Nitrate In The Mississippi River And Its Tributaries, 1980 .

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National Water-Quality Assessment ProgramNitrate in the Mississippi River and Its Tributaries, 1980–2010:An Updateri RwaRin o!IOWA-WAPMIZZ-HEMissouri RiverMSSP-CL! R iv e risIoippiRM issouissIOWA-WAPIowa River!MississippiR! MSSP-CLILLI-VCIllinois River!! MSSP-GR!! MSSP-THOHIO-GRCH! Ohio RiverKnox Landing, La. ! MSSP-OUT!Old River! Tarbert Landing, Miss.Outflow Channel! St. Francisville, La.Mississippi RiverGulf of MexicoAtchafalaya River!MSSP-OUTArkansas RiverRed RiverArkansas RiverRI ll! ILLI-VCO hio! ! MSSP-GRMIZZ-HEMSSP-TH ! !OHIO-GRCHMississippi RiverMissGulf of MexicoFigure 1. Map of Mississippi River Basin and study sites, and a schematic line drawing of the relative locations of study sites(orange circles), major tributaries, and additional sites used for streamflow data (black dots, see footnotes in Table 1). Fluxestimates at each site include entire upstream drainage basin.Scientific Investigations Report 2013–5169U.S. Department of the InteriorU.S. Geological Survey

Cover. Mississippi River Basin and study sites, and a schematic line drawing of the relative locations of study sites, major tributaries, andadditional sites used for streamflow data.

Nitrate in the Mississippi River and ItsTributaries, 1980–2010: An UpdateBy Jennifer C. Murphy, Robert M. Hirsch, and Lori A. SpragueNational Water-Quality Assessment ProgramScientific Investigations Report 2013–5169U.S. Department of the InteriorU.S. Geological Survey

U.S. Department of the InteriorSALLY JEWELL, SecretaryU.S. Geological SurveySuzette M. Kimball, Acting DirectorU.S. Geological Survey, Reston, Virginia: 2013For more information on the USGS—the Federal source for science about the Earth, its natural and livingresources, natural hazards, and the environment, visit http://www.usgs.gov or call 1–888–ASK–USGS.For an overview of USGS information products, including maps, imagery, and publications,visit http://www.usgs.gov/pubprodTo order this and other USGS information products, visit http://store.usgs.govAny use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by theU.S. Government.Although this report is in the public domain, permission must be secured from the individual copyright owners toreproduce any copyrighted materials contained within this report.Suggested citation:Murphy, J.C., Hirsch, R.M., and Sprague, L.A., 2013, Nitrate in the Mississippi River and its tributaries, 1980–2010—An update: U.S. Geological Survey Scientific Investigations Report 2013–5169, 31 p., http://pubs.usgs.gov/sir/2013/5169/.

iiiContentsAbstract.1Introduction.1Methods .3Trends in Nitrate Concentration and Flux in the Mississippi River and Its Tributaries: An Update.4Annual Trends .4The 30-Year Annual Trends: 1980–2010.4The 20-Year and 10-Year Trends: 1980–2000 and 2000–2010.4Changes in Relative Contributions between 1980 and 2010.6Spring Trends .6Site-Specific Observations and Interpretations .6Mississippi River at Clinton, Iowa .8Flow-Normalized Nitrate Concentration and Flux.8Comparison of Nitrate Concentrations over Time and with Streamflow.8Iowa River at Wapello, Iowa.9Flow-Normalized Nitrate Concentration and Flux.9Comparison of Nitrate Concentrations over Time and with Streamflow.9Illinois River at Valley City, Illinois.10Flow-Normalized Nitrate Concentration and Flux.10Comparison of Nitrate Concentrations over Time and with Streamflow.10Mississippi River below Grafton, Illinois.11Flow-Normalized Nitrate Concentration and Flux.11Comparison of Nitrate Concentrations over Time and with Streamflow.11Missouri River at Hermann, Missouri.12Flow-Normalized Nitrate Concentration and Flux.12Comparison of Nitrate Concentrations over Time and with Streamflow.12Mississippi River at Thebes, Illinois.13Flow-Normalized Nitrate Concentration and Flux.13Comparison of Nitrate Concentrations over Time and with Streamflow.13Ohio River at Dam 53 near Grand Chain, Illinois.14Flow-Normalized Nitrate Concentration and Flux.14Comparison of Nitrate Concentrations over Time and with Streamflow.14Mississippi River above Old River Outflow Channel, Louisiana.15Flow-Normalized Nitrate Concentration and Flux.15Comparison of Nitrate Concentrations over Time and with Streamflow.15Effect of Calibration Period on Estimates of Nitrate Concentration and Flux.16Summary and Conclusions.16Acknowledgments.16References Cited.17Appendix 1.18Appendix 2.25

ivFigures1. Map showing the Mississippi River Basin and study sites, and a schematicline drawing of the relative locations of study sites, major tributaries, andadditional sites used for streamflow data.22–17. Graphs showing—2. Annual mean estimated concentration and flow-normalizedconcentration and total annual estimated flux and flow-normalized fluxfrom 1980 through 2010 for the Mississippi River at Clinton, Iowa (MSSP-CL).83. Expected nitrate concentrations at Mississippi River at Clinton,Iowa (MSSP-CL) from 2000 through 2010.84. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980 through2010 for the Iowa River at Wapello, Iowa (IOWA-WAP).95. Expected nitrate concentrations at Iowa River at Wapello, Iowa(IOWA-WAP) from 2000 through 2010.96. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980through 2010 for the Illinois River at Valley City, Illinois (ILLI-VC).107. Expected nitrate concentrations at Illinois River at Valley City,Illinois (ILLI-VC) from 2000 through 2010.108. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980 through2010 for the Mississippi River below Grafton, Illinois (MSSP-GR).119. Expected nitrate concentrations at Mississippi River below Grafton,Illinois (MSSP-GR) from 2000 through 2010.1110. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980through 2010 for the Missouri River at Hermann, Missouri (MIZZ-HE).1211. Expected nitrate concentrations at Missouri River at Hermann,Missouri (MIZZ-HE) from 2000 through 2010.1212. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980 through2010 for the Mississippi River at Thebes, Illinois (MSSP-TH).1313. Expected nitrate concentrations at Mississippi River at Thebes,Illinois (MSSP-TH) from 2000 through 2010.1314. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980 through2010 for the Ohio River at Dam 53 near Grand Chain, Illinois (OHIO-GRCH).1415. Expected nitrate concentrations at Ohio River at Dam 53 near Grand Chain,Illinois (OHIO-GRCH) from 2000 through 2010.1416. Annual mean estimated concentration and flow-normalized concentrationand total annual estimated flux and flow-normalized flux from 1980 through2010 for the Mississippi River above Old River Outflow Channel,Louisiana (MSSP-OUT).1517. Expected nitrate concentrations at Old River Outflow Channel, Louisiana(MSSP-OUT) from 2000 through 2010.15

vTables1.Site and data characteristics of the eight Mississippi River Basin sites used in thisstudy (1980–2010).22. The 30-year (1980–2010) annual and spring trends in flow-normalized nitrateconcentration and flux at eight sites in the Mississippi River Basin.53. The 20-year (1980–2000) and 10-year (2000–2010) annual trends in flow-normalizednitrate concentration and flux at eight sites in the Mississippi River Basin.74. The 20-year (1980–2000) and 10-year (2000–2010) spring trends in flow-normalizednitrate concentration and flux at eight sites in the Mississippi River Basin.7Conversion FactorsSI to Inch/PoundMultiplymeter (m)kilometer (km)square meter (m2)square kilometer (km2)cubic meter per second (m3/s)kilogram (kg)ByLength3.2810.6214Area10.760.3861Flow rate35.31Mass2.205To obtainfoot (ft)mile (mi)square foot (ft2)square mile (mi2)cubic foot per second (ft3/s)pound avoirdupois (lb)Concentrations of chemical constituents in water are given in milligrams per liter (mg/L).

Nitrate in the Mississippi River and Its Tributaries,1980–2010: An UpdateBy Jennifer C. Murphy, Robert M. Hirsch, and Lori A. SpragueAbstractIntroductionNitrate concentration and flux were estimated from 1980through 2010 at eight sites in the Mississippi River Basin aspart of the National Water-Quality Assessment (NAWQA)Program of the U.S. Geological Survey (USGS). Theseestimates extend the results from a previous investigation thatprovided nitrate estimates from 1980 through 2008 at the samesites. From 1980 through 2010, annual flow-normalized (FN)nitrate concentration and flux in the Iowa and Illinois Riversdecreased by 11 to 15 percent. These two rivers had the highest FN nitrate concentration in 1980 (5.3 milligrams per liter[mg/L] and 3.9 mg/L, respectively) of any of the study sites.Nitrate increased in the Missouri River (79 and 45 percentincrease in FN concentration and flux, respectively), and at thefour sites on the Mississippi River (17 to 70 percent increasein FN concentration and 8 to 55 percent increase in FN flux)from 1980 through 2010. Nitrate in the Ohio River was generally stable during this time. Historically, nitrate was highand changed little in the Iowa and Illinois Rivers; however,nitrate concentrations began to decrease around 2000, and thisdecrease continued through 2010. Also during this time, nearflat nitrate trends in lower sections of the Mississippi Riverbegan increasing, likely reflecting the acceleration of alreadyincreasing nitrate trends in the upper Mississippi and MissouriRivers, in addition to increases in inputs from other tributariesin the lower part of the Mississippi River Basin. Spring trends(April through June) generally parallel annual trends at allsites from 1980 through 2010, except in the Iowa River wheredecreasing nitrate during the spring was not observed. In general, most sites had increases in nitrate concentration at lowstreamflows, which suggests increases in legacy nitrate fromgroundwater or point source contributions. In aggregate, thedecreases in nitrate concentrations from the Iowa and IllinoisRivers, which largely occurred during high flows, appear tobe overshadowed by increasing nitrate concentrations acrossmuch of the Mississippi River Basin.Nitrate flux from the Mississippi River is a major determinant of the extent and severity of the hypoxic zone that formsin the northern Gulf of Mexico every summer (Scavia and others, 2003; Turner and others, 2006, 2012). This hypoxic zoneis one of the largest in the world (Rabalais and others, 2002),and reducing its size is an important national goal (MississippiRiver/Gulf of Mexico Watershed Nutrient Task Force, 2008).Accurate estimation of nitrate flux from the Mississippi RiverBasin (MRB) to the Gulf is a vital step towards this goal andhas been a critical scientific task for over a decade (Goolsbyand others, 2000; Goolsby and Battaglin, 2001; McIssac andothers, 2001). A recent study by Sprague and others (2011)used a new approach, the “weighted regressions on time,discharge, and season” (WRTDS) method (Hirsch and others,2010), to estimate nitrate plus nitrite (termed nitrate hereafter)concentration and flux from 1980 through 2008 at eight sitesin the MRB (fig. 1). Sprague and others (2011) reported noconsistent declines in nitrate concentration or flux at any of thesites. Furthermore, from 1980 through 2008 nitrate increasedconsiderably in the upper Mississippi River and the MissouriRiver and remained the same or increased at a slower rate atthe other sites (Sprague and others, 2011). This report followsthat of Sprague and others (2011) and extends estimates ofnitrate concentration and flux through 2010.This report presents estimates of nitrate concentrationand flux at eight sites in the MRB from 1980 through 2010(table 1) and was completed as part of the National WaterQuality Assessment (NAWQA) Program of the U.S. Geological Survey (USGS). It is one of several studies that have beenconducted across the Nation to provide a better understandingof changes in nutrient concentrations and fluxes over time.Using the methods described in Sprague and others (2011),this report documents (1) noteworthy developments in trendswith the extension of estimates from 2008 (Sprague and others, 2011) through 2010, (2) 30-year, 20-year, and 10-yearannual trends in nitrate during 1980–2010, 1980–2000, and2000–2010, respectively, and (3) spring trends in nitrate (Aprilthrough June) for the same periods. This report also examinesthe variability of expected nitrate concentrations in relation toseason and streamflow at each of the eight sites for a recentperiod from 2000 through 2010.

2   Nitrate in the Mississippi River and Its Tributaries, 1980–2010: An Updateippri RwaRin o!IOWA-WAPMIZZ-HEMissouri RiverMSSP-CL! R iv e risIoIOWA-WAPIowa River!iRM issouissArkansas River!MSSP-OUTGulf of Mexico! MSSP-CLILLI-VCIllinois River!! MSSP-GR!! MSSP-THOHIO-GRCH! Ohio RiverKnox Landing, La. ! MSSP-OUT!Old River! Tarbert Landing, Miss.Outflow Channel! St. Francisville, La.Mississippi RiverAtchafalaya RiverMississippiRRed RiverArkansas RiverRI ll! ILLI-VCO hio! ! MSSP-GRMIZZ-HEMSSP-TH ! !OHIO-GRCHMississippi RiverMissGulf of MexicoFigureMap of MississippiRiverstudyand a schematicline ofdrawingof thelocationsrelative locationsof studysitesFigure1. 1. MississippiRiver BasinandBasinstudyandsites,andsites,a schematicline drawingthe relativeof study tnotesinTable1).Fluxtributaries, and additional sites used for streamflow data. Flux estimates at each site include entire upstream drainage basin.estimates at each site include entire upstream drainage basin.Table 1. Site and data characteristics of the eight Mississippi River Basin sites used in this study (1980–2010).[km2, square kilometers; USGS, U.S. Geological Survey]SiteabbreviationSite numberSite nameBasin area(km2)Number ofsamplesStart dateEnd pi River at Clinton, IAIOWA-WAP05465500Iowa River at Wapello, is River at Valley City, ssippi River below Grafton, uri River at Hermann, ssissippi River at Thebes, IL1,847,1801/30/19738/2/2011511OHIO-GRCH036125002 Ohio River at Dam 53 near Grand Chain, /22/2011589MSSP-OUT1---3Mississippi River above Old River Outflow Channel, LA221,703Model calibrationStreamflow measured at Mississippi River at Grafton, IL (USGS site 05587450).1Streamflow measured at Ohio River at Metropolis, IL (USGS site 03611500).2MSSP-OUT is meant to provide an approximation of streamflow, concentration, and flux just upstream of the Old River Outflow Channel. Streamflow isthe sum of Mississippi River at Tarbert Landing, MS (U.S. Army Corps of Engineers station 01100) and Old River Outflow Channel near Knox Landing, LA(U.S. Army Corps of Engineers station 02600), and nutrient data was sampled at Mississippi River near St. Francisville, LA (USGS site 07373420).3

Methods   3MethodsFollowing the methods of Sprague and others (2011),nitrate concentration and flux were estimated using theWRTDS method. WRTDS uses locally weighted regressionto estimate daily nitrate concentration. Sepa

R Oh i o I R l i n o i s R i v e I o w a R Gulf of Mexico Mississippi River!! MSSP-CL IOWA-WAP Iowa River Illinois River Missouri River Ohio River Arkansas River!!!!! ILLI-VC MSSP-GR MIZZ-HE MSSP-TH MSSP-OUT OHIO-GRCH Gulf of Mexico!!! Red River Atchafalaya River Mississippi River Tarbert Landing, Miss. St. Francisville, La.

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