Nutrient Trends in the Des Moines River Donna S. Lutz Des Moines River Water Quality Network What is the Des Moines River Water Quality Network? • Initiated in July 1967 as preimpoundment study for Saylorville Reservoir, expanded to Red Rock Reservoir in 1971 •Long-term record, 36 years at many sites, total of 182 parameters, nearly 445,000 individual data records • Currently 7 regular sampling sites, monitored 22 times per year for up to 50 parameters •Data available through annual reports, paradox database, webpage (soon to be on Iowa STORET) Des Moines River Basin •Length 350 mi •Width 50 mi •Basin 12,884 sq mi about ¼ size of Iowa Saylorville Reservoir •24 mi valley/54 mi flood •5,520 acres/ 16,100 flood •1,100 ac-ft/yr sedimentation Red Rock Reservoir •18 mi valley/33 mi flood •15,250 acres/ 1,625,00 fl •4,470 ac-ft/yr sedimentation Raccoon River Sub-basin North Raccoon/Middle Raccoon/South Raccoon Basin 3,411 sq mi Routine Parameters Physical Chemical temperature, flow/elevation turbidity, secchi disc depth, gas saturation dissolved oxygen, BOD, TOC, nutrients, suspended solids metals, pesticides Biological chlorophyll pigments bacteria Important Programs Short term bacteria at beaches safe for fish? overall monitoring why? what’s up? historical record safe to eat? total gas saturation Long term safe to swim? pesticides in fish trend analysis any improvement? suspended solids nutrient what is normal? ammonia, nitrate, phosphate pesticides chlorophyll pigments Significant Findings Non-point sources are the main contaminants; Point source loading has decreased soil erosion and siltation primary resource problem Ave. loading to Red Rock 5,400 metric tons/day Improved wastewater treatment has significantly reduced ammonia loading Nitrate levels increased until 1982, no current trend Total Phosphate levels have decreased slightly, but only by about 0.01 mg/year Significant Findings (cont’d) Overall, water quality has significantly improved at most sites, according to water quality index values Pesticide levels in fish are low, but may still be of concern Gas supersaturation-induced gas bubble trauma causes periodic fish kills below Red Rock Dam Nutrient Trends Total Nitrogen Nitrogen Forms Nitrate Ammonia Nutrient criteria – total nitrogen (rivers) Total Phosphorus Orthophosphate Nutrient criteria – total phosphorus (rivers) Phosphorus in sediment Importance of River Flow Low Flow Nutrients can decrease due to algal utilization However, nutrients may increase if there are point sources due to lack of dilution High Flow Nutrients, especially nitrate and total phosphate may increase with storm events Antecedent precipitation important Algal Utilization of nutrients under low flow Temp C Flow cfs 7/22/ 2003 22.9 3240 8/5/ 2003 24.4 856 Chl a mg/m3 NH4 mg/l NO3 mg/l T PO4 mg/l O PO4 mg/l 73 0.03 11.0 0.64 0.25 162 0.01 3.52 0.55 <0.03 Nitrogen Inputs Dry Deposition 7% Human <1% Industry <1% Manure 13% Soil N 26% Fertilizer 25% Legumes 20% Wet Deposition 9% Estimated Point and Non-Point Source Contributions to Stream N-Load Point Source 8% Non-Point Source 92% Nitrogen Forms, % Above Saylorville Reservoir (St. 1) Total N Organic N Ammonia N NO2+NO3 N 1967-76 1977-81 100 100 2000-03 100 14 16 21 7 4 1 79 80 78 Below Saylorville Reservoir (St.5) Total N Organic N Ammonia N NO2+NO3 N 1967-76 1977-81 100 100 2000-03 100 16 15 13 6 7 2 78 78 85 Nitrogen Forms Raccoon River near Van Meter Total N monthly mean 1972-81 7.45 mg/l 2000-03 8.55 mg/l 15% 12% 1% 4% 84% 1972-81 84% 2000-03 Organic N Ammonia N NO2+NO3 N 10 1967-76 1977-81 2000-03 8 Nitrogen Forms, Concentration Above Saylorville Reservoir (St. 1) 6 1967-76 1977-81 5.86 8.25 2000-03 7.89 4 Total N 2 Organic N 0.84 1.30 1.63 0 Ammonia N 0.40 0.30 0.06 NO3 NO2+NO3 N 4.62 6.65 6.20 2000-03 Below Saylorville Reservoir (St.5) Tot N Org N Amm 10 1967-76 1977-81 8 6 1967-76 1977-81 5.67 6.55 2000-03 7.25 4 Total N 2 Organic N 0.89 0.99 0.97 0 Ammonia N 0.32 0.43 0.15 NO2+NO3 N 4.46 5.13 6.13 Tot N Org N Amm NO3 Nitrite +Nitrate N Ammonia oxidized to nitrate (bacterially mediated) Sources Fertilizers, oxidation or organic N, fixation of N2, precipitation, sewage effluents Losses Nitrite, intermediate product, (1967-76, max 0.68 mg/l, 99% of samples <0.20 mg/l) Leaching, assimilation living organisms, conversion to other forms Soluble, easily leaches from soil Nitrate vs Flow Des Moines River near Boone Nitrate 12 12000 10 10000 8 8000 6 6000 4 4000 2 2000 0 0 Flow (cfs) Nitrate mg/l Flow 2002 2000 1998 1996 1994 1992 1990 1988 1986 1984 1982 1980 1978 1976 1974 1972 1970 1968 Nitrate vs Flow Raccoon River near Van Meter Nitrate 12 12000 10 10000 8 8000 6 6000 4 4000 2 2000 0 0 Flow (cfs) Nitrate mg/l Flow 2003 2001 1999 1997 1995 1993 1991 1989 1987 1985 1983 1981 1979 1977 1975 1973 Nitrate vs Flow Des Moines River near Boone R2 = 0.63 10 9 Nitrate (mg/l) 8 7 6 5 4 3 2 1 0 0 2000 4000 6000 Flow (cfs) 8000 10000 12000 Seasonality of Nitrate Concentrations Raccoon River, monthly means unadjusted Winter Spring Summer Fall Seasonality of Nitrate Concentrations Raccoon River, monthly means flow adjusted Winter Spring Summer Fall Seasonal Kendall Tau Trend Analysis, Significant Trends (95%) (from Monthly Mean Data, flow-adjusted) NO2+NO3 N NO2+NO3 N n mean slope Des Moines River near Boone 1967-2003 1967-1982 1983-2003 438 186 252 5.70 5.27 6.00 no trend + 0.23 no trend NO2+NO3 N n mean slope Raccoon River near Van Meter 1972-2003 1972-1982 1982-2000 377 125 252 7.00 6.55 7.22 no trend + 0.36 no trend Exceedance vs Flow Des Moines River near Boone Flow Linear (months) 9 12000 8 10000 7 6 8000 5 6000 4 3 4000 2 2000 1 0 0 Flow (cfs) # of months >10 mg/l Nitrate months 2002 2000 1998 1996 1994 1992 1990 1988 1986 1984 1982 1980 1978 1976 1974 1972 1970 1968 Exceedance vs Flow Raccoon River near Van Meter months Flow Linear (months) 6000 8 5000 7 6 4000 5 3000 4 3 2000 2 1000 1 0 0 Flow (cfs) # of months >10 mg/l Nitrate 9 2003 2001 1999 1997 1995 1993 1991 1989 1987 1985 1983 1981 1979 1977 1975 1973 1989 1986 1983 1980 1977 1974 1971 2001 1998 1995 Des Moines River 1992 0 1968 Nitrate mg/l Nitrate Concentration Raccoon River 12 10 8 6 4 2 Nitrate Transport Raccoon River Des Moines River Nitrate Transport (1,000 kg/day) 160 140 120 100 80 60 2001 1998 1995 1992 1989 1986 1983 1980 1977 1974 1971 1968 40 20 0 Nutrient Criteria T N in rivers 2.62 mg/l Data from 5/2000-03 DMR Boone DMR Sayl Rac R Van Meter ave 7.89 7.25 8.52 8.38 8.19 6.45 min 1.36 1.41 1.24 3.00 3.46 1.40 max 17.0 14.4 17.7 15.3 14.6 11.4 9 5 4 0 0 2 n 44 44 44 44 44 44 % 20 11 9 0 0 5 #months <2.62 DMR DM DMR Runnells DMR Pella Transport of Nutrients and Effects of Reservoirs Stations 1 5 10 6 7a 9 Discharge (cfs) 3,192 3,428 2,085 6,064 7,662 7,525 Suspended solids (1,000 kg/day) 1,623 389 3,328 3,932 5,027 600 Ammonia N (kg/day) 1,084 1,497 915 3,256 3,156 3,669 Nitrate (kg/day) 66,000 67,000 46,000 125,000 145,000 125,000 Total phosphate 6,722 4,422 8,351 17,679 – 9,709 Water Year Mean Stream Flow Separation and Nitrate Nitrogen (Schilling and Lutz) Hydrograph separation using USGS program HYSEP (Sloto and Crouse, 1996) Regression analyses determined if annual Q vs P relationship changed over time Regression analyses of annual P, Q, Qb, Qs, and Q% over time Nitrate data summarized into monthly means Regression and correlation of monthly mean nitrate to streamflow components Baseflow Discharge (in) 25 20 15 10 5 0 15 10 5 0 1900 1920 1940 1960 1980 2000 1900 1920 1940 1960 1980 2000 15 Baseflow Percentage Stormflow Discharge (in) Total Discharge (in) Results – Streamflow Changes 10 5 0 1900 1920 1940 1960 1980 2000 80 70 60 50 40 30 20 1900 1920 1940 1960 1980 2000 Streamflow Changes, cont. Annual precipitation also increased during 1916-2000 period Regression residuals indicate change in rainfall-runoff relationship since 1916 (p<0.05) Thus, more precipitation is being routed into streamflow as baseflow in latter portion of 20th century Regression Models Relating Baseflow to Nitrate Mean Annual NO3-N Concentration (mg/l) Annual NO3-N Conc. Versus Baseflow Discharge (in) 14 y = 0.6202x + 3.9537 R2 = 0.6098 12 10 8 6 4 2 0 0 2 4 6 8 10 12 14 Discharge (in) Qb provided best r2 value (0.61) compared to Q (0.59), Qs (0.48) or Q% (0.27) What role might changing streamflow hydrology in the Raccoon River have had on nitrate concentrations? NO3-N Concentration (mg/l) 16 14 12 10 8 6 4 1945-46 1972-2000 2 0 1 2 3 4 5 Log Mean Monthly Qb 12 NO3-N Concentration (mg/l) Historical Perspective 10 1972-2000 8 6 4 2 WY1946 0 1 2 3 Log Mean Annual Qb 4 5 Ammonia N Sources Biological degradation of organic matter Point source - wastewater effluent Nonpoint sources - fertilizer, feedlots Importance Oxidation of ammonia exerts an oxygen demand Unionized ammonia form toxic to aquatic life /1 9 /1 9 77 77 77 /1 9 /1 9 3/ 1/ 19 2/ 22 2/ 15 77 77 77 77 25 20 15 250 Fish Kill Event 200 150 5 100 50 0 0 Flow cfs Ammonia 2/ 8/ 19 2/ 1/ 19 /1 9 /1 9 77 Ammonia mg/l 10 1/ 25 1/ 18 /1 9 77 76 76 1/ 4/ 19 /2 8 /2 1 1/ 11 12 12 Point Source Event 1977 Flow 400 350 300 /1 9 /1 9 77 77 77 /1 9 /1 9 3/ 1/ 19 2/ 22 2/ 15 77 77 77 77 18 400 16 350 14 300 12 250 10 Fish Kill Event 200 6 150 4 100 2 50 0 0 Flow cfs Temperature 2/ 8/ 19 2/ 1/ 19 /1 9 /1 9 77 Temperature C 8 1/ 25 1/ 18 /1 9 77 76 76 1/ 4/ 19 /2 8 /2 1 1/ 11 12 12 Point Source Event 1977 Flow /1 9 /1 9 77 77 77 /1 9 /1 9 3/ 1/ 19 2/ 22 2/ 15 77 77 77 77 8 400 7 350 6 300 5 250 Fish Kill Event 200 3 150 2 100 1 50 0 0 Flow cfs Total Phosphorus 2/ 8/ 19 2/ 1/ 19 /1 9 /1 9 77 Tot Phosphorus mg/l 4 1/ 25 1/ 18 /1 9 77 76 76 1/ 4/ 19 /2 8 /2 1 1/ 11 12 12 Point Source Event 1977 Flow Ammonia N DMR below DM Ammonia N Flow 18 100000 16 10000 12 1000 10 8 100 6 4 10 2 0 Jul-71 1 Jul-74 Jul-77 Jul-80 Jul-83 Jul-86 Jul-89 Jul-92 Jul-95 Jul-98 Jul-01 Flow (cfs) Ammonia N (mg/l) 14 Unionized Ammonia Unionized Ammonia DMR near Boone R River near Van Meter DMR below Des Moines DMR near Boone R River near Van Meter DMR below Des Moines 19672003 19722003 19712003 19992003 19722003 19992003 439 378 391 60 60 60 mean 0.009 0.006 0.015 0.002 0.004 0.004 Min <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 Max 0.267 0.093 0.373 0.013 0.040 0.026 %<0.016 13% 7% 27% 0% 3% 2% Date No. months Phosphorus Major sources Nonpoint - fertilizers associated with sediment Point – wastewater & food processing plant effluents Importance Limiting nutrient (when N:P ratio >16:1) Can be re-suspended or released from sediments Phosphorus Inputs Human 1% Industry <1% Manure 45% Fertilizer 54% Estimated Point versus Non-Point Contributions to Stream P-Load Point Source 20% Non-Point Source 80% Jul-03 Jul-01 Jul-99 Jul-97 Jul-95 Jul-93 Jul-91 20 16 12 1000 10 8 100 6 4 10 2 0 1 Flow cfs TPO4 Jul-89 Jul-87 Jul-85 Jul-83 Jul-81 Jul-79 Jul-77 Jul-75 Jul-73 Jul-71 Total Phosphate mg/l Total Phosphate Des Moines River below DM Flow (cfs) 100000 18 10000 14 Total Phosphate Des Moines River near Boone TPO4 Flow (cfs) 20 100000 16 10000 12 1000 10 8 100 6 4 10 2 Feb-01 Feb-98 Feb-95 Feb-92 Feb-89 Feb-86 Feb-83 Feb-80 Feb-77 1 Feb-74 0 Flow cfs 14 Feb-71 Total Phosphate mg/l 18 Seasonal Kendall Tau Trend Analysis, Significant Trends (95%) (from Monthly Mean Data, flow adjusted) Total Phosphate Tot Phosphate n mean slope Des Moines River near Boone 1971-2003 1971-1986 1999-2003 188 129 59 0.93 1.07 0.62 -0.013 no trend -0.054 Tot Phosphate n mean slope Raccoon River near Van Meter 1972-2003 1972-1986 1999-2003 194 135 59 1.10 1.17 0.94 -0.004 0.017 no trend Tot Phosphate n mean slope Des Moines River below Des Moines 1971-2003 1971-1986 1999-2003 207 148 59 1.98 2.15 1.57 -0.018 -0.038 no trend 1999-03 Phosphorus DMR Boone DMR Sayl RR Van Meter ave 0.05 0.10 0.11 0.46 0.47 0.18 min 0.01 0.01 0.01 0.10 0.11 0.04 max 0.39 0.40 0.49 2.08 1.19 0.45 ave 0.21 0.13 0.29 0.51 0.59 0.24 min 0.04 0.03 0.05 0.21 0.17 0.10 max 0.56 0.43 1.19 1.55 1.34 1.16 26 72 36 90 78 78 DMR DM DMR Runnells DMR Pella OP TP %OP Nutrient Criteria T P in rivers 0.118 mg/l Data from 1999-03 DMR Boone DMR Sayl Rac R Van Meter ave 0.21 0.13 0.29 0.51 0.59 0.24 min 0.04 0.03 0.05 0.21 0.17 0.10 max 0.56 0.43 1.19 1.55 1.34 1.16 8 4 6 0 0 1 n 59 59 59 59 59 59 % 14 7 10 0 0 2 #months <0.118 DMR DM DMR Runnells DMR Pella Total Phosphorus Saylorville Reservoir Sediments ave Depth (cm) Water Content (%) Dry Bulk Density (g/cm3) Head 8 241 0.33 946 Head 26 190 0.38 817 Dam 12 304 0.28 1232 Dam 22 220 0.35 1019 Dam 46 198 0.37 920 TP (mg/kg) Cheney Reservoir, Kansas, USGS, Dam 647 mg/kg, Headwaters 477 mg/kg For more information dslutz@iastate.edu http://www.ccee.iastate.edu/research/lutz/homepage.html If interested contact me about statistical methods employed or see notes from this slide Notes are available by saving this presentation and opening it with Powerpoint