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SPATIAL AND SPECTRAL MODELS OF SOIL CARBON AT MULTIPLE SCALES IN FLORIDA By GUSTAVO DE MATTOS VASQUES A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2009 1 © 2009 Gustavo de Mattos Vasques 2 To all Floridians and environmental enthusiasts 3 ACKNOWLEDGMENTS I thank the University of Florida, the Soil and Water Science Department, the Alumni Fellowship program, and my parents for giving me the opportunity and the resources to conduct this study. I thank my major advisor Sabine Grunwald for her wise words of advice and guidance for research and life, and my supervisory committee members Nicholas Comerford, Willie Harris, Timothy Fik and Wendell Cropper, as well as James Sickman for their guidance and support. I also thank the Information Technology experts Brandon Hoover, Steve Bloom and William Deich IV, and my working colleagues from the Geographic Information Systems Laboratory Jinseok Hong, Brent Myers, Sanjay Lamsal, Rosanna Rivero, Deoyani Sarkhot, Mi- youn Ann, Jongsung Kim and Ho-young Kwon for their friendship and help. I also thank my cousins Robert, Sílvia and Luís Cláudio for the love and support that made my stay in the U.S. so pleasant, my friends in Gainesville for the wonderful talks, parties, trips, laughs, and cries, and my family in Brazil, who always encouraged me to pursue my dreams, and whom I miss so much. I give special thanks to my wife and best friend Patricia, whose love, friendship, enthusiasm, guidance and support were essential in everything that I have accomplished. I cannot express enough my love for her. Funding for this doctoral research was provided from various projects including “Linking Experimental and Soil Spectral Sensing for Prediction of Soil Carbon Pools and Carbon Sequestration at Landscape Scales” (Cooperative Ecosystem Studies Unit, Natural Resources Conservation Service, U.S. Department of Agriculture), and “Rapid Assessment and Trajectory Modeling of Changes in Soil Carbon across a Southeastern Landscape” (National Research Initiative, U.S. Department of Agriculture). 4 TABLE OF CONTENTS page ACKNOWLEDGMENTS ...............................................................................................................4 LIST OF TABLES ..........................................................................................................................9 LIST OF FIGURES ....................................................................................................................... 12 ABSTRACT .................................................................................................................................. 15 CHAPTER 1 INTRODUCTION ................................................................................................................. 17 Rationale and Significance ..................................................................................................... 17 Overview ................................................................................................................................ 20 2 COMPARISON OF MULTIVARIATE METHODS FOR INFERENTIAL MODELING OF SOIL CARBON USING VISIBLE/NEAR-INFRARED SPECTRA ........ 23 Summary ................................................................................................................................ 23 Introduction ............................................................................................................................ 24 Materials and Methods ........................................................................................................... 27 Study Area ...................................................................................................................... 27 Field Sampling ................................................................................................................ 28 Laboratory Analysis ........................................................................................................ 28 Spectroscopy ................................................................................................................... 29 Pre-processing Transformations ..................................................................................... 29 Multivariate Techniques ................................................................................................. 30 Results and Discussion ........................................................................................................... 33 Descriptive Statistics ....................................................................................................... 33 Stepwise Multiple Linear Regression ............................................................................. 33 Principal Components Regression .................................................................................. 34 Partial Least Squares Regression .................................................................................... 35 Regression Tree .............................................................................................................. 36 Committee Trees ............................................................................................................. 38 Variable Selection ........................................................................................................... 39 Pre-processing Transformations ..................................................................................... 39 Conclusions ............................................................................................................................ 41 3 MODELING OF SOIL ORGANIC CARBON FRACTIONS USING VISIBLE/NEAR- INFRARED SPECTROSCOPY ............................................................................................ 61 Summary ................................................................................................................................ 61 Introduction ............................................................................................................................ 62 Materials and Methods ........................................................................................................... 63 5 Field and Laboratory Measurements ............................................................................... 63 Pre-treatment of Soil Spectra and Multivariate Methods ................................................ 65 Results and Discussion ........................................................................................................... 68 Descriptive Statistics ....................................................................................................... 68 Visible/Near-Infrared Spectroscopy Models of Soil Organic Carbon Properties ........... 70 Conclusions ............................................................................................................................ 75 4 BUILDING A SPECTRAL LIBRARY TO ESTIMATE SOIL ORGANIC CARBON IN FLORIDA ......................................................................................................................... 88 Summary ................................................................................................................................ 88 Introduction ............................................................................................................................ 88 Materials and Methods ........................................................................................................... 91 Study Area ...................................................................................................................... 91 Field and Laboratory Measurements ............................................................................... 92 Soil Scanning and Data Preparation ................................................................................ 93 Multivariate Calibration .................................................................................................. 94 Results and Discussion ........................................................................................................... 97 Descriptive Statistics ....................................................................................................... 97 Performance of the Different Multivariate Calibration Methods .................................... 99 Effect of the Inclusion of Soil Order Data, or Stratification by Soil Order .................. 101 Explanatory Wavelengths for Soil Organic Carbon ...................................................... 102 Conclusions .......................................................................................................................... 103 5 REGIONAL MODELING OF SOIL CARBON AT MULTIPLE DEPTHS WITHIN A SUBTROPICAL WATERSHED ......................................................................................... 113 Summary .............................................................................................................................. 113 Introduction .......................................................................................................................... 114 Materials and Methods ......................................................................................................... 116 Study Area .................................................................................................................... 116 Field Sampling .............................................................................................................. 117 Laboratory Analysis ...................................................................................................... 118 Comparison of Soil Total Carbon at Different Depths ................................................. 119 Relationship between Soil Total Carbon and Environmental Landscape Factors ........ 119 Scaling-up of Soil Total Carbon in the Santa Fe River Watershed ............................... 120 Results and Discussion ......................................................................................................... 123 Descriptive Statistics ..................................................................................................... 123 Relationship between Soil Total Carbon and Environmental Landscape Factors ........ 125 Scaling-up of Soil Total Carbon in the Santa Fe River Watershed ............................... 131 Conclusions .......................................................................................................................... 138 6 UPSCALING OF DYNAMIC SOIL ORGANIC CARBON POOLS IN A NORTH- CENTRAL FLORIDA WATERSHED ............................................................................... 153 Summary .............................................................................................................................. 153 Introduction .......................................................................................................................... 153 6 Materials and Methods ......................................................................................................... 157 Study Area .................................................................................................................... 157 Field Sampling and Laboratory Methods ...................................................................... 157 Upscaling Methods ....................................................................................................... 158 Results and Discussion ......................................................................................................... 160 Descriptive Statistics ..................................................................................................... 160 Upscaling of Soil Organic Carbon Properties ............................................................... 162 Conclusions .......................................................................................................................... 168 7 INFLUENCE OF GRAIN, EXTENT, AND GEOGRAPHIC REGION ON SOIL CARBON MODELS IN FLORIDA, USA .......................................................................... 180 Summary .............................................................................................................................. 180 Introduction .......................................................................................................................... 181 Materials and Methods ......................................................................................................... 183 Study Areas, Sampling Designs, and Laboratory Methods .......................................... 183 The state of Florida ................................................................................................ 184 The Santa Fe River watershed ............................................................................... 186 The University of Florida Beef Cattle Station ....................................................... 187 Conversion of Soil Organic Carbon Measurements to Soil Total Carbon .................... 188 Calculation of Profile Soil Total Carbon at 0-100 cm .................................................. 188 Regression Modeling of Soil Total Carbon .................................................................. 189 Preparation of soil total carbon data ...................................................................... 190 Preparation of environmental Geographic Information System layers .................. 191 Evaluating the influence of grain ........................................................................... 192 Evaluating the influence of extent ......................................................................... 193 Evaluating the influence of geographic regions ..................................................... 194 Results and Discussion ......................................................................................................... 194 Descriptive Statistics ..................................................................................................... 194 Influence of Grain on Soil Total Carbon Regression Models ....................................... 195 Transferability of Soil Total Carbon Regression Models across Grains ....................... 198 Influence of Extent on Soil Total Carbon Regression Models ...................................... 199 Transferability of Soil Total Carbon Regression Models across Extents ..................... 200 Influence of Geographic Region on the Distribution of Soil Total Carbon .................. 201 Transferability of Soil Total Carbon Regression Models across Geographic Regions . 202 Conclusions .......................................................................................................................... 205 8 MULTI-SCALE BEHAVIOR OF SOIL CARBON AT NESTED REGIONS IN FLORIDA, USA .................................................................................................................. 221 Summary .............................................................................................................................. 221 Introduction .......................................................................................................................... 222 Materials and Methods ......................................................................................................... 225 Study Area .................................................................................................................... 225 Field Sampling and Laboratory Analysis ...................................................................... 226 Characterization of the Spatial Dependence of Soil Total Carbon ............................... 228 Results and Discussion ......................................................................................................... 229 7 Descriptive Statistics ..................................................................................................... 229 Spatial Dependence of Soil Total Carbon ..................................................................... 230 Variogram analysis ................................................................................................ 230 Fractal analysis ...................................................................................................... 233 Conclusions .......................................................................................................................... 236 9 SYNTHESIS AND OUTLOOK .......................................................................................... 247 LIST OF REFERENCES ............................................................................................................ 256 BIOGRAPHICAL SKETCH ....................................................................................................... 273 8 LIST OF TABLES Table page 2-1 Investigations on diffuse reflectance spectroscopy of soil carbon and soil organic matter. ................................................................................................................................ 42 2-2 Pre-processing transformations applied to the spectral curves of soil samples. ................ 45 2-3 Soil total carbon (TC) and log-transformed TC (LogTC) descriptive statistics for the whole dataset, calibration set, and validation set. ............................................................. 46 2-4 Summary statistics for the spectral models of log-transformed soil total carbon (LogTC) produced by stepwise multiple linear regression (SMLR). ................................ 47 2-5 Descriptive statistics of predicted log-transformed soil total carbon (LogTC) for the calibration and validation sets for the best models obtained from the five multivariate calibration techniques tested. ............................................................................................ 48 2-6 Summary statistics for the spectral models of log-transformed soil total carbon (LogTC) produced by principal components regression (PCR). ....................................... 49 2-7 Summary statistics for the spectral models of log-transformed soil total carbon (LogTC) produced by partial least squares regression (PLSR). ........................................ 50 2-8 Summary statistics for the spectral models of log-transformed soil total carbon (LogTC) produced by regression tree (RT). ...................................................................... 51 2-9 Summary statistics for the spectral models of log-transformed soil total carbon (LogTC) produced by committee trees (CT). .................................................................... 52 3-1 Descriptive statistics of measured soil organic carbon properties. .................................... 77 3-2 Pearson’s correlation coefficients between the measured soil organic carbon properties. .......................................................................................................................... 79 3-3 Summary statistics of the models obtained for each soil organic carbon property by the different multivariate methods, associated with their respective best pre- processing transformations. ............................................................................................... 80 3-4 Summary statistics of the models obtained for each soil organic carbon fraction by simple linear regression, and by partial least squares regression, using both soil reflectance and LogTC as predictors. ................................................................................ 82 4-1 Descriptive statistics of soil organic carbon (SOC) and ln-transformed SOC (LnSOC) for the whole dataset, and stratified soil horizons. .......................................... 105 9 4-2 Summary statistics for the spectral models of soil organic carbon (SOC) produced by committee trees (CT). ...................................................................................................... 106 4-3 Summary statistics for the spectral models of ln-transformed soil organic carbon (LnSOC) produced by partial least squares regression (PLSR). ..................................... 107 5-1 Environmental data and sources used to model the global spatial trend of log- transformed soil total carbon (LogTC). ........................................................................... 140 5-2 Descriptive statistics of observed soil total carbon (TC) and log-transformed TC (LogTC) at different depths. ............................................................................................ 142 5-3 Pair-wise comparison of log-transformed soil total carbon (LogTC) at different depths. ............................................................................................................................. 144 5-4 Analyses of variance (ANOVA) between log-transformed soil total carbon at 0-100 cm (LogTC100) and selected environmental variables. .................................................. 145 5-5 Homogeneous groups of log-transformed soil total carbon at 0-100 cm (LogTC100) based on land use/land cover, soil order, soil drainage class, and geologic unit, respectively, according to Dunnett’s T3 test at the 0.05 confidence level. ..................... 146 5-6 Comparative results of the three geostatistical methods used to model soil total carbon (TC) at different depths. ...................................................................................... 147 5-7 Semivariogram parameters of the fitted exponential model of the best geostatistical method identified for soil total carbon (TC) at each depth. ............................................. 148 6-1 Descriptive statistics of measured soil organic carbon (C) properties. ........................... 171 6-2 Comparative results of the three geostatistical methods used to model soil organic carbon (C) properties at 0-30 cm. .................................................................................... 173 6-3 Stepwise multiple linear regression (SMLR) models, and variables selected by regression tree (RT) models of the global trend of soil organic carbon (C) properties. .. 174 6-4 Semivariogram parameters of the fitted exponential models of the soil organic carbon (C) properties. ...................................................................................................... 175 7-1 Environmental Geographic Information Systems (GIS) layers used as explanatory variables in the stepwise multiple linear regression models of soil total carbon. ............ 209 7-2 Descriptive statistics of soil total carbon (TC) and ln-transformed TC (LnTC) at the three study areas. ............................................................................................................. 210 7-3 Regression coefficients and goodness-of-fit statistics of the stepwise multiple linear regression model of ln-transformed soil total carbon in ln% derived at different grains in the Santa Fe River watershed. .......................................................................... 211 10

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