Plan of Study to Determine the Occurrence of Sulfonylurea, Sulfonamide, and Imidazolinone Herbicides in Surface and Ground-Water of the Midwestern United States
Plan of Study to Determine the Occurrence of Sulfonylurea, Sulfonamide, and
Imidazolinone Herbicides in Surface and Ground-Water of the Midwestern United
States
Abstract
This plan of study outlines an approach to determine if sulfonylurea (SU), sulfonamide (SA), or imidazolinone (IMI) herbicides can be detected in surface or groundwater samples collected from sites across the midwestern United States. The use of these three relatively new classes of herbicides has increased dramatically over the past decade. Currently, little is known about the occurrence, fate, or transport of SUs, SAs, and IMIs in water resources of the United States. The purpose of this study is to refine the methodology needed to analyze for selected SUs, SAs, and IMIs at sub parts-per-billion levels, and to conduct a reconnaissance to determine if, where, and at what concentrations SUs, SAs, and IMIs occur. Approximately 200 samples will be collected from small streams, larger rivers, reservoirs, and wells during the spring and summer of 1998. This study is the result of a cooperative research and development agreement (CRADA) between the U.S. Geological Survey (USGS) and DuPont Agricultural Products (DuPont).
Introduction
Background
During the last 20 years, a generation of low application rate herbicides has been developed that act by inhibiting the action of a key plant enzyme, resulting in stopped growth and eventual plant death. These herbicides are gaining in popularity among farmers (fig. 1). Sulfonylurea (SU), sulfonamide (SA), and imidazolinone (IMI) herbicides are three classes of compounds that function in this manner (table 1). These compounds typically are applied at much lower rates than triazine or acetanilide herbicides. SUs, SAs, and IMIs act upon a specific plant enzyme that is not found in mammals or other animals and they are reported to have very low toxicities in animals (Brown, 1990, Meister, 1997). Crops that can be treated with SUs, SAs, and IMIs include barley, corn, cotton, durum wheat, rice, canola, peanuts, soybeans, sugar beets, spring wheat, and winter wheat. Some of these compounds are also approved for use on Conservation Reserve Program (CRP) acreage and for noncropland weed control.
Plants demonstrate a wide range in sensitivity to SUs, SAs, and IMIs (Peterson et. al., 1994) with over a 1,000 fold difference in observed toxicity levels for some compounds. The EC50 (concentration causing a 50 percent reduction in a chosen toxicity endpoint, for example lab tests measuring biomass development) values for 5 aquatic plants are shown on figure 2 (U.S. Environmental Protection Agency, Office of Pesticide Programs, Environmental Fate and Effects Division, Tox One-Liner Database, 1997). The EC50 values plotted are for green algae (Selenastrum capricornutum), duckweed (Lemna gibba), blue-green algae (Anabaena flos-aquae), freshwater algae (Scenedesmus costatum), and freshwater diatom (Navicula pelliculosa). EC50 values for several herbicide range over 3 orders of magnitude. A concentration of 0.1 µg/L in water is currently believed to be the baseline for possible non-target aquatic plant toxicity. The available EC50 data plotted on figure 2 support this hypothesis.
Crop toxicities reported as EC25 values (application rates in pounds per acre resulting in a 25% reduction in a chosen toxicity endpoint, for example lab tests of juvenile plant growth) were used to estimate the herbicide concentrations in soil water that could result in non-target crop stress (U.S. Environmental Protection Agency, Office of Pesticide Programs, Environmental Fate and Effects Division, Tox One-Liner Database, 1997). EC25 values ranged from less than 0.00002 to more than 1.0 pounds per acre. The soil water concentrations resulting from the EC25 application rate were calculated assuming that the upper portion of an acre of a typical cropped loam soil has approximately 50 percent pore space which under ideal growing conditions is occupied half by water and half by air (Buckman and Brady, 1969). Thus, the top 1 foot of soil would contain 3 inches of water and this water would weigh 679,100 pounds. If we assume that rain/irrigation water distributes the mass of herbicide equal to the EC25 value to this water, then the herbicide concentration in that soil water can be estimated as:
Soil water concentration in
parts per billion (ppb) = (EC25 (lbs/acre) / (679,100 (lbs/acre)) * 109 (1)
Note that 1 ppb is equal to 1 µg/L. This estimate does not account for herbicide degradation. For example, using equation (1) the concentration of prosulfuron in soil water which may be of concern for juvenile soybean plants can be estimated as:
Estimated soil water concentrations computed using the above equation for 9 crops are shown on figure 3. The crops for which data are plotted are corn, soybeans, sorghum, canola, sugar beets, radish, onion, lettuce, and cabbage. These data indicate that non-target crop stress is unlikely to occur when soil water concentrations of SUs, SAs, and IMIs remain below 0.1 µg/L. Herbicide performance and non-target crop toxicity have been reported to vary by soil pH, soil organic content, and climate (Blair and Martin, 1988).
SUs, SAs, and IMIs are generally applied postemergence at extremely low rates (0.001 to 0.5 pounds of product per acre), hence their overall use amount is small. Estimates of the use of 8 SUs, one SAs and 3 IMIs on field crops (corn, soybeans, cotton, and wheat) in the major producing States in 1995 (USDA, 1996), totaled only about 1,430 tons of active ingredient. In comparison, atrazine use for the same year was estimated at over 22,000 tons of active ingredient (USDA, 1996). Maps showing estimated 1992 county-level use rate of imazethapyr (Pursuit) and nicosulfuron (Accent) are shown in figure 4. Maps showing estimated 1992 county-level use rate of flumetsulam (Broadstrike) and imazaquin (Scepter) are shown in figure 5.
Because SUs, SAs, and IMIs are active at very low concentrations they can cause a problem with plant vigor in some crop rotations even when only 1% or less of the originally applied material remains. Some of these herbicides have demonstrated residual phytotoxicity to rotation crops like corn, sunflowers, sugar beets, and dry beans for a year or more after application (Anderson and Barrett, 1985; Anderson and Humburg, 1987). Fletcher and others (1994) indicated that spray drift containing SUs at concentrations less than 1 percent of the recommended application rate may adversely impact fruit tree yields. However, Obrigawitch and others (1998) question the validity of Fletcher’s findings and the results of other studies that based there findings on short- term plant-response assessments. Obrigawitch’s (1998) extensive review of existing field data suggests that a treatment rate of 0.1 grams of the most active SU ingredient per hectare represents a "threshold dose" and would be unlikely to reduce the yields of even the most sensitive non-target plants. This threshold dose represent 1/100 or less of the use rates of SUs. Marrs and others noted that a buffer of 5-10 meters is needed for ground sprayers to minimize SU impacts on non- target native plants. Environment Canada uses a calculated Expected Environmental Concentration (ECC) in evaluating the potential hazard of pesticides to nontarget aquatic organisms. ECC values for selected SUs ranged from 3 to 20 µg/L and equaled 67 µg/L for imazethapyr (Peterson et. al., 1994). For comparison, ECC values for selected triazine herbicides were more than 100 times greater at 2,667 to 2,867 µg/L. These are worst case exposure estimates and assume overspray of a 15 cm water body with the maximum application rate. These results all suggest that there is a potential for SU, SA, and IMI herbicide to have an adverse effect on aquatic plants or crops if they were to occur in river water, rainwater, irrigation water, or soil water at concentrations greater than 0.1 µg/L.
The soil half-life of SUs, SAs, and IMIs generally ranges from 1 to 25 weeks depending on soil pH and temperature. The water solubility of SUs, SAs, and IMIs generally ranges from 6 to 40,000 part per million and is usually dependent on water pH.
Previous Investigations
Herbicide concentrations in 52 Midwestern river were sampled by the USGS (Goolsby et. al., 1994) during runoff events that occurred soon after herbicide application in 1989, 1990, 1994 and 1995. The median concentration of herbicides in these samples represent an estimate of expected environmental concentrations based upon observation. Median atrazine concentration from the four years ranged from 4.0 to 10.9 µg/L while median cyanazine concentrations ranged from 1.2 to 2.7 µg/L, and median metolachlor concentrations ranged from 1.7 to 3.1 µg/L. Maximum concentrations for these three compound for the 4 years ranged from 10.6 to 108 µg/L. Because of their low application rates and low overall use amounts, concentrations of SUs, SAs, and IMIs are expected to be low or nondetectible in midwestern water resources. One can assuming based upon application rates and acres treated that individual SUs, SAs, and IMIs herbicides would be expected to occur at 1/100th to 1/1,000th or less of concentration of common triazine herbicides. Thus, one would expected to commonly observed SUs, SAs, and IMIs herbicides in Midwestern rivers during post-application runoff events at concentrations ranging from 0.001 to 0.1 µg/L. Further, one would expect maximum concentrations of SUs, SAs, and IMIs herbicides to range from 0.01 to 1.0 µg/L.
To Date (May, 1998), detections of SUs, SAs, and IMIs in water collected from environmental settings have been rare and the few reported detections have been at nanogram per liter concentrations (Bergstrom, 1990; Michael and Neary, 1993). However, several studies indicate that some SUs, SAs, and IMIs herbicides may leach beyond the active root zone and enter groundwater or surface water systems (Anderson and Humburg, 1987; Bergstrom, 1990; Flury et. al., 1995; Veeh et. al., 1994). Once in groundwater or surface-water, some SUs, SAs, and IMIs would tend to persist as the parent compound while others would tend to hydrolyze (Dinelli et. al., 1997; Harvey et. al., 1985). A study by Afyuni et. al. (1997) indicated that between 1.1 and 2.3 percent of an applied SU was lost in runoff during a simulated rainfall event 24 hours after herbicide application.
Objectives and Hypotheses
Currently, little is known about the occurrence, fate, or transport of SUs, SAs, and IMIs in surface water and groundwater in the United States. The overall objective of this project is to determine if and at what concentrations selected SUs, SAs, and IMIs occur in surface and ground water resources of the midwestern United States. Specific objectives include: (1) validate an existing analytical method for selected SUs, SAs, and IMIs provided by DuPont; (2) lower the limit of quantitation of this method; (3) add other herbicides and herbicide degradation products to the list of analytes, (4) conduct a reconnaissance to determine the environmental occurrence and distribution of SUs, SAs, and IMIs herbicides in surface and ground water in the midwestern United States, and (5) determine the frequency of detections and concentrations of selected other pesticides in midwestern rivers. Specific hypotheses to be tested are:
1. SU, SA and IMI herbicides will be detected in surface water and groundwater in the midwest.
2. The frequency of detections and concentrations of SU, SA, and IMI herbicides will be significantly less than that of other herbicides that are applied in greater total amounts.
3. The frequency of detections and concentrations of SU, SA, and IMI herbicides will be greater in post-emergence runoff samples than in pre-emergence runoff samples.
4. The frequency of detections and concentrations of SU, SA, and IMI herbicides will be greater in streams and reservoirs than in groundwater.
5. The frequency of detections and concentrations of SU, SA, and IMI herbicides will be greater in smaller watersheds that are predominantly agricultural than in larger watersheds that are more diverse.
Plan of Study
This study will involve collecting approximately 200 samples during a 1998 reconnaissance. Samples will be collected from small streams, larger rivers, reservoir outflows, and wells. When possible samples will be collected in conjunction with NASQAN and NAWQA activities, both to reduce the cost of sample collection and to insure availability of QA/QC and other water- quality data (herbicides, insecticides, and nutrients). All 1998 SU reconnaissance samples will be sent to the Methods Research and Development Program (MRDP) personnel at the USGS National Water Quality Lab (NWQL) in Denver, Colorado and analyzed for a minium of 16 herbicides (table 1) using high performance liquid chromatography coupled with mass spectrometry. The method will have quantification limits of less than 0.1 µg/L for all analytes.
Sampling sites
One hundred sites will be sampled in this study (figure 6). The majority of the water samples will be collected from surface-water sites in the Upper Mississippi, Missouri, and Ohio River basins. Many of the sites to be sampled have been studied in previous Midcontinent Herbicide Initiative (MHI) investigations (Thurman et. al., 1992; Goolsby et. al., 1994; Kolpin et. al., 1994; Coupe et. al., 1995). Samples will also will be collected at selected NASQAN and NAWQA sites and just downstream from five reservoirs at locations that were sampled in a previous investigation (Scribner et. al., 1996). Surface-water sampling site names, locations, site-ids, and drainage areas are listed in table 2. Site locations are shown on figure 6. The majority of groundwater samples will be collected from a network of wells in Iowa that are part of the Iowa Groundwater Monitoring (IGWM) program (Detroy et. al., 1988; Kolpin et. al., 1997). Wells from this network have been sampled systematically since 1982. Samples will also be collected from selected wells in the Lower Illinois NAWQA study unit. Groundwater sampling site names, locations, and site-ids are listed in table 3.
Sampling Schedule
Two samples will be collected at each surface-water and reservoir site (one on each of two site visits), and one sample will be collected at each groundwater site. The first surface-water samples will be collected after pre-emergence herbicides have been applied (usually May or June) and following a precipitation event that produces a significant increase in streamflow. Ideally, streamflow should be representative of runoff conditions with flow at or above the 50th percentile (50 percent exceeds values for the period of record, published in State USGS Water Resources Data reports). These samples will be referred to as pre-emergence runoff samples. The second surface-water samples will be collected after post-emergence herbicides have been applied (usually June or July) again following a precipitation event that produces runoff conditions and streamflows at or above the 50th percentile. These samples will be referred to as post-emergence runoff samples. The first NASQAN and reservoir samples will be collected in May or June, 2-3 weeks after the first surface-water samples were collected from nearby sites. The second NASQAN and reservoir samples will be collected in June or July, 2-3 weeks after the second surface-water samples were collected from nearby sites. Collection of these surface-water and reservoir samples may require special visits to sites. Groundwater samples will be collected in July or August. See Appendix 1 for more detailed sample collection instructions.
Sampling Procedure
Samples will be collected using protocols that are identical to those used for the collection of samples for 2001 or 2050 analysis (Shelton, 1994). The equal-width-increment sampling method (Edwards and Glysson, 1988) is recommended, but equal-discharge-increment sampling is also acceptable on larger rivers. See appendix 1 for step-by-step sampling procedure. All equipment will be precleaned with a Liquinox/tap-water solution, rinsed with tap water, D.I. water, and then methanol, and air dried. Sample volume will be a minimum of ~8 liters. {1-liter - Furlong, 1- liter - DuPont (via Ed Furlong), 0.625-liter - Thurman, 125-ml - NWQL nutrients, 1-liter - NWQL-2001, plus water for filter rinsing, field measurements and QC samples, if required}. All pesticide samples will be filtered through 0.7-µm pore-size baked glass-fiber filters using an aluminum plate filter holder and a ceramic piston fluid metering pump with all teflon tubing into precleaned 1-liter or 125-ml amber glass bottles. Samples will be immediately chilled and shipped on ice within two days of collection. Samples may be sun sensitive, so care should be taken to avoid exposing them to direct sunlight when possible.
Five 125-ml amber glass bottles from each site will be sent to the USGS laboratory in Lawrence, KS (shipping address below) for analysis of herbicide compounds. Two 1-liter glass bottles from each site will be sent to Ed Furlong at the NWQL in Denver (shipping address below) for SU, SA, and IMI herbicide analysis. One 1-liter glass bottle and one 125-ml polyethylene bottle will be sent to the USGS NWQL in Denver for 2001 herbicide and 2752 nutrient analysis. If nutrient and 2001 herbicide samples are already being collected (i.e. at most NAWQA or NASQAN sites) then these bottles are not needed. If possible samples should be shipped early in the week, as the Mike Thurman’s lab does not receive samples during the weekend. Also EMAIL Bill Battaglin (wbattagl@usgs.gov) and Ed Furlong (efurlong@usgs.gov) with the date and time of sample collection as soon as possible after samples are shipped. Field measurements for specific conductance, pH, and temperature will be taken for all samples and a discharge will be obtained by direct measurement, from a rating curve, or estimated from a nearby gaging station.
Sample bottles will be clearly labeled with waterproof marker or preprinted labels. The minimum information on the label will be the site id, site name, date and time of sample collection, sampler name(s), and the following phrase "USGS-DUPONT SU STUDY" as shown below:
DBD-1
05465500
Iowa River at Wapello, IA
06-18-97 @ 10:00 am
Joe Sample and Jane Stream
"USGS-DUPONT SU STUDY"
Shipping Addresses:
E. M. Thurman Ed Furlong/Mark Burkhardt U.S. Geological Survey, WRD U.S. Geological Survey 4821 Quail Crest Place National Water Quality Lab Lawrence, KS 66049 5293-B Ward Road, MS407 (913) 832-9909 Arvada, CO 80002 (303) 467-8000
Analytical Methods Methods Research and Development Program personnel at the USGS NWQL will validate and improve a routine analytical method, provided by DuPont Agricultural Products, for measuring trace (ng/L) concentration of selected SU, SA, and IMI herbicides in water samples. The method will use high performance liquid chromatography (HPLC) coupled with mass spectrometry. The analytical method to be validated was developed by DuPont as one of five methods developed in association with the EPA/Industry Multianalyte Methods (MAM) group. The DuPont method (Rodriguez and Orescan, 1996) uses electrospray LC/MS to detect 16 (table 1) SUs, SAs, and IMIs with a limit of quantification of 100 PPT for all analytes. Other analytical methods with similar or lower reporting limits for selected compounds have also been reported (Di Corcia et. al., 1997; Dinelli et. al., 1993; Nilve et. al., 1994). Improvements to the DuPont method will include (1) switching from external standard quantitation to internal standard quantitation, (2) increasing the sample size for extraction from 250 ml to 1 liter, (3) testing several new extraction media, and (4) expanding the list of target analytes to include other SU, SA, and IMI herbicides and herbicide metabolites. In addition, all samples will also be analyzed for several other classes of pesticides and for nutrients. Samples will be analyzed for 12 herbicides and 5 or more herbicide metabolites by gas chromatography/mass spectrometry (GC/MS) using methods described by Thurman et. al. (1990), Meyer et. al. (1993) and Aga et. al., (1994) by staff at the USGS lab in Lawrence, KS. This method has an analytical reporting limit of 0.05 µg/L for most analytes. Samples will be analyzed for 41 pesticides and pesticide metabolites by GC/MS with selected-ion monitoring using methods described by Zaugg and others (1995) by staff at the USGS lab in Arvada, CO. This method has analytical reporting limits that range from 0.001 to 0.018 µg/L. All samples will be analyzed for dissolved nitrite, nitrate plus nitrite, ammonia, and orthophosphate by an automated colorimetric procedure (Fishman and Friedman, 1989) by staff at the USGS lab in Arvada, CO. Between 50 and 75 samples will be analyzed using both the original DuPont method and the modified DuPont method. Splits from these samples will also be sent to DuPont for confirmatory analysis at a DuPont laboratory. Quality Assurance Quality control (QA) samples will be collected at selected sites to provide information on the variability and bias of the measured SU, SA, and IMI concentrations. These samples will consist of concurrent replicates (CR), which are two samples collected as closely as possible in time and space, but processed, handled, and analyzed separately; laboratory spikes (LS), which are collected like concurrent replicates, then spiked in the lab with a known quantity of selected target analytes, and analyzed separately; or field blanks (FB), which are blank solutions that are subject to the same aspects of sample collection, field processing, preservation, transportation, and laboratory handling as the environmental samples. Concurrent replicates will be submitted blindly to the Ed Furlong’s laboratory, while laboratory spikes and field blanks will be identified as such. Site at which QA samples will be collected are identified in table 4. QA sample will only be collected and process for the SU, SA, and IMI analysis, and not for the schedule 2001 and nutrient samples sent to the NWQL, or for the herbicide samples sent to Mike Thurman’s laboratory. Budget A proposed budget for this study is presented in table 5. Where possible, sampling has been planned in conjunction with on going NAWQA and NASQAN investigations to minimize costs and maximize information. Districts will be compensated for expenses associated with collection, processing, and shipment of samples to appropriate laboratories. The majority of costs associated with this effort will be covered by funds originating from the USGS-DuPont CRADA (Battaglin et. al., 1998). Prepared by William Battaglin, Edward Furlong, and Mark Burkhardt References
Afyuni, M.M., Wagger, M.G., and Leidy, R.B., 1997. Runoff of two sulfonylurea herbicides in relation to tillage system and rainfall intensity. J. Environ. Qual., 26:1318-1326.
Aga, D.S., Thurman, E.M., and Pomes, M.L., 1994. Determination of alachlor and its ethane-sulfonic acid metabolite in water by solid-phase extraction and enzyme-linked immunosorbent assay. Analytical Chemistry 66(9):1495-1499.
Anderson, R.L., and M.R. Barrett, 1985. Residual phytotoxicity of chlorsulfuron in two soils. J. Environ. Qual., 14(1):111-114.
Anderson, R.L., and N.E. Humburg, 1987. Field duration of chlorsulfuron bioactivity in the central great plains. J. Environ. Qual., 16(3):263-266.
Battaglin, W.A., Furlong, E.T., and Peter, C.J., 1998. A reconnaissance for sulfonylurea herbicides in waters of the midwestern USA: An example of collaboration between the public and private sectors. U.S. Geological Survey Fact Sheet FS-046-98.
Bergstrom, L., 1990. Leaching of chlorsulfuron and metsulfuron methyl in three swedish soils measured in field lysimeters. J. Environ. Qual. 19:701-706.
Blair, A.M., and Martin, T.D., 1988. A review of the activity, fate, and mode of action of sulfonylurea herbicides. Pestic. Sci., 22:195-219.
Brown, H. M., 1990. Mode of action, crop selectivity, and soil relations of the sulfonylurea herbicides. Pestic. Sci., 29:263-281.
Buckman, H.O., and Brady, N.C., 1969. The Nature and Properties of Soils. The MacMillan Company, New York, New York 653 p.
Coupe, R.H., Goolsby, D.A., Iverson, J.L., Markovchick, D.J., and Zaugg, S.D., 1995. Pesticide, nutrient, water-discharge and physical-property data for the Mississippi River and some of its tributaries, April 1991-September 1992. U.S. Geological Survey Open-File Report 93-657, 116 p.
Detroy, M.G., Hunt, P.K.B., and Holub, M.A., 1988. Ground-water-quality-monitoring program in Iowa: Nitrate and pesticides in shallow aquifers. U.S. Geological Survey Open-File Report 88-4123, 32 p.
Di Corcia, A., Crescenzi, C., Samperi, R., and Scappaticcio, L., 1997. Trace analysis of sulfonylurea herbicides in water: Extraction and purification by a carbograph 4 cartridge, followed by liquid chromatography with UV detection, and confirmatory analysis by an electrospray/ mass detector. Anal. Chem., 69:2819-2826.
Dinelli, G., Vicari, A., and Catizone, P., 1994. Use of capillary electrophoresis for detection of metsulfuron and chlorsulfuron in tap water. J. Agric. Food Chem., 41:742-746.
Dinelli, G., Vicari, A., Bonetti, A., and Catizone, P., 1997. Hydrolytic dissipation of four sulfonylurea herbicides. J. Agric. Food Chem., 45:1940-1945.
Edwards, T.K. and Glysson, D.G., 1988. Field methods for measurement of fluvial sediment. U.S. Geological Survey OFR 86-531, 118 p.
Fishman, M.J. and Friedman, L.C., 1989. Methods for determination of inorganic substances in water and fluvial sediments. U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, chap. A1, 545 p.
Fletcher, J.S., Pfleeger, T.G., and Ratsch, H.C., 1993. Potential environmental risks associated with the new sulfonylurea herbicides. Environ. Sci. Technol. 27(10):2250-2252.
Flury, M., Leuenberger, J., Studer, B., and Fluhler, H., 1995. Transport of anions and herbicides in a loamy and a sandy field soil. Water Resources Research 31(4):823-835.
Goolsby, D.A., Boyer, L.L., and Battaglin, W.A., 1994. Plan of study to determine the effect of changes in herbicide use on herbicide concentrations in midwestern streams, 1989-94. U.S. Geological Survey Open-File Report 94-347, 14 p.
Harvey, J., Dulka, J.J., and Anderson, J.J., 1985. Properties of sulfometuron methyl affecting its environmental fate: Aqueous hydrolysis and photolysis, mobility and adsorption on soils, and bioaccumulation potential. Journal of Agricultural and Food Chemistry 33:590-596.
Kolpin, D.W., Burkart, M.R., and Thurman, E.M., 1994. Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991. U.S. Geological Survey Water-Supply Paper 2413, 34 p.
Kolpin, D.W., Kalkhoff, S.J., Goolsby, D.A., Sneck-Fahrer, D.A., and Thurman, E.M., 1997. Occurrence of selected herbicides and herbicide degradation products in Iowa’s ground water, 1995. Ground Water 35(4):679-688.
Meister, R.T., 1995. Farm Chemicals Handbook’95. Meister Publishing Company, Willoughby, OH
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|
Common name |
Class |
Trade names1 |
Crops Treated |
|
bensulfuron methyl |
sulfonylurea |
Londax |
rice |
|
chlorimuron ethyl |
sulfonylurea |
Classic, Canopy, Reliance |
soybeans, peanuts |
|
chlorsulfuron |
sulfonylurea |
Glean, Telar, Finesse |
grains, CRP |
|
flumetsulam |
sulfonamide |
Broadstrike, Preside, Scorpion |
corn, soybeans |
|
halosulfuron methyl |
sulfonylurea |
Battalion, Manage, Permit |
corn, sorghum, turf |
|
imazapyr |
imidazolinone |
Arsenal, Chopper |
noncropland |
|
imazaquin |
imidazolinone |
Scepter, Detail |
soybeans |
|
imazethapyr |
imidazolinone |
Pursuit |
soybeans, corn |
|
metsulfuron methyl |
sulfonylurea |
Allie, Ally, Escort |
grains, pasture, noncrop |
|
nicosulfuron |
sulfonylurea |
Accent |
corn |
|
primisulfuron methyl |
sulfonylurea |
Beacon, Tell |
corn |
|
prosulfuron |
sulfonylurea |
Peak |
corn, sorghum, grains |
|
sulfometuron methyl |
sulfonylurea |
Oust |
trees, noncrop, turf |
|
thifensulfuron methyl |
sulfonylurea |
Pinnacle, Reliance |
soybeans, grains, corn |
|
triasulfuron |
sulfonylurea |
Amber, Logran |
grain, fallow |
|
triflusulfuron methyl |
sulfonylurea |
Upbeet |
sugarbeets |
1Any use of trade, product, or firm names in this publication is for descriptive purposes only and does not imply endorsement by the U.S. Government.
|
No |
Site id |
Site name |
Site type |
Basin area (mi2) |
Latitude |
Longitude |
|
1 |
03378000 |
Bonpas Creek at Browns, IL |
MHI |
228 |
382311 |
875832 |
|
2 |
03378500 |
Wabash River at New Harmony, IN |
NASII |
29,234 |
380755 |
875625 |
|
3 |
03381495 |
Little Wabash River at Carmi, IL |
MHI |
3,088 |
380532 |
880922 |
|
4 |
05439500 |
S. Branch Kishwaukee River near Fairdale, IL |
MHI |
387 |
420640 |
885400 |
|
5 |
05526000 |
Iroquois River near Chebanse, IL |
MHI |
2,091 |
410032 |
874927 |
|
6 |
05540500 |
Dupage River near Shorwood, IL |
MHI |
324 |
413120 |
881135 |
|
7 |
05543500 |
Illinois River at Marseilles, IL |
NAWQA |
8,259 |
411940 |
884310 |
|
8 |
05569500 |
Spoon River at London Mills, IL |
MHI |
1,072 |
404232 |
901653 |
|
9 |
05572000 |
Sangamon River near Monticello, IL |
NAWQA |
550 |
400151 |
883520 |
|
10 |
05576500 |
Sangamon River at Riverton, IL |
MHI |
2,618 |
395034 |
893252 |
|
11 |
05584500 |
LaMoine River at Colmar, IL |
NAWQA |
655 |
401945 |
905355 |
|
12 |
05586100 |
Illinois River at Valley City, IL |
NAWQA |
26,742 |
394212 |
903846 |
|
13 |
05587455 |
Mississippi River below Grafton, IL |
NASII |
171,300 |
385704 |
902216 |
|
14 |
05592100 |
Kaskaskia River near Cowden, IL |
MHI |
1,330 |
391350 |
885033 |
|
15 |
05594000 |
Shoal Creek near Breese, IL |
MHI |
735 |
383635 |
892940 |
|
16 |
03338890 |
Vermillion River north of Danville, IL (just below Lake Vermillion dam, IL05) |
Reservoir |
298 |
400924 |
873906 |
|
17 |
05411600 |
Turkey River at Spillville, IA |
MHI |
177 |
431228 |
915656 |
|
18 |
05420500 |
Mississippi River at Clinton, IA |
NASII |
85,600 |
414650 |
901507 |
|
19 |
05420680 |
Wapsipinicon River near Tripoli, IA |
NAWQA |
343 |
425010 |
921526 |
|
20 |
05421000 |
Wapsipinicon River at Independence, IA |
MHI |
1,048 |
422749 |
915342 |
|
21 |
05449500 |
Iowa River near Rowan, IA |
NAWQA |
429 |
424536 |
933723 |
|
22 |
05455100 |
Old Mans Creek near Iowa City, IA |
MHI |
201 |
413623 |
913656 |
|
23 |
05464220 |
Wolf Creek near Dysart, IA |
NAWQA |
299 |
421506 |
921755 |
|
24 |
05465500 |
Iowa River at Wapello, IA |
NAWQA |
12,499 |
411041 |
911055 |
|
25 |
05472500 |
N. Skunk River near Sigourney, IA |
MHI |
730 |
411803 |
921216 |
|
26 |
05474000 |
Skunk River at Augusta, IA |
MHI |
4,303 |
404513 |
911640 |
|
27 |
05480500 |
Des Moines River at Fort Dodge, IA |
MHI |
4,190 |
423022 |
941204 |
|
28 |
05484500 |
Raccoon River at Van Meter, IA |
MHI |
3,441 |
413202 |
935659 |
|
29 |
06606600 |
Little Sioux River at Correctionville, IA |
MHI |
2,500 |
422820 |
954749 |
|
30 |
06607200 |
Maple River at Mapleton, IA |
MHI |
669 |
420925 |
954835 |
|
31 |
06609500 |
Boyer River at Logan, IA |
MHI |
871 |
413833 |
954657 |
|
32 |
06903900 |
Chariton River near Rathbun, IA (just below Rathbun Lake dam, IA01) |
Reservoir |
549 |
404922 |
925322 |
|
33 |
03275000 |
Whitewater River near Alpine, IN |
MHI |
522 |
393446 |
850929 |
|
34 |
03302800 |
Blue River at Fredricksburg, IN |
MHI |
283 |
382602 |
861131 |
|
35 |
03327000 |
Mississinewa River at Peoria, IN (just below Mississinewa Lake dam, IN06) |
Reservoir |
808 |
404324 |
855727 |
|
36 |
03328500 |
Eel River near Logansport, IN |
MHI |
789 |
404655 |
861550 |
|
37 |
03333450 |
Wildcat Creek near Jerome, IN |
MHI |
146 |
402629 |
855508 |
|
38 |
03335000 |
Wildcat Creek near Lafayette, IN |
MHI |
243 |
402504 |
864605 |
|
39 |
03351000 |
White River near Nora, IN |
MHI |
1,219 |
395435 |
860620 |
|
40 |
03362500 |
Sugar Creek near Edinburgh, IN |
MHI |
474 |
392139 |
855951 |
|
41 |
03371500 |
E. Fork White River near Bedford, IN |
MHI |
3,861 |
384610 |
862430 |
|
42 |
05317000 |
Cottonwood River near New Ulm, MN |
MHI |
1,280 |
441729 |
942624 |
|
43 |
05320270 |
Little Cobb River near Beauford, MN |
NAWQA |
130 |
435900 |
935200 |
|
44 |
05330000 |
Minnesota River near Jordan, MN |
NAWQA |
16,200 |
444135 |
933830 |
|
45 |
05331580 |
Mississippi River at Hastings, MN |
NAWQA |
37,050 |
444448 |
925108 |
|
46 |
05476000 |
Des Moines River at Jackson, MN |
MHI |
1,220 |
433710 |
945910 |
|
47 |
06483000 |
Rock River at Luverne, MN |
MHI |
425 |
433915 |
961203 |
|
48 |
06885500 |
Black Vermillion River at Frankfort, KS |
MHI |
410 |
394103 |
962615 |
|
49 |
06887000 |
Big Blue River at Manhattan, KS (downstream from Tuttle Creek Lake dam) |
Reservoir |
9,628 |
391516 |
963608 |
|
50 |
06890100 |
Delaware River near Muscotah, KS |
MHI |
431 |
393117 |
953157 |
|
51 |
06817700 |
Nodaway River near Graham, MO |
MHI |
1,320 |
401208 |
950407 |
|
52 |
06770195 |
North Dry Creek near Kearney, NE |
NAWQA |
~40 |
403600 |
990830 |
|
53 |
06800000 |
Maple Creek near Nickerson, NE |
NAWQA |
450 |
413339 |
963227 |
|
54 |
06803000 |
Salt Creek at Roca, NE |
MHI |
167 |
403929 |
963955 |
|
55 |
06804000 |
Wahoo Creek at Itica, NE |
MHI |
271 |
410840 |
963210 |
|
56 |
06805500 |
Platte River at Louisville, NE |
NASII |
6,800 |
410055 |
960928 |
|
57 |
06815000 |
Big Nemaha River at Falls City, NE |
MHI |
1,340 |
400208 |
953545 |
|
58 |
06880800 |
W. Fork Big Blue River, Dorchester, NE |
MHI |
1,206 |
404352 |
971038 |
|
59 |
06882000 |
Big Blue River at Barneston, NE |
MHI |
4,447 |
400240 |
963512 |
|
60 |
06884000 |
Little Blue River near Fairbury, NE |
MHI |
2,350 |
400654 |
971013 |
|
61 |
03157000 |
Clear Creek near Rockbridge, OH |
MHI |
89 |
393518 |
823443 |
|
62 |
03219500 |
Scioto River near Prospect, OH |
MHI |
567 |
402510 |
831150 |
|
63 |
03223000 |
Olentangy River at Claridon, OH |
MHI |
157 |
403458 |
825920 |
|
64 |
03225500 |
Olentangy River near Delaware, OH (just below Delaware Lake dam, OH01) |
Reservoir |
393 |
402118 |
830402 |
|
65 |
03230500 |
Big Darby Creek at Darbyville, OH |
MHI |
534 |
394202 |
830637 |
|
66 |
03234500 |
Scioto River at Higby,OH |
MHI |
5,131 |
391244 |
825150 |
|
67 |
03240000 |
L. Miami River near Oldtown, OH |
MHI |
129 |
394454 |
835553 |
|
68 |
03267900 |
Mad River at Eagle City, OH |
MHI |
310 |
395751 |
834954 |
|
69 |
03303280 |
Ohio River at Cannelton Dam, KY |
NASII |
97,000 |
375358 |
864220 |
|
70 |
04185000 |
Tiffin River at Stryker, OH |
NAWQA |
410 |
413016 |
842547 |
|
71 |
04186500 |
Auglaize River at Fort Jennings, OH |
NAWQA |
332 |
405655 |
841558 |
|
72 |
04087240 |
Root River at Racine, WI |
MHI |
190 |
424505 |
874925 |
|
73 |
05340500 |
St. Croix River at St. Croix Falls, WI |
MHI |
6,240 |
452425 |
923849 |
|
74 |
05407000 |
Wisconsin River at Muscoda, WI |
MHI |
10,400 |
431154 |
902626 |
|
75 |
05430500 |
Rock River at Afton, WI |
MHI |
3,340 |
423633 |
890414 |
|
State |
Site id |
Site name |
Depth to the top of the screen in feet |
Latitude |
Longitude |
|
IL |
1 |
LUS1-4 |
15.5 |
410502 |
893925 |
|
IL |
2 |
LUS1-14 |
24.0 |
404603 |
885635 |
|
IL |
3 |
LUS1-26 |
8.33 |
403759 |
884226 |
|
IL |
4 |
LUS2 - 9 |
12.50 |
401327 |
890252 |
|
IL |
5 |
LUS2 - 22 |
7.66 |
395853 |
883644 |
|
IA |
6 |
Blockton 1 |
271 |
403659 |
942853 |
|
IA |
7 |
Fort Madison 4 |
147 |
403745 |
911747 |
|
IA |
8 |
Shambaugh 3 |
30 |
403906 |
950150 |
|
IA |
9 |
Nodaway 4 |
36 |
405632 |
945344 |
|
IA |
10 |
Silver City 3 |
60 |
410656 |
953802 |
|
IA |
11 |
Carson (5), 3 |
28 |
411501 |
952513 |
|
IA |
12 |
Cumberland 1 |
155 |
411622 |
945209 |
|
IA |
13 |
Fontanelle 5 |
39 |
411727 |
943740 |
|
IA |
14 |
Menlo 3 |
20 |
412852 |
942751 |
|
IA |
15 |
Carlisle 5 |
30 |
413040 |
932905 |
|
IA |
16 |
Newton 13 |
45 |
413913 |
930700 |
|
IA |
17 |
Belle Plaine 4 |
42 |
415417 |
921801 |
|
IA |
18 |
Cedar Rapids S6 |
65 |
420005 |
914312 |
|
IA |
19 |
Vail 1 |
32 |
420336 |
951156 |
|
IA |
20 |
Marshalltown 8 |
223 |
420405 |
925456 |
|
IA |
21 |
Boone 20 |
63 |
420451 |
935613 |
|
IA |
22 |
Boxholm 2 |
49 |
421025 |
940630 |
|
IA |
23 |
Holstein 3 |
54 |
422915 |
953235 |
|
IA |
24 |
Kingsley 1 |
37 |
423537 |
955839 |
|
IA |
25 |
Sheffield 2 |
27 |
425341 |
931325 |
|
No |
Site id |
Site name |
First sample |
Second sample |
|
1 |
03378500 |
Wabash River at New Harmony, IN |
CR |
|
|
2 |
05526000 |
Iroquois River near Chebanse, IL |
CR |
|
|
3 |
05540500 |
Dupage River near Shorwood, IL |
LS |
|
|
4 |
05569500 |
Spoon River at London Mills, IL |
FB |
|
|
5 |
05584500 |
LaMoine River at Colmar, IL |
CR |
|
|
6 |
05594000 |
Shoal Creek near Breese, IL |
CR |
|
|
7 |
05420680 |
Wapsipinicon River near Tripoli, IA |
FB |
|
|
8 |
05464220 |
Wolf Creek near Dysart, IA |
LS |
|
|
9 |
05480500 |
Des Moines River at Fort Dodge, IA |
CR |
|
|
10 |
06607200 |
Maple River at Mapleton, IA |
LS |
|
|
11 |
06890100 |
Delaware River near Muscotah, KS |
FB |
|
|
12 |
03275000 |
Whitewater River near Alpine, IN |
LS |
|
|
13 |
03328500 |
Eel River near Logansport, IN |
FB |
|
|
14 |
05317000 |
Cottonwood River near New Ulm, MN |
CR |
|
|
15 |
05331580 |
Mississippi River at Hastings, MN |
CR |
|
|
16 |
06800000 |
Maple Creek near Nickerson, NE |
LS |
|
|
17 |
06805500 |
Platte River at Louisville, NE |
CR |
|
|
18 |
06882000 |
Big Blue River at Barneston, NE |
FB |
|
|
19 |
03223000 |
Olentangy River at Claridon, OH |
FB |
|
|
20 |
03225500 |
Olentangy River near Delaware, OH (just below Delaware Lake dam, OH01) |
CR |
|
|
21 |
04185000 |
Tiffin River at Stryker, OH |
CR |
|
|
22 |
05407000 |
Wisconsin River at Muscoda, WI |
LS |
|
|
23 |
2 |
LUS1-14 |
CR |
|
|
24 |
10 |
Silver City 3 |
CR |
|
|
25 |
17 |
Belle Plaine 4 |
LS |
|
|
26 |
24 |
Kingsley 1 |
FB |
|
Task/analysis |
Expected Cost |
|
|
FY98 |
FY99 |
|
|
work plan development and implementation |
9,600 |
- |
|
sample collection |
60,000 |
- |
|
sample analysis - SUs, SAs, and IMIs |
100,000 |
20,000 |
|
sample analysis - 2001 150 @ $323.93 |
48,560 |
- |
|
sample analysis - nutrients 150 @ $101.56 |
15,234 |
- |
|
sample analysis - Thurman 150 @$300 |
30,000 |
15,000 |
|
supplies/equipment |
10,000 |
|
|
travel/other |
5,000 |
5,000 |
|
data analysis/reports preparation |
1,200 |
9,600 |
Appendix 1 -- Sample collection and processing instructions
Determining where and when to sample:
(1) Determine which sites are to be sampled in your State from tables 2 and 3.
(2) Determine which sites are to have QA samples collected from table 4.
(3) Follow news on progress of planting and weather (Battaglin will provide weekly data).
(4) Collect the first surface-water samples at NAWQA and MHI sites after pre-emergence herbicides have been applied (usually May or June) when corn is at least 50% planted and following a precipitation event that produces a significant increase in streamflow. Ideally, streamflow should be representative of runoff conditions with flow at or above the 50th percentile, which is equal to the "50 percent exceeds" flow value for the period of record, published for most sites in State USGS Water Resources Data reports.
(6) Continue to follow news on progress of plant development and weather.
(7) Collect the second surface-water samples at NAWQA and MHI sites after post-emergence herbicides have been applied (usually June or July) and corn is 100% emerged and again following a precipitation event that produces runoff conditions and streamflows at or above the 50th percentile.
(8) Collect the first NASQAN or reservoir samples in May or June, 2-3 weeks after the first surface-water samples were collected from nearby sites.
(9) Collect the second NASQAN or reservoir samples in June or July, 2-3 weeks after the second surface-water samples were collected from nearby sites.
(10) Collect ground water samples in July or August.
Sample Collection
(1) Preclean all equipment with a Liquinox/tap-water solution, rinsed with tap water, D.I. water, and then methanol, and then air dry.
(2) Collect and composite a minimum of ~8 liters of water using equal-width-increment sampling on smaller rivers or equal-discharge-increment sampling on larger rivers into a large pre-cleaned glass carboy.
(3) filter 2 liters of sample water through a 0.7-µm pore-size baked glass-fiber filter using an aluminum plate filter holder and a ceramic piston fluid metering pump with all teflon tubing into 2 precleaned 1-liter amber glass bottles after first leaching filter with 200 ml of sample. These bottles will be shipped to Ed Furlong at the NWQL in Denver (see address below) for analysis of SU, SA, and IMI herbicides. Fill out a separate ARS form for this sample using the example in appendix 2 as a guide.
(4) filter 0.625 liters of sample water through a 0.7-µm pore-size baked glass-fiber filter after a 100 ml rinse of the filter with sample water, into five 125-ml baked amber glass bottles. These bottles will packed on ice and shipped to the USGS laboratory in Lawrence, KS (see address below) for analysis of herbicide compounds.
(5) If the site or well is NOT one where regular NAWQA or NASQAN samples are being collected then process one liter of sample for a schedule 2001 pesticide analysis and 125- ml of sample for a schedule 2752 nutrient analysis (use one 125 mL brown polyethylene bottle, sample is filtered and chilled to preserve) using the standard procedures. These bottles will be sent to the USGS NWQL in Denver for analysis. Only collect these samples if they are NOT being collected concurrently as part of other sampling activities. Fill out a separate ARS form for these samples and charge the project account number 4600-31800 for the analyses. These samples and the 2 liters for Ed Furlong can be shipped to the NWQL in the same cooler.
6) Label all sample bottles clearly with waterproof marker or preprinted labels (a paper label completely covered with clear packing tape is preferred). The minimum information on the label for bottles sent to the Ed Furlong and Mike Thurman at the NWQL will be the project code, site id, site name, date and time of sample collection, sampler name(s), and the phrase "USGS-DUPONT SU STUDY" as shown below:
Project code and round number (1 or 2) DBD-1
station id 05465500
stream name/location Iowa River at Wapello, IA
date and time 06-18-98 @ 1015
sampler name/initials Joe Sample and Jane Stream
USGS-DUPONT SU STUDY
(7) Collect and record field measurements including specific conductance, pH, and temperature for all samples and obtain a discharge by direct measurement, a rating curve, or an estimate from a nearby gaging station.
(8) All samples will be immediately chilled and will be shipped on ice as soon as possible after collection. Samples may be sensitive to the sun, so care should be taken to avoid exposing them to direct sunlight when possible. If possible samples should be shipped early in the week, as Ed Furlong and Mike Thurman’s laboratories do NOT receive samples during the weekend.
(9) EMAIL Bill Battaglin (wbattagl@usgs.gov) and Ed Furlong (efurlong@usgs.gov) with the date and time of sample collection as soon as possible after samples are shipped.
In the NWQL Laboratory
(10) Samples will be logged in and a running sequence number assigned (i.e. SU-1, SU-2, etc.). All even numbered samples will be analyzed using both the original DuPont method and the modified DuPont method.
(11) NWQL staff will prepare and chill 0.5 liter splits of the even numbered samples. These samples will be clearly labeled with the sequence number and shipped overnight express to DuPont (see address below) weekly on Tuesdays.
E. M. Thurman Ed Furlong
U.S. Geological Survey U.S. Geological Survey 4821 Quail Crest Place National Water Quality Lab Lawrence, KS 66049 5293-B Ward Road, MS407 (913) 832-9909 Arvada, CO 80002 (303) 467-8000
DuPont Ag Products
Experiment Station Rt 141 Bldg. 402, Dock 1 Wilmington, Del. 19880-0402 Attn. Dave Orescan (contact Al Mesina, Shipping and Receiving, 302-695-3957 prior to shipping samples)
Figure titles