors (BCF) in Corbicula of DDT, DDD, and DDE at Orestimba Creek were greater than predicted values. Streams of the western San Joaquin Valley can potentially transport significant amounts of chlorinated pesticides to the San Joaquin River, the delta, and San Francisco Bay. Organochlorine compounds accumulate in bivalves and sediment and may pose a problem to other biotic species in this watershed.

California

Inputs of the Dormant-Spray Pesticide, Diazinon, to the San Joaquin River, California, February 1993

INTRODUCTION The objective of the National Water Quality Assessment (NAWQA) Program of the U.S. Geological Survey is to describe the status and trends of the Nation's water quality with respect to natural features of the environment and human activities or land-use. Pesticides are a major water-quality issue in the San Joaquin Valley of California (fig. 1), and pesticide residues may be transported to rivers and streams in agricultural runoff following winter storms. Three sites in the western San Joaquin Valley were monitored during and after two February 1993 storms. The storms occurred after extensive spraying of organophosphate insecticides, mostly diazinon, on almond and other stone-fruit orchards.

Fact Sheet

Nonpoint sources of pesticides in the San Joaquin River, California; input from winter storms, 1992-93

Organophosphate insecticides, including chlor- pyrifos, diazinon, and methidathion, are applied to dormant orchards in the San Joaquin Valley, California, during late December through January. This time frame coincides with the period of heaviest rainfall in the valley, and rainfall mobilizes a portion of these pesticides from the orchards. The pesticides enter the San Joaquin River and have been detected along the perennial reach of the river. A storm on the evening of February 7 and the morning of February 8, 1993, deposited more than an inch and a half of rain in the San Joaquin Valley. Two distinct peaks of organophosphate pesticide concentrations were measured at the mouth of the San Joaquin River during a single rise in discharge. Both peaks were attributed to contrasts between the soil texture and hydrology of the eastern and western valley. The fine soil texture and small size of the western tributary basins contributed to rapid runoff. Diazinon concentrations peaked within hours after rainfall ended and then decreased because of a combination of dilution with pesticide-free runoff from the nearby Coast Ranges and decreased pesticide concentrations in the agricultural runoff. Data for the Merced River, a large tributary of the eastern San Joaquin Valley, are sparse, but indicate that peak concentrations occurred at least a day after those of the western tributary streams. That delay may be due to the presence of well-drained soils, the larger size of the drainage basins, and the management of surface-water drainage networks. Runoff from a subsequent storm, on February 18 and 19, contained significantly lower concentrations of most organophosphate pesticides, indicating that runoff from the first storm had already removed most of the pesticides available for rainfall-induced transport.

Open-File Report

National Water-Quality Assessment Program: The Sacramento River Basin

In 1991, the U.S. Geological Survey (USGS) began to implement a full-scale National Water-Quality Assessment (NAWQA) program. The long-term goals of the NAWQA program are to describe the status of and trends in the quality of a large, representative part of the Nation's surface- and ground-water resources and to identify the major natural and human factors that affect the quality of those resources. In addressing these goals, the program will provide a wealth of water- quality information that will be useful to policy makers and managers at the national, State, and local levels. A major asset of the NAWQA program is that it will allow for the integration of water-quality information collected at several scales. A major component of the program is the study-unit investigation-the foundation of national- level assessment. The 60 study units of the NAWQA program are hydrologic systems that include parts of most major river basins and aquifer systems of the conterminous United States. These study units cover areas of 1,000 to more than 60,000 square miles and represent 60 to 70 percent of the Nation's water use and population served by public water supplies. Investigations of the first 20 study units began in 1991. In 1994, the Sacramento River Basin was among the second set of 20 NAWQA study units selected for investigation.

Fact Sheet

Methods of analysis and quality-assurance practices of the U.S. Geological Survey organic laboratory, Sacramento, California: Determination of pesticides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry

Analytical method and quality-assurance practices were developed for a study of the fate and transport of pesticides in the Sacramento-San Joaquin Delta and the Sacramento and San Joaquin River. Water samples were filtered to remove suspended parti- culate matter and pumped through C-8 solid-phase extraction cartridges to extract the pesticides. The cartridges were dried with carbon dioxide, and the pesticides were eluted with three 2-milliliter aliquots of hexane:diethyl ether (1:1). The eluants were analyzed using capillary-column gas chromatography/mass spectrometry in full-scan mode. Method detection limits for analytes determined per 1,500-milliliter samples ranged from 0.006 to 0.047 microgram per liter. Recoveries ranged from 47 to 89 percent for 12 pesticides in organic-free, Sacramento River and San Joaquin River water samples fortified at 0.05 and 0.26 microgram per liter. The method was modified to improve the pesticide recovery by reducing the sample volume to 1,000 milliliters. Internal standards were added to improve quantitative precision and accuracy. The analysis also was expanded to include a total of 21 pesticides. The method detection limits for 1,000-milliliter samples ranged from 0.022 to 0.129 microgram per liter. Recoveries ranged from 38 to 128 percent for 21 pesticides in organic-free, Sacramento River and San Joaquin River water samples fortified at 0.10 and 0.75 microgram per liter.

California

Distributions of pesticides and organic contaminants between water and suspended sediment, San Francisco Bay, California

Suspended-sediment and water samples were collected from San Francisco Bay in 1991 during low river discharge and after spring rains. All samples were analyzed for organophosphate, carbamate, and organochlorine pesticides; petroleum hydrocarbons; biomarkers; and polynuclear aromatic hydrocarbons. The objectives were to determine the concentrations of these contaminants in water and suspended sediment during two different hydrologic conditions and to determine partition coefficients of the contaminants between water and sediment. Concentrations of hydrophobic contaminants, such as polynuclear aromatic hydrocarbons, varied with location of sample collection, riverine discharge, and tidal cycle. Concentrations of hydrophobic contaminants in suspended sediments were highest during low river discharge but became diluted as agricultural soils entered the bay after spring rains. Polynuclear aromatic hydrocarbons defined as dissolved in the water column were not detected. The concentrations sorbed on suspended sediments were variable and were dependent on sediment transport patterns in the bay. In contrast, the relatively hydrophilic organophosphate pesticides, such as chlorpyrifos and diazinon, has a more uniform concentration in suspended sediment. These pesticides were detected only after spring rains. Most of the measured diazinon, at least 98% for all samples, was in the dissolved phase. Measured partition coefficients for diazinon generally were uniform, which suggests that suspended-sediment concentrations were close to equilibrium with dissolved concentrations. The concentration of diazinon sorbed to suspended sediments, at any given sampling site, was driven primarily by the more abundant solution concentration. The concentrations of diazinon sorbed to suspended sediments, therefore, were independent of the patterns of sediment movement.

California

Pesticide residues in ground water of the San Joaquin Valley, California

A regional assessment of non-point-source contamination of pesticide residues in ground water was made of the San Joaquin Valley, an intensively farmed and irrigated structural trough in central California. About 10% of the total pesticide use in the USA is in the San Joaquin Valley. Pesticides detected include atrazine, bromacil, 2.4-DP, diazinon, dibromochloropropane, 1,2-dibromoethane, dicamba, 1,2-dichloropropane, diuron, prometon, prometryn, propazine and simazine. All are soil applied except diazinon. Pesticide leaching is dependent on use patterns, soil texture, total organic carbon in soil, pesticide half-life and depth to water table. Leaching is enhanced by flood-irrigation methods except where the pesticide is foliar applied such as diazinon. Soils in the western San Joaquin Valley are fine grained and are derived primarily from marine shales of the Coast Ranges. Although shallow ground water is present, the fewest number of pesticides were detected in this region. The fine-grained soil inhibits pesticide leaching because of either low vertical permeability or high surface area; both enhance adsorption on to solid phases. Soils of the valley floor tend to be fine grained and have low vertical permeability. Soils in the eastern part of the valley are coarse grained with low total organic carbon and are derived from Sierra Nevada granites. Most pesticide leaching is in these alluvial soils, particularly in areas where depth to ground water is less than 30m. The areas currently most susceptible to pesticide leaching are eastern Fresno and Tulare Counties. Tritium in water molecules is an indicator of aquifer recharge with water of recent origin. Pesticide residues transported as dissolved species were not detected in non-tritiated water. Although pesticides were not detected in all samples containing high tritium, these samples are indicative of the presence of recharge water that interacted with agricultural soils.

Journal of Hydrology

Organic geochemistry and brine composition in Great Salt, Mono, and Walker Lakes

Samples of Recent sediments, representing up to 1000 years of accumulation, were collected from three closed basin lakes (Mono Lake, CA, Walker Lake, NV, and Great Salt Lake, UT) to assess the effects of brine composition on the accumulation of total organic carbon, the concentration of dissolved organic carbon, humic acid structure and diagenesis, and trace metal complexation. The Great Salt Lake water column is a stratified Na-Mg-Cl-SO 4 brine with low alkalinity. Algal debris is entrained in the high density (1.132–1.190 g/cc) bottom brines, and in this region maximum organic matter decomposition occurs by anaerobic processes, with sulfate ion as the terminal electron acceptor. Organic matter, below 5 cm of the sediment-water interface, degrades at a very slow rate in spite of very high pore-fluid sulfate levels. The organic carbon concentration stabilizes at 1.1 wt%. Mono Lake is an alkaline (Na-CO 3 -Cl-SO 4 ) system. The water column is stratified, but the bottom brines are of lower density relative to the Great Salt Lake, and sedimentation of algal debris is rapid. Depletion of pore-fluid sulfate, near l m of core, results in a much higher accumulation of organic carbon, approximately 6 wt%. Walker Lake is also an alkaline system. The water column is not stratified, and decomposition of organic matter occurs by aerobic processes at the sediment-water interface and by anaerobic processes below. Total organic carbon and dissolved organic carbon concentrations in Walker Lake sediments vary with location and depth due to changes in input and pore-fluid sulfate concentrations. Nuclear magnetic resonance studies ( 13 C) of humic substances and dissolved organic carbon provide information on the source of the Recent sedimentary organic carbon (aquatic vs. terrestrial), its relative state of decomposition, and its chemical structure. The spectra suggest an algal origin with little terrestrial signature at all three lakes. This is indicated by the ratio of aliphatic to aromatic carbon and the absence of chemical structures indicative of the lignin of vascular plants. The dissolved organic carbon of the Mono Lake pore fluids is structurally related to humic acid and is also related to carbohydrate metabolism. The alkaline pore fluids, due to high pH, solubilize high molecular weight organic matter from the sediments. This hydrophilic material is a metal complexing agent. Despite very high algal productivities, organic carbon accumulation can be low in stratified lakes if the anoxic bottom waters are hypersaline with high concentrations of sulfate ion. Labile organic matter is recycled to the water column and the sedimentary organic matter is relatively nonsusceptible to bacterial metabolism. As a result, pore-fluid dissolved organic carbon and metal-organic complexation are low.

Geochimica et Cosmochimica Acta