Final Draft Sensitivity of Ecological Risk Assessment to Model Parameters Masters of Engineering Report Jeffrey S. Paley Department of Biological and Environmental Engineering Cornell University, Ithaca, NY 5/12/2011 EXECUTIVE SUMMARY: Ecological risk assessments employ mathematical fate and transport models to estimate pesticide concentrations in the environment. Results are highly based upon input data, yet the sensitivity of such models to specific parameters is unknown. The purpose of this study is to investigate the sensitivity of one such model, TPQPond (Haith, 2010), a model of pesticide runoff and subsequent accumulation in a receiving pond from various types of grass surfaces. The analysis was based on one-in-10 year maximum pond concentrations of 38 different pesticides from 100 year simulations. The simulations were conducted for nine geographic locations and three golf course surface types. These concentrations are then compared to toxicity endpoints of target species (invertebrates, fish, plants, and algae). Seven input parameters were modified in order to create a range of values over which calculated risk quotients could be compared to the original values. It was determined that the model was most sensitive to changes in pond depth and turf organic carbon content. It was moderately sensitive to pond half life and turf organic carbon content values and mildly sensitive to changes in the application dates. Changes in values for minimum pond volume did not affect the calculated risk quotients, and, due to the high carbon content, both high and low modification of total suspended solids led to decreases in risk quotients. Based on these findings, it is important to choose values for input parameters carefully for a given risk assessment as small changes in parameter values that the model is sensitive to can have significant impacts on the results of the assessment. CHAPTER 1: INTRODUCTION Ecological risk assessments of pesticides are performed using mathematical fate and transport models that estimate pesticide concentrations in receiving waters. By comparing these concentrations to toxicity endpoints (LC50, EC50) of selected species, the threat posed by the pesticide in the runoff can be analyzed (Haith, 2010). Although the quantitative results may imply a high degree of precision, the results depend heavily on the input data used in the simulations. The sensitivity of the model to these parameters is largely unknown and the purpose of this study is to examine the extent to which ecological risks are modified by altering the input parameters. This study had two 2 goals: one was to determine the likely range of values for parameters and data used in modeling pesticide runoff from grassed surfaces and associated impacts to receiving waters and the other was to identify model parameters and data which have the largest impacts on ecological risk assessment of pesticide runoff from grassed surfaces. CHAPTER 2: METHODS: This work builds upon a previous paper (Haith and Rossi, 2003) in which the TurfPQ model was used to determine runoff susceptibility of turf pesticides, assess the severity of the pollution hazards to aquatic organisms, and to evaluate importance of regional weather variations on runoff loads and concentrations. It was found that runoff varied greatly depending on the geographic location as well as the surface due to differences in winter precipitation and soil permeability. Concentrations in these runoffs frequently exceeded the toxicity endpoints for water fleas and rainbow trout but without a method to model the receiving water it is difficult to determine the true threat posed by the pesticide in the runoff. A subsequent paper (Haith, 2010) extended the work through use of TPQPond, a model which combined the pesticide runoff calculations of TurfPQ with a simulation of pesticide and water mass balances in a receiving pond. Pond pesticide concentrations were used in an ecological risk assessment of 38 turf pesticides for 3 surfaces in 9 U.S. locations. This risk assessment formed the basis of the current study, which determined the sensitivity of the risk assessment results to variations in selected model input parameters. Risks were evaluated for four types of aquatic target species: invertebrates, fish, plants, and algae. An acute risk quotient, RQ, was calculated for each target species by comparing toxicity endpoints with the pond pesticide concentrations estimated by TPQPond, as indicated in Table 1. The toxicity endpoint values, listed in Table 2, were taken from the Pesticide Properties Database developed by the University of Hertfordshire (2009) and were the lowest literature values for the most sensitive species (University of Hertfordshire, 2009). For fish the species were rainbow trout (Oncorhynchus mykiss), bluegill sunfish (Lepomis macrochirus), or zebra fish (Brachydanio rerio). For invertebrates, values from the water flea (Daphnia magna) were used, and for algae Raphidocelis subcapitata or Pseudokirchneriella subcapitata 3 were chosen. For plants duckweed (Lemna gibba) was used. For pesticides which toxicity endpoints were unavailable for certain species, those species were omitted from those simulations. Target Species Risk Quotient Equation Invertebrates 1 ππ 10 π¦πππ πππ₯. 48βπ ππππ πππππππ‘πππ‘πππ 48βπ πΈπΆ50 1 ππ 10 π¦πππ πππ₯. 96βπ ππππ πππππππ‘πππ‘πππ 96βπ πΏπΆ50 1 ππ 10 π¦πππ πππ₯. 96βπ ππππ πππππππ‘πππ‘πππ 7 πππ¦ πΏπΆ50 Fish Plants Algae 1 ππ 10 π¦πππ πππ₯. 48βπ ππππ πππππππ‘πππ‘πππ 72βπ πΏπΆ50 Table 1: Risk Quotient Calculations for Target Species 4 Pesticide Herbicides 24-D Benefin Bispyribac-sodium Carfentrazone-ethyl Clopyralid Dithiopyr Fluroxypyr Isoxaben MCPA Mecoprop-p oryzalin Oxadiazon Pendimethalin Penoxsulam Prodiamine Rimsulfuron Sulfentrazone Sulfosulfuron Triclopyr Trifluralin Fungicides Chlorothalonil Cyazofamid Fluopicolide Iprodione Mancozeb Metconazole Myclobutanil Propamocarb-hydCl Thiophanate-methyl Insecticides Acephate Bacillus thuringiensis Bifenthrin Chlorantraniliprole Clothianidin Halofenozide Imidacloprid Indoxacarb Permethrin Invertabrate EC50(48h) (mg/L) Fish LC50(96h) (mg/L) 100 100 95 9.8 100 14 100 1.3 190 91 1.02 2.4 0.28 98.3 0.658 360 60.4 96 131 0.245 100 0.081 95 1.6 100 0.36 14.3 0.87 50 100 3.54 1.2 0.138 100 0.829 390 94 91 117 0.088 0.084 0.19 1.8 0.66 0.073 4.2 17 100 5.4 0.038 0.56 0.36 3.7 0.074 2.1 2 99 11 67.2 13 0.0016 0.0116 40 3.2 85.2 0.6 0.006 110 0.656 0.00015 13.8 104.2 8.6 211 0.65 0.0125 Plants LC50(7d) (mg/L) Algae LC50(72h) (mg/L) 0.58 0.02 0.0127 0.0057 89 12.3 0.011 0.051 1.6 0.0154 0.057 0.012 0.003 0.009 0.29 0.00096 0.8 0.0435 0.29 0.033 3.2 1 105 18 4.7 24.2 100 3.2 0.012 30.5 0.02 49.8 1.4 79.8 16.2 18.1 0.004 0.006 0.49 0.003 0.029 32.8 0.221 75.8 0.0122 0.21 0.025 0.029 1.8 0.044 1.7 2.66 85 25.4 980 2 121 0.084 50 2 55 0.63 10 0.11 0.0125 Table 2: Toxicity Endpoints for Target Species (Source: Haith, 2010) Simulation Scenarios For this study, I repeated the 100-yr simulations carried out in Haith (2010) for three different surface types, fairways, lawns, and greens, in nine different locations: 5 Albany, NY; Atlanta, GA; Bismarck, ND; Columbus, OH; Fresno, CA; Houston, TX; Madison, WI; Olympia, WA; and Roswell, NM. These locations, as shown in Table 3, were chosen in order to obtain a wide variation of U.S. climate conditions (Haith, 2010). Mean Annual Mean Annual Growing Season Temperature Precipitation Location (°C) (mm) Growing Season Albany, NY 9 441 May-Sept Atlanta, GA 16 696 April-Oct Bismarck, ND 5 273 May-Oct Columbus, OH 11 554 May-Oct Fresno, CA 17 135 Mar-Nov Houston, TX 20 917 Mar-Nov Madison, WI 7 443 May-Sept Olympia, WA 10 344 May-Oct Roswell, NM 16 264 April-Oct Table 3: Weather Data for the Investigation Locations (Haith, 2010) Properties of the 38 pesticides included in the study are listed in Table 4. water/sediment values were not available for all pesticides and in those cases, soil values were used for both watershed and pond calculations. 6 Half life (d) Pesticide Herbicides 24-D Benefin Bispyribac-sodium Carfentrazone-ethyl Clopyralid Dithiopyr Fluroxypyr Isoxaben MCPA Mecoprop-p oryzalin Oxadiazon Pendimethalin Penoxsulam Prodiamine Rimsulfuron Sulfentrazone Sulfosulfuron Triclopyr Trifluralin Fungicides Chlorothalonil Cyazofamid Fluopicolide Iprodione Mancozeb Metconazole Myclobutanil Propamocarb-hydCl Thiophanate-methyl Insecticides Acephate Bacillus thuringiensis Bifenthrin Chlorantraniliprole Clothianidin Halofenozide Imidacloprid Indoxacarb Permethrin Soil Lawn Appications Water/Sediment 10 40 13 0.5 34 39 3 105 15 8 20 135 90 32 120 24.3 541 24 39 181 22 10 271 84 0.1 84 306 39.3 0.6 3 3 26 210 545 219 191 17 13 29 1 35 0.4 25 17 17 50 33 113 16 Rate (g/ha) Fairway Applications #/Year 1650 1260 2 1 60 3 430 260 840 800 230 1400 3360 2250 40 1210 1 2 1 2 2 1 1 1 2 1 280 70 840 1260 3 2 3 1 0.1 14 777 30 76 465 626 17 2 860 240 2 2 18300 480 770 2370 2900 910 140 190 220 1130 450 150 730 251 56 129 6 40 #/Year Rate (g/ha) #/Year 1650 1260 110 60 140 430 260 840 800 230 1400 3360 2250 40 1210 30 280 70 840 1260 2 1 3 3 2 1 2 1 2 2 1 1 1 2 1 3 3 2 3 1 1650 2 60 3 260 2 1400 1 2250 1 30 3 2 2 2 2 2 11200 860 240 2170 18300 480 1080 2370 1450 3 3-4 2 5 5-13 5 3-7 2 4 11200 860 240 2170 18300 480 1080 2370 2900 5-9 3-4 2 5 5-13 5 3-7 2 5-10 1 1 1 1 1 1 1 1 3030 910 140 190 220 1130 450 150 730 4-6 4 2 3 2 2 1 4-6 3 3030 910 140 190 220 1130 450 150 730 4-6 4 2 3 2 2 1 4-6 3 6 26 29 6 Rate (g/ha) Green Applications Table 4: Pesticide Properties (Haith, 2010) The parameters I investigated were pesticide application dates, soil and pond degradation half lives of each pesticide, minimum pond volume, organic carbon content of the runoff surface, maximum pond depth, and total suspended solids (TSS) within the pond. In order to determine sensitivity, ranges of values for the parameters were established. For each of these parameters, simulations were run using the high and low 7 values, while keeping all other input parameters constant. The high and low values are listed in Table 5. Parameter Original Value (Haith, 2010) Application Dates Label Recommendations Soil Half Life Minimum Pond Volume Organic Carbon Content (kg/ha): Fairways Greens Lawns Pesticide Properties Database 308% of Original 50% of Maximum Pond 75% of Maximum Volume Pond Volume 10200 6000 15000 Modification High Modification Low Shifted Two Weeks Shifted Two Ealier Weeks Later 30000 13700 24500 Pond Half Life Pesticide Properties Database 308% of Original Maximum Pond Depth 2m 4m TSS 30mg/L, OC 4% 380 mg/L, OC 3% 27% of Original 25% of Maximum Pond Volume 8900 4500 9300 27% of Original 1m 15 mg/L, OC 85% Table 5: Ranges for Chosen Parameters For the application dates, I reasoned that golf course superintendents could feasibly decide to delay or advance their application schedule based on predicted weather patterns. Two weeks seemed like a reasonable shift to both keep it feasible from a reality standpoint as well as providing enough of a difference to be reflected in the simulations. The half life (τ1/2) of a pesticide is reflective of its persistence in the environment after application, i.e. how long it takes to degrade. The model assumes a first order, or exponential, pesticide decay rate α, where α = -0.693/ln(τ1/2). In this case, soil half life values are used for τ1/2. The original soil half lives are listed in Table 4. In their review of turf pesticide properties, Magri and Haith (2009) determined minimum and maximum field dissipation rates for five of the 38 pesticides I investigated. By calculating the percentage differences between the high and low values and the original value used and averaging them, respectively, I was able to create factors by which to multiply all of 8 the original pesticide half lives. I also used these factors when adjusting the pond half lives of the pesticides. Minimum pond volume and maximum pond depth were chosen arbitrarily. Minimum pond volume refers to the lowest acceptable amount of water a pond can contain in relation to its full volume. Water may be added if the volume drops below this value. Maximum pond depth determines the total volume of water the pond can contain. Reducing and increasing the original values for minimum pond volume by 50% and pond depth by a factor of two seemed feasible to me as management plans and pond sizes are far from uniform. By keeping minimum pond volume and pond depth high, I reasoned that pesticide concentrations would be lower simply by the fact that they would be more diluted in a larger volume of water. Organic carbon content of the surfaces proved to be the most challenging parameter to create upper and lower limits for. Organic matter, namely organic carbon (OC) plays a significant role in the sorption of pesticides by acting as a medium into which nonionic compounds adsorb and are removed from the runoff. This prevents the pesticide from reaching the receiving water by reducing its mobility and exposing it to a highly active microbial system (Magri and Haith, 2009). However, this high adsorption also prevents the pesticides from infiltrating into the soil and, in effect, makes it available for transport in the runoff. Although soil may have high organic matter content, the majority of the OC on the turf surfaces is found within the foliage and thatch. For foliage, OC was estimated as described in Haith (2010) using a 38% OC content measured by Lickfeldt and Branham (1995). Madison (1962) measured foliage dry matter of five bentgrasses and three different clipping heights. The data are summarized in Figure 1 and exhibit a typical inverse relationship of density with height (Turgeon, 1991). I used linear interpolation of the grass heights and their corresponding OC contents in order to obtain OC values for the heights of grasses I selected. 9 Figure 1: Linear Interpolation of Bentgrass Heights and OC Thatch is defined by Beard (1973) as “a tightly intermingled layer of dead and living stems and roots that develop(s) between the zone of green vegetation and the soil surface.” Building upon Lickfeldt and Branham (1995), Haith (2001) determined that a value of 1120 kg/ha per mm of thatch depth was a plausible default value. The published values I found for maximum and minimum grass heights extended beyond the data provided by Madison (1962) (Figure 1), I used his maximum and minimum grass heights along with thatch depths that I found (Richards, et al., 2008; Provey, 2002; Harivandi, et al., 2007; Harivandi, 1984; Madison, 1962; Wood and Burke, 1961), to create upper and lower bounds for OC of fairways and lawns. The resulting values are shown in Table 6. As I was unable to find a published value for a minimum thatch depth of greens that was lower than the original, I used the average percent differences in OC of both fairways and lawns as multiplication factors for greens. 10 Grass Height Grass OC (mm) (kg/mm*ha) Fairways Minimum Maximum Lawns Minimum Maximum Grass OC (kg/ha) Thatch Depth Thatch OC (mm) (kg/mm*ha) Thatch OC (kg/ha) Total OC (kg/ha) 12.7 34.9 170 90 2157 3128 6 24 1120 1120 6720 26880 8877 30008 12.7 34.9 170 90 2157 3128 6.35 19.05 1120 1120 7112 21336 9269 24464 Table 6: Calculation of OC Values Total suspended solids (TSS) is the sum of all solids, organic and inorganic, suspended in the pond. In the TPQPond, the pesticide is partitioned into adsorbed and dissolved forms (Haith, 2010). For the purposes of the risk assessment, only the dissolved pesticide concentration is considered meaning that any pesticide adsorbed to solids is disregarded. As the concentration of suspended solids increases, more surface becomes available to adsorb pesticide, thereby lowering the dissolved concentration. The range for TSS was determined using data from a case study performed by Clearflow Enviro Systems Group Inc. in Alberta, Canada that provides pond clarification services. High TSS values can pose problems to golf course superintendents as they can clog irrigation systems as well as be aesthetically unappealing. The “before clarification” and “after clarification” values of TSS and organic carbon content of the suspended solids served as feasible limits on the range of parameter values. Higher TSS and organic carbon values may cause the pesticides to settle to the bottom of the pond by becoming adsorbed to suspended solids. While this may lower the concentration in the water, the sediment at the bottom of the pond would become increasingly more concentrated. CHAPTER 3: RESULTS Seventeen sets of simulation results were used to evaluate parameter sensitivity: the original runs from Haith (2010) and the 14 sets described previously: high and low values for each of the seven parameters or conditions listed in Table 5. Each simulation set estimated 1 in 10 yr pond concentrations of the various pesticides for each location and grass surface. These concentrations were used to determine RQ values for each 11 species as shown in Table 1. Parameter sensitivity was measured by determining percent difference in the new RQ (based on a higher or lower parameter value) and the original RQ. The percent differences were then averaged over all pesticides at a given location and grass surfaces. In general, results were similar between all four species for each surface type. Additional results for all species and surface types can be found in the Appendix. Table 7 shows the change in RQs for fairways averaged over all target species. The increased modification of turf OC content seems to have a significantly greater impact on the RQs than that of the decreased modification. Invertebrates, Fish, Application Turf Half Plants, and Algae: Date Life Fairways Low -16% -44% Albany High -6% 59% Low -10% -33% Atlanta High -5% 33% Low -8% -54% Bismarck High 4% 54% Low 8% -35% Columbus High -4% 29% Low 12% -67% Fresno High 9% 169% Low -20% -33% Houston High 4% 32% Low -1% -45% Madison High 16% 41% Low -16% -79% Olympia High 26% 197% Low -14% -49% 1% 49% Roswell High Mean (Low): -7% -49% Mean (High): 5% 74% Median Low): -10% -45% Median (High): 4% 49% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Content Half Life 8% -17% -44% 33% 8% -15% -50% 16% 7% -15% -48% 33% 11% 0% -48% 21% 2% -25% -27% 85% 8% 10% -49% 47% 8% -18% -48% 29% 1% -21% -24% 23% 8% -22% -43% 36% 7% -14% -42% 36% 8% -17% -48% 33% Pond Depth 81% -46% 70% -46% 88% -48% 80% -46% 89% -48% 64% -43% 73% -46% 53% -39% 90% -49% 77% -46% 80% -46% TSS -1% -1% -2% -2% -1% -1% -1% -1% -1% -1% -2% -2% -3% -3% -2% -2% -1% -1% -2% -2% -1% -1% Table 7: Percent Changes for 1 in 10 year Risk Quotients for Fairways Averaged across All Species 12 Table 8 shows the change in RQs for greens averaged over all target species. Of all the surfaces, modification of turf half life for greens creates the biggest impact on RQ values, whereas the impact from turf OC content is lowest. Application Turf Half Invertebrates, Fish, Date Life Plants, and Algae: Greens Low -28% -79% Albany High 33% 381% Low 7% -53% Atlanta High 4% 127% Low -34% -61% Bismarck High 680% 691% Low 15% -40% Columbus High -3% 58% Low 0% -100% Fresno High 0% 0% Low -22% -49% Houston High 8% 71% Low -8% -65% Madison High -12% 115% Low -28% -87% Olympia High 46% 383% Low -1% -27% High 3% 58% Roswell Mean (Low): -11% -62% Mean (High): 84% 209% Median Low): -8% -61% Median (High): 4% 115% Turf Min Organic Pond Carbon Pond Size Content Half Life 0% 2% -15% 0% 6% 31% 0% 13% -11% 0% -33% 17% 0% -30% -93% 0% -8% 797% 0% 10% 0% 0% -30% 0% 0% 0% -100% 0% 0% 800% 0% 14% 17% 0% -39% 109% 0% 13% -13% 0% -34% 24% 0% 2% -10% 0% -8% 15% 0% -8% -73% 0% -5% 388% 0% 2% -33% 0% -17% 242% 0% 2% -13% 0% -8% 31% Pond Depth 92% -46% 82% -47% 741% -50% 84% -47% 0% 0% 76% -46% 90% -47% 88% -47% 82% -46% 148% -42% 84% -47% TSS -3% -3% -2% -2% 0% 0% -1% -1% 0% 0% -2% -2% -3% -2% -5% -3% 0% 0% -2% -1% -2% -2% Table 8: Percent Changes for 1 in 10 year Risk Quotients for Greens Averaged across All Species The results for lawns are shown below in Table 9. Aside from TSS and minimum pond size, the magnitudes of the differences in RQs were quite similar for both the high and low modifications of the input parameters. 13 Application Turf Half Invertebrates, Fish, Date Life Plants, and Algae: Lawns Low -8% -51% Albany High 7% 73% Low -14% -31% Atlanta High -18% 32% Low -8% -49% Bismarck High 4% 69% Low 1% -38% Columbus High -2% 41% Low 4% -80% Fresno High 7% 172% Low -26% -37% Houston High -13% 45% Low -1% -62% Madison High 24% 54% Low -11% -82% Olympia High 13% 126% Low 2% -82% 22% 62% Roswell High Mean (Low): -7% -57% Mean (High): 5% 75% Median Low): -8% -51% Median (High): 7% 62% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Content Half Life 20% -27% -16% 32% 32% -29% -24% 33% 25% -23% -23% 55% 27% 0% -25% 0% -3% -26% -7% 81% 35% -16% -23% 65% 27% -20% -22% 35% 3% -27% -12% 26% 22% -26% -17% 50% 21% -22% -19% 42% 25% -26% -22% 35% Pond Depth 70% -43% 65% -43% 92% -48% 72% -45% 82% -48% 59% -40% 73% -45% 49% -39% 89% -47% 72% -44% 72% -45% TSS -2% -1% -1% -1% -1% -1% -2% -2% -1% -1% -2% -1% -2% -1% -2% -2% -1% -1% -2% -1% -2% -1% Table 9: Percent Changes for 1 in 10 year Risk Quotients for Lawns Averaged across All Species Based upon the median high and low values, the risk assessment appears to be most sensitive to changes in the values chosen for turf half life and pond depth or size. It was moderately sensitive to pond half life and turf organic carbon content values and mildly sensitive to changes in the application dates. There does not seem to be much correlation across location in terms of adjusting application date; advancing or delaying the pesticide application schedule does not elicit the same response from each location, i.e. in Albany delaying the schedule decreases the risk quotient while in Fresno it increases. However, with more precise, locationspecific scheduling based on historic precipitation data it may be possible to reduce the risk posed by pesticide runoff. 14 As the turf and pond half lives increased, the RQs increased and vice versa. With longer half lives on the turf, pesticides are more likely to persist until they are carried into the pond by sufficient runoff. Once in the pond, pesticides with longer half lives would remain in the pond for a longer period of time, thus allowing pesticide inflows from multiple runoff events to sum together and increase the pesticide concentrations in the pond. Interestingly enough, TPQPond did not show any sensitivity to minimum pond size change across all of the simulations. On the whole, RQs decreased with the increased surface OC modification. However, the magnitude of the effect varied widely from location to location and from surface to surface. This is most likely due to the dual effect of pesticide adsorption. While it is true that high OC will adsorb pesticide more strongly and expose it to highly active microbial systems (Magri and Haith, 2009), it also prevents infiltration of the pesticide and makes it more available to runoff. From these results, it appears that the contribution from each phenomenon varies in relative importance from location to location as for some an increase in OC creates a decrease in RQs while for others RQs increase. For the modifications in maximum pond depth, it makes sense that for a larger volume of water the same amount of pesticide would be more diluted, thus leading to lower concentrations and corresponding RQs. In regards to modifications to TSS and its associated organic carbon content, looking at the modified RQ values would lead one to believe that any deviation from the original value would generate lower RQs as both the high and low modifications caused reductions in the calculated RQs. However, this could be attributed to the fact that, in the case study (Clearflow), the organic carbon fraction of the suspended solids increased dramatically after clarification. The total amount of carbon suspended remained close to the same and higher than the value used in the original runs as shown in Table 10. This would cause more pesticide to become adsorbed and settle 15 out in both cases, suggesting that the most important factor in TSS is the amount of carbon. TSS (mg/L) Organic Carbon Fraction Total Organic Carbon (mg/L) Original Low High (Haith, 2010) Modification Modification 30 15 380 0.04 0.85 0.03 1.2 12.75 11.4 Table 10: Total Pond Organic Carbon for Original and Modified Simulations CHAPTER 4: CONCLUSIONS In this study I conducted a sensitivity analysis of the program TPQPond to seven different input parameters. This was accomplished by establishing a reasonable range of parameter values, running the model for 100 years of weather and irrigation data, and comparing the one-in-10 year RQs for four different target species for each parameter modification. Based on the results, I conclude the following: ο· With increasing turf half life and pond half life, risk quotients had a tendency to increase. The model was most sensitive to changes in these two parameters. ο· With increasing turf organic carbon and pond size, averaged risk quotients had a tendency to decrease although this is not the case for all specific locations. ο· Although the model does appear to be sensitive to changes in application dates, the effects of such changes on RQs are most likely location specific. ο· The model appeared completely insensitive to minimum pond volume based on the range chosen for this study. ο· Risk quotients decreased for both high and low pond TSS modifications. This is most likely attributed to an increase in the suspended carbon content within the pond. Based on these findings, when using risk assessment models it is important to choose the input values carefully. While changes in some parameters, such as 16 minimum pond volume, may not affect the model significantly, small changes, specifically for parameters that the model is especially sensitive to, can cause drastic differences in the calculated risk quotients. Accurate input values are essential to conducting an ecological risk assessment that correctly reflects the area of study. TPQPond, while providing quantitative results, is not precise. As these simulations have shown, the model is extremely dependent upon certain input parameters and the results might reflect the sensitivity of the model to the parameters rather than a correlation between the magnitudes of the parameter changes and those of the risk quotients. 17 REFERENCES Beard, J.B. 1973. Turfgrass: Science and culture. Prentice-Hall, Englewood Cliffs, NJ. Clearflow Enviro Systems Group. 2010. "Golf Course - Pond Clarification." <http://www.clearflowconsulting.com/content.asp?ID=23>. Haith, D. A. 2010. 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Crop Science 101: 31718. 19 APPENDIX Application Turf Half Date Life Invertebrates: Fairways Low -19% -36% Albany High -8% 37% Low -13% -29% Atlanta High -1% 25% Low -10% -48% Bismarck High 5% 40% Low 6% -29% Columbus High -12% 18% Low 26% -62% Fresno High 12% 77% Low -12% -21% Houston High 14% 22% Low 1% -41% Madison High 6% 29% Low -17% -58% Olympia High 28% 86% Low -24% -39% -19% 34% Roswell High Mean (Low): -7% -40% Mean (High): 3% 41% Median Low): -12% -39% Median (High): 5% 34% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS 7% -20% 78% -1% -43% 39% -45% -1% 8% -14% 65% -1% -48% 18% -44% -1% 7% -19% 87% -1% -48% 39% -48% -1% 9% 0% 72% -1% -50% 23% -45% -1% -3% -16% 87% 0% -11% 67% -48% 0% 10% -8% 62% -1% -52% 17% -43% -1% 8% -20% 65% -1% -47% 35% -43% -1% -4% -20% 50% -1% 1% 22% -37% -1% 8% -24% 89% -1% -52% 36% -49% -1% 5% -16% 73% -1% -39% 33% -45% -1% 8% -19% 72% -1% -48% 35% -45% -1% Table A 1: Percent Changes in Invertebrate 1-in-10 year Risk Quotients (EC50, 48 hr) for Fairways 20 Application Turf Half Date Life Invertebrates: Greens Low -32% -62% Albany High 14% 163% Low 7% -48% Atlanta High 0% 82% Low -28% -72% Bismarck High 2641% 2666% Low -9% -35% Columbus High 7% 23% Low 0% -100% Fresno High 0% 0% Low -20% -46% Houston High 5% 51% Low -1% -59% Madison High -6% 83% Low -34% -72% Olympia High 45% 237% Low 0% -40% High 35% 26% Roswell Mean (Low): -13% -59% Mean (High): 305% 370% Median Low): -9% -59% Median (High): 7% 82% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS -15% -10% 98% 0% 15% 45% -50% 0% 8% -9% 88% -1% -22% 19% -48% -1% -19% -93% 2707% 0% -13% 2793% -50% 0% 0% 0% 75% 0% -11% 0% -45% 0% 0% -100% 0% 0% 0% 800% 0% 0% 11% -10% 73% -1% -34% 32% -45% -1% 6% -11% 89% -1% -19% 33% -47% -1% -14% -19% 83% -2% 6% 14% -47% -2% -13% -73% 85% 0% 9% 248% -44% 0% -4% -36% 366% -1% -8% 443% -42% -1% 0% -11% 85% 0% -11% 33% -47% 0% Table A 2 Percent Changes in Invertebrate 1-in-10 year Risk Quotients (EC50, 48 hr) for Greens 21 Application Date Invertebrates: Lawns Low -10% Albany High 16% Low -14% Atlanta High -14% Low 1% Bismarck High -3% Low 11% Columbus High -9% Low 1% Fresno High 11% Low -18% Houston High -18% Low 1% Madison High 10% Low -14% Olympia High 14% Low 20% High 15% Roswell Mean (Low): -2% Mean (High): 2% Median Low): 1% Median (High): 10% Turf Min Half Pond Life Size -40% 0% 38% 0% -21% 0% 17% 0% -37% 0% 49% 0% -28% 0% 30% 0% -86% 0% 105% 0% -23% 0% 19% 0% -93% 0% 34% 0% -69% 0% 47% 0% -98% 0% 29% 0% -55% 0% 41% 0% -40% 0% 34% 0% Turf Organic Pond Carbon Half Pond Content Life Depth TSS 11% -31% 61% -1% -13% 37% -43% -1% 33% -31% 57% -1% -21% 48% -41% -1% 20% -35% 103% 0% -27% 78% -49% 0% 24% 0% 71% -2% -28% 0% -45% -2% -40% -15% 76% -1% 19% 53% -50% -1% 24% -28% 45% -1% -24% 41% -38% -1% 27% -21% 71% -1% -22% 41% -44% -1% -19% -28% 43% 0% 0% 24% -39% 0% 30% -36% 96% 0% -19% 78% -47% 0% 12% -25% 69% -1% -15% 45% -44% -1% 24% -28% 71% -1% -21% 41% -44% -1% Table A 3: Percent Changes in Invertebrate 1-in-10 year Risk Quotients (EC50, 48 hr) for Lawns 22 Application Turf Half Date Life Fish: Fairways Low -27% -38% Albany High -23% 58% Low -11% -35% Atlanta High 1% 40% Low -7% -57% Bismarck High 1% 46% Low 16% -32% Columbus High -13% 32% Low 22% -62% Fresno High 4% 205% Low -18% -29% Houston High 15% 28% Low -3% -54% Madison High 2% 48% Low -21% -78% Olympia High 37% 386% Low -20% -42% -25% 37% Roswell High Mean (Low): -8% -47% Mean (High): 0% 98% Median Low): -11% -42% Median (High): 1% 46% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Half Pond Content Life Depth 12% -11% 86% -60% 40% -47% 11% -12% 76% -61% 13% -49% 12% -13% 92% -60% 27% -49% 18% 0% 90% -62% 22% -45% 3% -37% 79% -27% 66% -48% 11% -6% 68% -62% 11% -43% 10% -18% 71% -61% 25% -49% 2% -18% 49% -31% 16% -39% 11% -25% 91% -61% 35% -51% 10% -15% 78% -54% 28% -47% 11% -13% 79% -61% 25% -48% TSS -1% -1% -6% -5% -1% -1% -1% -1% -2% -1% -3% -3% -7% -7% -2% -2% -1% -1% -3% -3% -2% -1% Table A 4: Percent Changes in Fish 1-in-10 year Risk Quotients (LC50, 96hr) for Fairways 23 Application Turf Half Date Life Fish: Greens Low -34% -85% Albany High 55% 585% Low 10% -51% Atlanta High -4% 101% Low -22% -63% Bismarck High 10% 25% Low 24% -41% Columbus High -42% 36% Low 0% -100% Fresno High 0% 0% Low -22% -50% Houston High 6% 64% Low -5% -72% Madison High -26% 119% Low -37% -93% Olympia High 60% 478% Low -7% -22% -10% 13% Roswell High Mean (Low): -10% -64% Mean (High): 5% 158% Median Low): -7% -63% Median (High): 0% 64% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS 0% -11% 89% 0% -8% 22% -47% 0% 19% -3% 89% -1% -41% 13% -48% -1% -15% -87% 79% 0% -13% 50% -50% 0% 19% 0% 87% -2% -45% 0% -49% -1% 0% -100% 0% 0% 0% 800% 0% 0% 14% -9% 76% -1% -43% 30% -46% -1% 18% -4% 91% -1% -44% 15% -48% -1% 5% -3% 88% -1% -26% 13% -48% -1% -5% -70% 76% 0% -12% 265% -46% 0% 6% -32% 75% -1% -26% 134% -42% -1% 5% -9% 87% -1% -26% 22% -48% -1% Table A 5: Percent Changes in Fish 1-in-10 year Risk Quotients (LC50, 96hr) for Greens 24 Application Turf Half Date Life Fish:Lawns Low -13% -48% Albany High -5% 74% Low -36% -24% Atlanta High -38% 30% Low -7% -51% Bismarck High 10% 69% Low -20% -33% Columbus High -16% 50% Low 21% -73% Fresno High 0% 156% Low -40% -29% Houston High -23% 68% Low -10% -54% Madison High 6% 73% Low -11% -76% Olympia High 11% 114% Low -3% -89% 8% 54% Roswell High Mean (Low): -13% -53% Mean (High): -5% 77% Median Low): -11% -51% Median (High): 0% 69% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS 26% -38% 64% -2% -20% 41% -40% -2% 42% -51% 54% -2% -30% 49% -40% -2% 27% -32% 89% -2% -24% 75% -48% -2% 38% 0% 61% -3% -30% 0% -42% -3% 5% -39% 78% -1% -10% 80% -47% -1% 69% -45% 68% -3% -29% 103% -37% -2% 31% -33% 61% -2% -25% 48% -41% -2% 3% -27% 42% -3% -11% 22% -36% -3% 24% -37% 80% -2% -25% 55% -46% -2% 29% -33% 66% -2% -23% 53% -42% -2% 27% -37% 64% -2% -25% 49% -41% -2% Table A 6: Percent Changes in Fish 1-in-10 year Risk Quotients (LC50, 96hr) for Lawns 25 Application Turf Half Date Life Plants: Fairways Low -6% -49% Albany High 9% 49% Low -14% -26% Atlanta High -18% 22% Low -7% -52% Bismarck High 11% 47% Low 11% -34% Columbus High 7% 29% Low 2% -76% Fresno High 10% 230% Low -37% -37% Houston High -25% 29% Low 1% -36% Madison High 44% 31% Low -16% -90% Olympia High 25% 174% Low -1% -62% High 49% 61% Roswell Mean (Low): -7% -51% Mean (High): 12% 75% Median Low): -6% -49% Median (High): 10% 47% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth 3% -17% 87% -23% 15% -49% 5% -16% 82% -34% 11% -47% 2% -14% 89% -29% 16% -48% 5% 0% 84% -24% 15% -47% 2% -22% 100% -25% 124% -48% 3% 71% 74% -27% 141% -45% 5% -19% 85% -28% 16% -48% 1% -25% 61% -25% 26% -42% 2% -14% 93% -5% 21% -49% 3% -6% 84% -24% 43% -47% 3% -16% 85% -25% 16% -48% TSS -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -2% -2% -1% -1% -1% -1% -1% -1% Table A 7: Percent Changes in Plant 1-in-10 year Risk Quotients (LC50, 7d) for Fairways 26 Application Turf Half Date Life Plants: Greens Low -15% -93% Albany High 38% 541% Low 9% -67% Atlanta High 10% 201% Low -40% -54% Bismarck High 66% 69% Low 15% -57% Columbus High 2% 131% Low 0% -100% Fresno High 0% 0% Low -18% -61% Houston High 4% 101% Low -10% -79% Madison High -6% 171% Low -20% -97% Olympia High 40% 481% Low 6% -27% High -5% 187% Roswell Mean (Low): -8% -71% Mean (High): 17% 209% Median Low): -10% -67% Median (High): 4% 171% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS 33% -5% 115% 0% -8% 41% -40% 0% 14% -9% 84% -5% -36% 16% -47% -5% -39% -95% 122% 0% -4% 328% -50% 0% 18% 0% 101% -1% -34% 0% -49% -1% 0% -100% 0% 0% 0% 800% 0% 0% 16% 110% 81% -3% -40% 321% -47% -3% 21% -13% 97% -4% -42% 22% -47% -4% 14% -12% 95% -9% -19% 19% -48% -9% -3% -83% 81% 0% -15% 838% -45% 0% 8% -23% 86% -2% -22% 265% -42% -2% 14% -12% 95% -1% -19% 41% -47% -1% Table A 8: Percent Changes in Plant 1-in-10 year Risk Quotients (LC50, 7d) for Greens 27 Application Turf Date Half Life Plants: Lawns Low -8% -54% Albany High 12% 57% Low -5% -29% Atlanta High -13% 24% Low -16% -49% Bismarck High 23% 52% Low 20% -41% Columbus High 11% 31% Low -3% -81% Fresno High 10% 221% Low -36% -37% Houston High -19% 28% Low 7% -43% Madison High 68% 41% Low -12% -92% Olympia High 16% 188% Low -2% -69% High 57% 74% Roswell Mean (Low): -6% -55% Mean (High): 18% 80% Median Low): -5% -49% Median (High): 12% 52% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth 8% -18% 87% -9% 13% -47% 15% -14% 83% -15% 10% -47% 13% -12% 90% -11% 20% -48% 7% 0% 83% -8% 0% -47% 3% -25% 88% -13% 108% -48% 12% 27% 75% -10% 92% -46% 10% -14% 83% -10% 12% -47% 10% -27% 60% -13% 27% -43% -4% -13% 100% 4% 15% -49% 8% -11% 83% -10% 33% -47% 10% -14% 83% -10% 15% -47% TSS -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -1% -3% -2% -1% -1% -1% -1% -1% -1% Table A 9: Percent Changes in Plant 1-in-10 year Risk Quotients (LC50, 7d) for Lawns 28 Application Turf Half Date Life Algae: Fairways Low -12% -52% Albany High -1% 92% Low -2% -41% Atlanta High -1% 45% Low -8% -58% Bismarck High -1% 82% Low -3% -44% Columbus High 2% 38% Low -2% -66% Fresno High 9% 163% Low -14% -45% Houston High 11% 48% Low -3% -51% Madison High 11% 56% Low -10% -91% Olympia High 13% 142% Low -13% -53% High 0% 66% Roswell Mean (Low): -8% -56% Mean (High): 5% 81% Median Low): -8% -52% Median (High): 2% 66% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth TSS 9% -20% 73% -2% -52% 40% -46% -2% 9% -17% 58% -2% -56% 24% -43% -2% 9% -14% 85% -2% -55% 51% -48% -2% 11% 0% 75% -2% -57% 23% -45% -2% 7% -22% 91% -2% -45% 81% -48% -2% 9% -17% 53% -2% -55% 18% -41% -2% 9% -16% 70% -2% -55% 41% -44% -2% 3% -22% 50% -3% -40% 30% -38% -2% 10% -25% 88% -2% -55% 51% -47% -2% 8% -17% 72% -2% -52% 40% -44% -2% 9% -17% 73% -2% -55% 40% -45% -2% Table A 10: Percent Changes in Algae 1-in-10 year Risk Quotients (LC50, 72hr) for Fairways 29 Application Turf Half Date Life Algae: Greens Low -29% -76% Albany High 23% 236% Low 4% -48% Atlanta High 11% 127% Low -46% -54% Bismarck High 2% 5% Low 31% -26% Columbus High 21% 41% Low 0% -100% Fresno High 0% 0% Low -28% -41% Houston High 15% 67% Low -16% -51% Madison High -11% 87% Low -21% -86% Olympia High 38% 338% Low -4% -16% High -7% 6% Roswell Mean (Low): -12% -55% Mean (High): 10% 101% Median Low): -16% -51% Median (High): 11% 67% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth -8% -33% 64% 27% 15% -48% 13% -23% 64% -32% 20% -44% -44% -98% 55% -2% 15% -50% 4% 0% 74% -30% 0% -45% 0% -100% 0% 0% 800% 0% 16% -24% 73% -40% 53% -44% 7% -26% 85% -32% 26% -46% 3% -5% 87% 6% 14% -47% -11% -67% 87% -1% 201% -47% -2% -42% 66% -12% 127% -41% 3% -26% 73% -2% 20% -46% TSS -10% -10% -4% -4% 0% 0% -1% -1% 0% 0% -3% -3% -6% -3% -6% 0% 0% 0% -3% -2% -3% -1% Table A 11: Percent Changes in Algae 1-in-10 year Risk Quotients (LC50, 72hr) for Greens 30 Application Turf Date Half Life Algae: Lawns Low -2% -61% Albany High 7% 120% Low 0% -49% Atlanta High -6% 56% Low -8% -60% Bismarck High -16% 104% Low -5% -49% Columbus High 4% 52% Low -4% -78% Fresno High 7% 206% Low -11% -58% Houston High 7% 66% Low 0% -58% Madison High 11% 67% Low -9% -91% Olympia High 10% 154% Low -7% -72% High 9% 90% Roswell Mean (Low): -5% -64% Mean (High): 4% 102% Median Low): -5% -60% Median (High): 7% 90% Min Pond Size 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% Turf Organic Carbon Pond Pond Content Half Life Depth 33% -23% 69% -23% 38% -42% 37% -20% 64% -32% 26% -44% 40% -11% 87% -31% 49% -48% 39% 0% 72% -33% 0% -45% 21% -24% 85% -23% 82% -48% 33% -19% 48% -29% 22% -39% 41% -12% 75% -32% 39% -46% 17% -26% 50% -23% 29% -40% 35% -20% 80% -29% 52% -45% 33% -17% 70% -28% 38% -44% 35% -20% 72% -29% 38% -45% TSS -2% -2% -2% -2% -2% -2% -2% -2% -3% -3% -2% -2% -2% -2% -2% -2% -2% -2% -2% -2% -2% -2% Table A 12: Percent Changes in Algae 1-in-10 year Risk Quotients (LC50, 72hr) for Lawns 31