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Isotopic and Chemical Composition of Inorganic and Organic Water-Quality Samples from the Mississippi River Basin, 1997–98

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Isotopic and Chemical Composition of Inorganic and Organic Water-Quality Samples from the Mississippi River Basin, 1997–98 Isotopic and Chemical Composition of Inorganic and Organic Water-Quality Samples from the Mississippi River Basin, 1997–98 By William A. Battaglin, Carol Kendall, Cecily C.Y.Chang, Steve R. Silva, and Donald H. Campbell U.S. GEOLOGICAL SURVEY Water-Resources Investigations Report 01-4095 Prepared in cooperation with the U.S. ENVIRONMENTAL PROTECTION AGENCY GULF OF MEXICO PROGRAM Denver, Colorado 2001 U.S. DEPARTMENT OF THE INTERIOR GALE A. NORTON, Secretary U.S. GEOLOGICAL SURVEY Charles G. Groat, Director The use of firm, trade, and brand names in this report is for identification purposes only and does not constitute endorsement by the U.S. Geological Survey. For additional information write to: Copies of this report can be purchased from: District Chief U.S. Geological Survey U.S. Geological Survey Information Services Box 25046, Mail Stop 415 Box 25286 Denver Federal Center Federal Center Denver, CO 80225-0046 Denver, CO 80225 CONTENTS Abstract.................................................................................................................................................................................. 1 Introduction............................................................................................................................................................................ 1 Problem........................................................................................................................................................................ 1 Objectives and Hypotheses.......................................................................................................................................... 2 Background.................................................................................................................................................................. 2 Gulf of Mexico Hypoxia and Mississippi River Discharge............................................................................... 2 Nitrogen Sources ............................................................................................................................................... 3 Previous Isotope Investigations ......................................................................................................................... 5 Nitrogen Transformations.................................................................................................................................. 6 Acknowledgments ....................................................................................................................................................... 7 Methods ................................................................................................................................................................................. 7 Plan of Study................................................................................................................................................................ 7 Sampling Stations ........................................................................................................................................................ 7 Large River Stations .......................................................................................................................................... 7 Small Stream Stations........................................................................................................................................ 7 Sampling Schedule and Procedure .............................................................................................................................. 7 Lagrangian Samples........................................................................................................................................... 10 Analytical Methods...................................................................................................................................................... 11 δ15 δ18 Analysis of N and O of NO3 in Water ..................................................................................................... 11 Analysis of δ15N, δ13C, and δ34S of Suspended POM in Water........................................................................ 15 Nutrients and Major Ions ................................................................................................................................... 15 Discharge and Physical Properties..................................................................................................................... 15 GIS Data and Analysis................................................................................................................................................. 15 Quality Assurance........................................................................................................................................................ 16 Sample Collection.............................................................................................................................................. 16 NO3 in Water Isotope Analysis.......................................................................................................................... 16 Particulate Organic Material Isotope Analysis .................................................................................................. 16 Results.................................................................................................................................................................................... 18 δ15 δ18 N and O of NO3 Isotope Ratio Values ............................................................................................................... 18 Large Rivers ...................................................................................................................................................... 18 Small Streams ................................................................................................................................................... 24 δ15N and δ13C of POM Isotope Ratio Values ............................................................................................................. 30 Large Rivers ...................................................................................................................................................... 30 Small Streams ................................................................................................................................................... 30 Concentrations of Nutrients and Major Ions ............................................................................................................... 34 Large Rivers ...................................................................................................................................................... 34 Small Streams ................................................................................................................................................... 44 Physical Properties and Field Chemistry..................................................................................................................... 46 Relations Between Isotopic Ratios and Basin Characteristics .................................................................................... 46 Evidence for Sources of Nitrogen in the Mississippi River......................................................................................... 46 Evidence for Transformation of Nitrogen in the Mississippi River............................................................................. 51 Conclusions............................................................................................................................................................................ 53 Suggestions for Future Research ................................................................................................................................. 54 References Cited.................................................................................................................................................................... 54 CONTENTS III FIGURES 1. Graph showing estimated annual nitrogen inputs in the 20 States that comprise most of the agricultural land in the Mississippi River basin, 1951 to 1999............................................................................................................. 4 2–4. Maps showing: 2. Locations of sampling stations and associated drainage basins for: (a) large rivers, and (b) small streams ..... 5 3. Land cover in the Mississippi River basin ......................................................................................................... 9 4. Land cover in the Sugar Creek at New Providence, IN basin............................................................................ 17 5–15. Graphs showing: δ15 δ18 5. Differences between: (a) NO2 plus NO3 concentrations (in mg/L), and N and O of NO3 values (in per mil) in 18 pairs of concurrent duplicate water samples; and (b) δ15N and δ13C of POM values (in per mil) in 8 pairs of field collected concurrent duplicate sediment samples. ................................. 18 6. Time series of 1997 data for large river stations; (a) discharge, (b) δ15N, (c) δ18O, and (d) NO2 plus NO3. ............................................................................................................................................. 20 7. Time series of 1998 data for large river stations; (a) discharge, (b) δ15N, (c) δ18O, and (d)
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