Distribution of Dissolved Pesticides and Other Water Quality Constituents in Small Streams, and their Relation to Land Use, In the Willamette River Basin,Oregon

Federal Geographic Data Committee (FGDC) Metadata:


Identification_Information:
Citation:
Citation_Information:
Originator: Chauncey W. Anderson, Tamara M. Wood and Jennifer L. Morace
Publication_Date: 1997
Title: Distribution of Dissolved Pesticides and Other Water Quality Constituents in Small Streams, and their Relation to Land Use, In the Willamette River Basin,Oregon
Edition:
Geospatial_Data_Presentation_Form: database
Series_Information:
Series_Name:
Issue_Identification:
Publication_Information:
Publication_Place: Portland, Oregon
Publisher: U.S. Geological Survey
Other_Citation_Details:
Online_Linkage:
Description:
Abstract:
Water quality samples were collected at sites in 16 randomly selected agricultural and 4 urban subbasins as part of Phase III of the Willamette River Basin Water Quality Study in Oregon during 1996. Ninety-five samples were collected and analyzed for suspended sediment, conventional constituents (temperature, dissolved oxygen, pH, specific conductance, nutrients, biochemical oxygen demand, and bacteria) and a suite of 86 dissolved pesticides. The data were collected to characterize the distribution of dissolved pesticide concentrations in small streams (drainage areas 2.6-13 square miles) throughout the basin, to document exceedances of water quality standards and guidelines, and to identify the relative importance of several upstream land use categories (urban, agricultural, percent agricultural land, percent of land in grass seed crops, crop diversity) and seasonality in affecting these distributions. A total of 36 pesticides (29 herbicides and 7 insecticides) was detected basinwide. The five most frequently detected compounds were the herbicides atrazine (99% of samples), desethylatrazine (93%), simazine (85%), metolachlor (85%), and diuron (73%). Fifteen compounds were detected in 12-35% of samples, and 16 compounds were detected in 1-9% of samples. Water quality standards or criteria were exceeded more frequently for conventional constituents than for pesticides. State of Oregon water quality standards were exceeded at all but one site for the indicator bacteria E. coli, 3 sites for nitrate, 10 sites for water temperature, 4 sites for dissolved oxygen, and 1 site for pH. Pesticide concentrations, which were usually less than 1 part per billion, exceeded State of Oregon or U.S. Environmental Protection Agency aquatic life toxicity criteria only for chlorpyrifos, in three samples from one site; such criteria have been established for only two other detected pesticides. However, a large number of unusually high concentrations (1-90 parts per billion) were detected, indicating that pesticides in the runoff sampled in these small streams were more highly concentrated than in the larger streams sampled in previous studies. These pulses could have had short term toxicological impli cations for the affected streams; however, additional toxicological assessment of the detected pesticides was limited because of a lack of available information on the response of aquatic life to the observed pesticide concentrations. Six pesticides, including atrazine, diuron, and metolachlor, had significantly higher (p<0.08 for metolachlor, p<0.05 for the other five) median concentrations at agricutural sites than at urban sites. Five other compounds--carbaryl, diazinon, dichlobenil, prometon, and tebuthiuron--had significantly higher (p<0.05) concentrations at the urban sites than at the agricultural sites. Atrazine, metolachlor, and diuron also had significantly higher median concentrations at southern agricultural sites (dominated by grass seed crops) than northern agricultural sites. Other compounds that had higher median concentrations in the south included 2,4-D and metribuzin, which are both used on grass seed crops, and triclopyr, bromacil, and pronamide. A cluster analysis of the data grouped sites according to their pesticide detections in a manner that was almost identical to a grouping made solely on the basis of their upstream land use patterns (urban, agricultural, crop diversity, percentage of basin in agricultural production). In this way inferences about pesticide associations with different land uses could be drawn, illustrating the strength of these broad land use categories in determining the types of pesticides that can be expected to occur. Among the associations observed were pesticides that occurred at a group of agricultural sites, but which have primarily noncropland uses such as vegetation control along rights-of-way. Also, the amount of forested land in a basin was negatively associated with pesticide occurrence, suggesting that riparian growth or runoff from forested lands helped reduce pesticide concentrations. Estimates of pesticide application also were made for the 16 agricultural study basins. Concentrations of pesticides in streams were significantly (albeit weakly) correlated (p<0.05) with estimated use for only a few compounds that are applied to a wide variety of crop types. Because of the large acreages involved, several compounds that are applied to grass seed were better cor related with the fraction of upstream land use in agricultural production or in grass seed crops than with their respective estimated applications. Application estimates for some compounds, including atrazine and metolachlor, were probably low because of uses that are not indicated in current literature. Significant correlations were also found among certain individual compound concentrations, and between these and concentrations of suspended sediment. Included in both groups were atrazine and metolachlor, suggesting that environmental factors that mobilize atrazine and metolachlor can mobilize other compounds, and that hydrologic conditions are as important as the specific amount and timing of application in determining the transport of many compounds to the streams. The suspended sediment concentration was not, however, significantly correlated with discharge, and concentrations of only one pesticide were correlated with discharge. Even though correlations between discharge and pesticide concentration were poor, the similar seasonal pattern in both variables is evidence that transport to the streams is related to discharge and consequently to the amount of runoff. Median concentrations of atrazine, metolachlor, diuron, metribuzin, pronamide, and suspended sediment were significantly higher in the late fall than in the summer. Additionally, winter "baseline" sampling for both atrazine and metolachlor confirmed that median concentrations as high as those in the fall or spring were maintained well past any periods of initial flushing, suggesting that a steady supply of atrazine and metolachlor is retained in soils in the study basins. Two intensive immunoassay studies illustrated variations in pesticide concentration over storm hydrographs. During a large storm with localized flooding, atrazine concentration increased on the rising limb of the hydrograph, started to decrease just prior to peak stage (indicating dilution), and continued to decrease as the water level decreased. Metolachlor concentrations decreased throughout the storm by a factor of two from their concentrations prior to the storm. The future prospects for successfully correlating the stream loads of certain pesticides with estimates of application rates may be good if current and locally specific rates of application to various crop types can be obtained. Alternatively, atrazine concentration appears to be at least a rough indicator for conditions that move several other compounds, and it was shown that it can be measured relatively cheaply and with good accuracy and precision, with enzyme immunoassays. However, the prevalence of atrazine in stream water throughout the basin precludes its use for prediction of occurrence or concentrations of specific compounds in the absence of other information.The primary purpose of the study was to describe the distribution of dissolved pesticide concentrations in selected small streams throughout the basin, (2) document exceedances of water quality guidelines for the targeted pesticides, and (3) identify the relative importance of broad measures of land use and seasonality in determining those concentrations. Secondary objectives are to (4) describe relations, where they exist, between selected pesticide applications and stream concentrations or loads and, (5) for those relations identified, to further describe their dependence on seasonality and on selected site and compound characteristics. A final objective is to further characterize water quality at the chosen sampling sites with respect to conventional constituents. Discharge was measured according to standard USGS guidelines as described by Rantz and others (1982). No sites were gauged. Discharge was measured twice during each of spring and fall and once during summer, when a complete set of samples were collected for analytical chemistry. However, many sites were visited at other times for a rapid collection of samples for immunoassay analysis of triazine (primarily atrazine) or chloroacetamide (primarily metolachlor) herbicides. In order to estimate the relative stage of streams when time constraints prohibited a full discharge measurement, reference points were established at each site from which to consistently measure either the depth of the water or the distance to the water surface. These reference point depths were noted at the time of each discharge measurement and also at any time that immunoassay samples were taken. Samples were collected at each site twice during spring and fall in order to assess stream responses to runoff, and once during summer to assess low-flow conditions. Basinwide samplings during spring and fall were timed to correspond to periods of rainfall runoff, with minimum intervals of approximately 1 week of dry weather required between samplings in each season, to allow pesticide applications to occur and stream discharges to return to steady flows. Rain storms during spring 1996 that produced runoff were well spaced, and samplings for successive storms were conducted in mid-April and mid-May. During fall, basinwide samplings were conducted in mid-October and in mid-November. Constituents collected during basinwide samplings in spring, summer, and fall included pesticides, conventional constituents, and suspended sediment; additional samplings were conducted at individual sites, and basinwide during the winter, using immunoassays as a screening tool to expand the number of samples for atrazine and metolachlor. Water samples for pesticides and conventional constituents were collected as grab samples from midstream. Samples for suspended sediment were collected using the equal-width-increment method, a depth- and width-integrating technique described by Edwards and Glysson (1988). Water temperature, DO, pH, and specific conductance were measured in place using Hydrolab multiparameter probes that were calibrated in the field according to the manufacturer's suggested methods. All samples were processed prior to shipment to laboratories for analysis. Grab samples were generally collected at the centroid of flow by wading. When safety considerations prevented wading, samples were collected using weighted bottle holders suspended from a bridge or culvert above the stream. Sampling personnel wore plastic gloves to minimize contamination. At each site, pesticide samples were collected into cleaned and baked (350 degrees Celsius, 12 hours) amber glass (GCC) bottles, nutrients and BOD5 were collected in polypropylene bottles, and bacteria samples were collected in autoclaved polycarbonate bottles. Additional samples for immunoassays were collected in GCC bottles as needed. GCC and bacterial bottles were not rinsed in the field, whereas bottles for nutrients and BOD5 were rinsed three times with stream water prior to filling. All sample bottles except those for suspended sediment were stored on ice until they were returned to the Oregon District Laboratory for processing, usually a period of 1 to 6 hours. At the Oregon District Laboratory, pesticide samples were immediately filtered into clean GCC bottles through 0.7 micrometer pore-sized baked glass-fiber filters and subsequently chilled. Small aliquots of the filtrate were subsampled for analysis of herbicides using immunoassay methods. The remaining filtrate was extracted onto a solid-phase sorbent material (Sandstrom, 1989), which was then shipped within 4 days of collection to the USGS National Water Quality Laboratory (NWQL) in Arvada, Colorado, for elution and subsequent analysis. Pesticide analysis was performed using gas chromatography/mass spectroscopy (GC/MS-USGS schedule 2010) or high-pressure liquid chromatography (HPLC-USGS schedule 2051). Procedures for filtration, solid-phase extraction, elution, and analysis of pesticides by GC/MS have been detailed by Zaugg and others (1955), and similar procedures describing sample preparation and analysis by HPLC are described by Werner and others (1996). The suite of 86 pesticides analyzed by the two methods is listed in table 2 of the Anderson, Wood and Morace, distribution of dissolved pesticides and other water quality constituents in small streams, and their relation to land use, in the Willamette River Basin, Oregon, 1996 publication and other constituents and their methods are listed in table 3 of the same publication. Units of concentration used are in terms of micrograms per liter equivalent to parts per billion, or ppb) for pesticides, and milligrams per liter equivalent to parts per million, or ppm for nutrients, BOD5 and suspended sediment. Water samples were also collected for the measurement of atrazine and metolachlor concentrations by enzyme-linked immunoabsorbent assays. This method, often referred to as "immunoassay", uses antibodies selective for the compound being analyzed for, making it possible to isolate the target compound and determine the concentrations at low levels (less than 1 part per billion). Immunoassay samples were collected for two purposes: (1) to assess the agreement between the immunoassay and GC/MS methods and (2) to provide better resolution of temporal variability, especially during storms and midwinter "baseline" conditions. The advantages of the immunoassay method over the more comprehensive GC/MS analysis include the lower cost and the timeliness of the data. However, the immunoassay method is less compound specific than GC/MS. Immunoassays for atrazine and metolachlor were chosen because these compounds were expected to be commonly detected on the basis of previous studies (Anderson and others, 1996) and because reliable test kits were available to them. Immunoassay kits were used according to the manufacturer's specifications (Ohmicron Environmental Diagnostics, Inc., written commun., March 1996). Analyses were performed in triplicate with the RPA-I RaPID Photometric Analyzer TM (Ohmicron Environmental Diagnostics, Inc., 1992). The lower limits of the NWQL's analytical capabilities are generally reported by one of two methods. The minimum reporting level (MRL) is the lowest measured concentration of a constituent that may be reliably reported using a given analytical method (Timme, 1994). For methods such as nutrient analysis that use MRLs' concentrations less than the MRL are consored, and the data are reported as being less than the value of the MRL. The method detection limit (MDL) is a statistically derived minimum concentration that can be identified, measured, and reported with a 99% confidence as being greater than zero (Sandstrom, 1989). That is, there is no more than a 1% chance that a concentration greater than the MDL was reported for a sample that actually did not contain the analyte (false positive). Concentrations may be reported that are less than the MDL, but the chance of a false positive detection is greater than 1%. In contrast, the actual concentration in a sample reported as a nondetection has up to a 50% chance of being equal to or greater than the MDL (false negative). Concentrations for compounds listed in table 2 (Anderson and others, 1997) are reported using MDLs. Pesticide analysis of several stream samples were qualified by NWQL analysts as particularly difficult due to interferences from nontarget compounds, sometimes at relatively high concentrations. As a special analysis, extracts from three of these "dirty" samples were re-analyzed by custom, high-resolution electron-capture negative-ion mass spectrometry in order to investigate the causes of the interferences. Identification of additional compounds observed in these samples (using a GC/MS spectral library) was provided where possible, and inferences about their sources were made with the assistance of NWQL analysts. The information for this metadata was taken from the Online Publications of the Oregon District at http://oregon.usgs.gov/pubs_dir/online_list.html .
Purpose:
Not Available
Supplemental_Information:
REFERENCE: Anderson, C. W., Wood, T.M., and Morace, J.M., 1997, Distribution of Dissolved Pesticides and Other Water Quality Constituents in Small Streams, and their Relation to Land Use, in the Willamette River Basin, Oregon, 1996. U.S. Geological Survey Water-Resources Investigations Report 97-4268, Portland, Oregon. U.S. Geological Survey http://oregon.usgs.gov/pubs_dir/Pdf/97-4268.pdf
Time_Period_of_Content:
Time_Period_Information:
Range_of_Dates/Times:
Beginning_Date: 19960301
Ending_Date: 19961130
Currentness_Reference:Unknown
Status:
Progress: Complete
Maintenance_and_Update_Frequency: As needed
Spatial_Domain:
Description_of_Geographic_Extent:
Bounding_Coordinates:
West_Bounding_Coordinate: -124.0
East_Bounding_Coordinate: -121.5
North_Bounding_Coordinate: 46.0
South_Bounding_Coordinate: 43.5
Keywords:
Theme:
Theme_Keyword_Thesaurus: GCMD SCIENCE PARAMETERS
Theme_Keyword_Thesaurus: ANCILLARY KEYWORDS
Theme_Keyword_Thesaurus: ISO TOPIC CATEGORY
Theme_Keyword_Thesaurus: DATA SET LANGUAGE
Theme_Keyword: EARTH SCIENCE > AGRICULTURE > AGRICULTURAL CHEMICALS > PESTICIDES
Theme_Keyword: EARTH SCIENCE > BIOSPHERE > VEGETATION > NITROGEN
Theme_Keyword: EARTH SCIENCE > BIOSPHERE > VEGETATION > NUTRIENTS
Theme_Keyword: EARTH SCIENCE > BIOSPHERE > VEGETATION > PHOSPHORUS
Theme_Keyword: EARTH SCIENCE > HUMAN DIMENSIONS > ENVIRONMENTAL IMPACTS > CONTAMINANT LEVELS/SPILLS > PESTICIDES
Theme_Keyword: EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > WATER QUALITY/WATER CHEMISTRY > CONTAMINANTS > PESTICIDES
Theme_Keyword: EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > WATER QUALITY/WATER CHEMISTRY > DISSOLVED GASES > DISSOLVED OXYGEN
Theme_Keyword: EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > WATER QUALITY/WATER CHEMISTRY > NITROGEN COMPOUNDS
Theme_Keyword: EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > WATER QUALITY/WATER CHEMISTRY > NUTRIENTS
Theme_Keyword: EARTH SCIENCE > TERRESTRIAL HYDROSPHERE > WATER QUALITY/WATER CHEMISTRY > PHOSPHOROUS COMPOUNDS
Theme_Keyword: EARTH SCIENCE > BIOSPHERE > AQUATIC ECOSYSTEMS > RIVERS/STREAM HABITAT > WILLAMETTE RIVER BASIN
Theme_Keyword: EARTH SCIENCE > BIOSPHERE > ECOLOGICAL DYNAMICS > ECOSYSTEM FUNCTIONS > NUTRIENT CYCLING
Theme_Keyword: Water Quality
Theme_Keyword: Suspended Sediment
Theme_Keyword: Conventional Constituents
Theme_Keyword: Temperature
Theme_Keyword: Dissolved Oxygen
Theme_Keyword: Ph
Theme_Keyword: Specific Conductance
Theme_Keyword: Nutrients
Theme_Keyword: Biochemical Oxygen Demand
Theme_Keyword: Bacteria
Theme_Keyword: Willamette River Basin
Theme_Keyword: Oregon
Theme_Keyword: Biological Data Profile
Theme_Keyword: Bdp
Theme_Keyword: FARMING
Theme_Keyword: BIOTA
Theme_Keyword: ENVIRONMENT
Theme_Keyword: GEOSCIENTIFIC INFORMATION
Theme_Keyword: INLAND WATERS
Theme_Keyword: ENGLISH
Place:
Place_Keyword_Thesaurus: GCMD
Place_Keyword: CONTINENT > NORTH AMERICA > UNITED STATES OF AMERICA > OREGON
Access_Constraints: None
Use_Constraints:
None
Point_of_Contact:
Contact_Information:
Contact_Person_Primary:
Contact_Person: CHAUNCEY W. ANDERSON
Contact_Position: TECHNICAL CONTACT
Contact_Address:
Address_Type: Mailing and Physical Address
Address: U.S. Geological Survey
Address: 10615 SE Cherry Blossom Dr.
City: Portland
State_or_Province: Oregon
Postal_Code: 97216
Country: USA
Contact_Voice_Telephone: (503) 251-3206
Contact_Facsimile_Telephone: (503) 251-3470
Contact_Electronic_Mail_Address: chauncey@usgs.gov
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Data_Quality_Information:
Attribute_Accuracy:
Attribute_Accuracy_Report:
In order to estimate variability in sampling and laboratory techniques, quality control (QC) samples were submitted to the NWQL for pesticides, and to the ODEQ and ACWA laboratories for the conventional constituents. Most QC samples were used to evaluate the potential for problems form the combination of field and laboratory procedures. QC samples for both pesticides and conventional constituents included (1) field and equipment blanks to test for contamination, (2) replicate native-water grab samples to test for precision, (3) depth and width integrated samples collected as replicates to compare with grab samples, and (4) distinct compounds, representing relevant pesticide families (surrogates), added in known amounds to each pesticide sample to monitor the analytical method's ability to quantify those sample types. Additional QC samples for pesticides included (5) native-water samples spiked with pesticide mixtures to test for accuracy, done at a range of concentrations (low, medium, and high)), and (6) replicate spike samples to test for accuracy and precision. Water for blank samples was carefully selected to be free fo the constituents of concern: organic-free water was used for pesticide, immunoassay, and BOD5 samples; inorganic-free water was used for nutrient samples; a peptone buffer solution was used for fecal coliform bacteria, and a sterile saline solution was used for E. Coli bacteria blanks. QC data for this study are presented in Appendix 1 of Anderson and others, 1997. The study design called for sample collection from 16 randomly selected subbasins that each had predominantly agricultural land uses upstream of the sampling site, and 4 subbasins having predominantly urban land use. In order to minimize inputs of water from undefined or highly varied sources, small drainage basins ranging from approximately 3 to 15 square miles were selected. The four urban sites were selected from a set of urban subbasins drawn on topographic maps, and the final choice was based primarily on the desire to sample urban drainages that had not been extensively sampled previously, the desire to sample sites in urban areas in the northern, central and southern Willamette Basin, and the suitability of a site for sampling. Land use information for the urban sites was derived fromthe GIS, with coverages for urban lands most recently updated on the basis of the 1990 census (Hitt, 1994). Due to rapid growth in many of western Oregon's cities during the 1990's data for urban land use taken from the GIS is expected to somewhat underestimate the proportion of urban lands and over estimate the proportion of agricultural or forested lands in the Phase III urban subbasins. However these data were considered adequate for the purposes of the study and the report.
Logical_Consistency_Report:
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Completeness_Report:
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Process_Date: Unknown
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Distribution_Information:
Distributor:
Contact_Information:
Contact_Organization_Primary:
Contact_Organization: DOI/USGS/WRD/OR > Water Resource Division, Oregon, U.S. Geological Survey, U.S. Department of the Interior
Contact_Person: DENNIS D. LYNCH
Contact_Position: DATA CENTER CONTACT
Contact_Address:
Address_Type: Mailing and Physical Address
Address: U.S. Geological Survey
Address: 10615 S.E. Cherry Blossom Drive
City: Portland
State_or_Province: Oregon
Postal_Code: 97216-3159
Country: USA
Contact_Voice_Telephone: (503) 251-3200
Contact_Facsimile_Telephone: (503) 251-3470
Contact_Electronic_Mail_Address: ddlynch@usgs.gov
Resource_Description: WRIR_97_4268
Distribution_Liability:
Not Available
Standard_Order_Process:
Digital_Form:
Digital_Transfer_Information:
Format_Name: Not Available
Digital_Transfer_Option:
Online_Option:
Computer_Contact_Information:
Network_Address:
Network_Resource_Name:
http://oregon.usgs.gov
Access_Instructions:
DATA CENTER URL
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Online_Option:
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Network_Address:
Network_Resource_Name:
http://mercury.ornl.gov/clearinghouse/send/xsltTex...
Access_Instructions:
Metadata in National Biological Information Infrastructure format.
Fees: Not Available
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Metadata_Reference_Information:
Metadata_Date: 20010627
Metadata_Review_Date: 20121129
Metadata_Future_Review_Date: 20020627
Metadata_Contact:
Contact_Information:
Contact_Person_Primary:
Contact_Person: TYLER B. STEVENS
Contact_Position: DIF AUTHOR
Contact_Address:
Address_Type: Mailing and Physical Address
Address: NASA Goddard Space Flight Center
Address: Global Change Master Directory
City: Greenbelt
State_or_Province: MD
Postal_Code: 20771
Country: USA
Contact_Voice_Telephone: (301) 614-6898
Contact_Facsimile_Telephone: 301-614-5268
Contact_Electronic_Mail_Address: Tyler.B.Stevens@nasa.gov
Metadata_Standard_Name: FGDC Content Standards for Digital Geospatial Metadata
Metadata_Standard_Version: FGDC-STD-001-1998
Metadata_Time_Convention: local time
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