Surface Drinking Water Assessment and Monitoring for Oxadiazon

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Chapter 5

Surface Drinking Water Assessment and Monitoring for Oxadiazon Herbicide on Golf Courses Ujjana B. Nandihalli, Russell L. Jones, Richard Allen, Tharacad S. Ramanarayanan, and George J. Sabbagh Bayer CropScience, 17745 South Metcalf, Stilwell, KS 66085

Modeling and drinking water monitoring studies were conducted to determine potential dietary exposure to oxadiazon as a result of its use on golf courses. As part of their Reregistration Eligibility Decision, the United States Environmental Protection Agency (USEPA) performed a worst case exposure estimation using the PRZM/EXAMS Index Reservoir model, assuming a maximum oxadiazon application rate (8.96 kg a.i/ha) and resulting in an acute potential exposure of 181 ppb and a long term mean of annual concentrations in drinking water of up to 56 ppb. A refined drinking water exposure assessment was conducted by the authors using the same modeling tools, but adopting more realistic assumptions reflecting that 90% of the product is used as a granular formulation, with typical use rates of 6.72 kg a.i./ha. In addition, a GIS evaluation of land use in Florida determined that golf courses represented a maximum of 6% of the surface area in watersheds. These and other refinements resulted in reductions in the estimated concentrations of over two orders of magnitude. To confirm the refined exposure assessments, a three-year surface water monitoring program was established in Florida and North Carolina to measure the potential for oxadiazon to reach surface drinking water sources in three community water systems, with the highest use of oxadiazon. Residues were detected in raw water in two of the three community water systems and in finished water in one. However the maximum observed concentrations from the monitoring program were more than three orders of magnitude © 2009 American Chemical Society In Turf Grass: Pesticide Exposure Assessment and Predictive Modeling Tools; Nett, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.

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lower than the acute drinking water concentration originally estimated and about 25 times lower than the refined assessment. These differences are associated with the assumptions concerning actual use in the watershed, spray drift and persistence of residues in the reservoir. The monitoring program also demonstrated that oxadiazon can be removed in drinking water treatment systems.

The Food Quality Protection Act (FQPA) mandated that risk contributions from the presence of pesticides in drinking water should be included in the overall human health risk assessment. The USEPA has been utilizing predictive models for estimating potential upper bound concentrations of pesticides in surface waters used as a source of drinking water. The linked PRZM/EXAMS model is commonly used by the agency as part of the screening process to assess the potential for drinking water-related exposures that may exceed the human health level of concern. Oxadiazon is an herbicide which is used on golf courses to control grassy weeds. This chapter describes (a) the drinking water exposure assessment for oxadiazon by USEPA, (b) the refined exposure assessment by the authors, and (c) surface water monitoring for oxadiazon residues.

Drinking Water Exposure Assessment by USEPA As part of a Reregistration Eligibility Document (RED), the USEPA performed a Tier II PRZM/EXAMS simulation using the Florida turf scenario, the Index Reservoir and the Percent Crop Area (PCA) adjustment to predict concentrations of oxadiazon in surface water that serve as a source of drinking water (1). Input parameters are summarized in Table I. PCA adjusting factors from the EFED guidance document for the turf scenario were used (2). The PCA values were 0.04 for golf course greens and tees, 0.23 for fairways, and 0.67 for roughs. The predicted concentrations from the model were multiplied by the PCA factor to arrive at the final Estimated Drinking Water Concentrations (EDWC) for each segment of turf. An example calculation is shown below (EEC = Estimated Environmental Concentration): Cancer Chronic EEC = (Mean of annual value) × (PCA tees & greens) = (52.56 µg/L) × (0.04) = 2.1 µg/L USEPA calculated EDWC values in surface water are as shown in Table II.

In Turf Grass: Pesticide Exposure Assessment and Predictive Modeling Tools; Nett, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2010.

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Table I. Simulation Paramaters Used by USEPA Parameters and Units Molecular weight (g mole-1) Vapor pressure (torr) Water solubility (mg L-1) Hydrolysis half-life at pH 5 (days) Hydrolysis half-life at pH 7 (days) Hydrolysis half-life at pH 9 (days) Aerobic soil metabolism half-life (days) Aerobic aquatic metabolism half-life (days) Anaerobic aquatic metabolism half-life (days) Direct aqueous photolysis (days) Soil water partition coefficient, Koc (L kg-1) Pesticide application rate, first application (kg ai/ ha) Pesticide application rate, second application (kg ai/ ha) Pesticide application rate, third application (kg ai/ ha) Date of first pesticide application Interval between first and second pesticide application (days) Interval between second and third pesticide application (days) Spray efficicieny (percent) Spray drift (percent)

Value Used 345.2 1.0 E-6 1.0† Stable Stable 38 841* 1682** 365 2.75 2352 2.24 2.24 4.48 March 15 30 135 99 6.40

† Measured water solubility was multiplied by 10 according to (2). * Meaured value was multiplied by 3 according to (2). ** Used two times the input value for the soil aerobic metabolism half-life according to (2).

Table II. Estimated Drinking Water Concentrations for Oxadiazon Calculated by USEPA Exposure Acute (90th percentile) Non-Cancer Chronic (90th percentile annual value) Cancer Chronic (mean 36year annual concentration)

Greens & Tees

Fairways

Roughs

Golf Course

7.7

44.3

128.7

180.6

2.8

15.9

46.2

64.9

2.1

18.6

35.2

56.0

Note: Units are µg/L (ppb) Source: Reference 1.


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Refined Drinking Water Exposure Assessment A refined drinking water exposure assessment was conducted by the authors using the same modeling tools as the USEPA, but adopting more realistic assumptions for product use. Oxadiazon is predominantly applied to golf course tees, greens, and fairways and therefore inclusion of roughs in the model would overestimate the predicted concentration. Over 90% of oxadiazon product is applied in granular formulation, and therefore spray drift should not be considered as a contributing factor. Also, a typical annual oxadiazon application rate is 6.72 kg. a.i/ha or less instead of the 8.96 lb. ai/ha that was applied in the USEPA assessment. Finally, the PCA assumptions used in the USEPA model are believed to be unrealistic, in the sense that they assume that 100% of the watershed area is covered with golf course. In the refined assessment, PCA factors were computed for surface water intakes in Florida using the Geographic Information System (GIS). Florida has the highest concentration of golf courses in the country and GIS technique would provide the most likely maximum PCA factor for golf course. The PCA factors were calculated in two different ways: • Land Cover: Area of recreational grasses class (includes golf courses) from National Land Cover Datasets (NLCD), divided by the watershed area. • Golf Course Yardage: Areas of fairways in the watershed divided by the watershed area (area was calculated by mulitpling the yards of fairways in the watershed and an average width of 25 yards and then an additional 25 percent of the total was added to be conservative). Golf courses in Florida and their yardage were identified from two sources, including the CNN/Sports Illustrated website. The maximum PCA was computed to be 5.77% (3). The EEC results (i.e. EECunadj) predicted by PRZM/EXAMS for each exposure were multiplied by PCA factors as follows. Golf course: [EECunadj] × 0.0577 Greens and tees: [EECunadj] × 0.0577 × 0.04 Fairways: [EECunadj] × 0.0577 × 0.23 Greens, tees, and fairways: [EECunadj] × 0.0577 × 0.27 The EDWCs from USEPA assessments were compared with the refined assessment for water supplies in Florida associated with oxadiazon use on golf course (Table III). The values represent the sum of greens, tees, and fairways only; oxadiazon application to roughs is insignificant.


61 Table III. Comparison of EDWCs Between USEPA Assessment and Refined Assessment


Simulation USEPA simulation (8.96 kg ai/ha)

Acute

Non-Cancer

Cancer Chronic

52.0

18.6

20.7

USEPA assessment with refined PCA

3.00

1.08

0.82

Refined assessment without drift (8.96 kg ai/ha)

2.62

0.91

0.61

Refined assessment without drift (6.72 kg ai/ha)

2.23

0.62

0.44

Note: Units are in µg/L (ppb). Source: Reference 3

Surface Water Monitoring To validate the predictions of the refined assessment, a surface water monitoring program with two sites in Florida and one site in North Carolina was instituted. The principal criteria used in the selection of sites were product sales by state, geographical distribution within the state and percent crop area within watersheds. Based on 2000-2001 oxadiazon sales by state, 27.8% of total sales in the U.S. occurred in Florida and North Carolina. The Florida sites were chosen because Florida is the state with the highest sales of RONSTAR® herbicide. Two community water systems (CWS) were chosen in Florida, the West Palm Beach CWS on the east coast and the City of Bradenton CWS on the west coast. These two locations are representative of community water system watersheds with a high intensity of golf courses, and they are the only sites where the watersheds are used continually to supply water and the PCA of golf courses exceeded one percent with both estimation procedures. The West Palm Beach CWS draws water from Clear Lake in Palm Beach County, which is supplied by a system consisting of a catchment area which captures rainfall and also stores water pumped from M-canal, which flows from Lake Okeechobee. A map showing intake location, golf course distribution and hydrology is presented in Figure 1. The Bradenton CWS draws water from Lake Ward in Manatee County, which is a relatively small reservoir on the Bradenton River. Specific watershed data and golf course information are presented in Table III. A map showing intake location, golf course distribution, and hydrology is presented in Figure 2. The Thomasville CWS in North Carolina was selected because it had the second highest PCA in the region. The City of Thomasville water treatment


62 plant draws water from Tom-A-Lex Lake. A map showing intake location and golf course distribution is presented in Figure 3. Specific watershed data and golf course information for all three sites are presented in Table IV.


Sampling and Residue Analysis Raw surface water and finished drinking water samples were collected either weekly (Bradenton and Thomasville) or bi-monthly (West Palm Beach). Initially, raw water samples were analyzed and finished water samples were analyzed only when oxadiazon residues were detected in the corresponding raw water sample. The residue analysis was performed by LC/MS/MS for oxadiazon parent only. The method detection limit was 0.01 ppb (µg/L) and the limit of quantification was 0.03 ppb.

Table IV. Specific Watershed Data

Intake

Treatment Plant

Land Cover PCA (%)

Yardage Watershed Number of PCA (%) Area (ha) Golf Courses

Lake Ward at City of Bradenton, FL Bradenton

5.54

1.24

14,200

5

Clear Lake at City of West West Palm Palm Beach Beach, FL

4.37

1.03

52,300

21

Not Available

0.46

14,600

4

Tom-A-Lex Lake at Thomasville, NC

City of Thomasville



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Clear Creek Legend Golf Course Surface Water Intake

±

Hydrology Lake / Pond Reservoir Stream / River NLCD Recreational Grasses HUC 18 0

1.25

2.5

5

Miles 7.5

Figure 1. Watershed map of West Palm Beach Community Water System. (see page 1 of color insert)



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Ward Lake Legend Golf Course

± 0

Surface Water Intake Hydrology Lake / Pond Stream / River

1

2

4

Miles 6

NLCD Recreational Grasses HUC 18

Figure 2. Watershed map of Bradenton Community Water System. (see page 2 of color insert)

Intake Golf course Hydrology Watershed boundary

Figure 3. Watershed map of Thomasville Community Water System. (see page 3 of color insert)


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Results The results of the three year monitoring program are summarized in Table V by year and by community water system. Residues of oxadiazon were not detected in raw water in the West Palm Beach community water system. Residues of oxadiazon were present in the raw water of the Bradenton community water system, but not in the finished. Residues of oxadiazon were present in both raw and finished water in the Thomasville community water system. The finding of residues in finished water in Thomasville but not Bradenton likely results from an activated carbon treatment step that is included at Bradenton but not at Thomasville. Figures 4 and 5 show the oxadiazon concentrations as a function of time at Bradenton and Thomasville.

Table V. Summary of Monitoring Results

Year

Raw Water

Finished Water

Time-Weighted Average (ppb) in Finished Water

1

0.059

0.005*

0.005*

2

0.175

0.005*

0.005*

3

0.086

0.005*

0.005*

1

0.005*

Not analyzed**

Not applicable

2

0.005*

Not analyzed**

Not applicable

3

0.005

Not analyzed**

Not applicable

1

0.170

0.127

0.025

2

0.049

0.047

0.013

3

0.051

0.055

0.015

Peak Residue Concentration (ppb) Site Name Bradenton, FL

West Palm Beach, FL

Thomasville, NC

* Residues were non-detectable (i.e.

Surface Drinking Water Assessment and Monitoring for Oxadiazon

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