title: GEMAS: prediction of solid-solution phase partitioning coefficients (Kd) for oxoanions and boric acid in soils using mid-infrared diffuse reflectance spectroscopy.
abstract: The authors' aim was to develop rapid and inexpensive regression models for the prediction of partitioning coefficients (Kd), defined as the ratio of the total or surface-bound metal/metalloid concentration of the solid phase to the total concentration in the solution phase. Values of Kd were measured for boric acid (B[OH]3(0)) and selected added soluble oxoanions: molybdate (MoO4(2-)), antimonate (Sb[OH](6-)), selenate (SeO4(2-)), tellurate (TeO4(2-)) and vanadate (VO4(3-)). Models were developed using approximately 500 spectrally representative soils of the Geochemical Mapping of Agricultural Soils of Europe (GEMAS) program. These calibration soils represented the major properties of the entire 4813 soils of the GEMAS project. Multiple linear regression (MLR) from soil properties, partial least-squares regression (PLSR) using mid-infrared diffuse reflectance Fourier-transformed (DRIFT) spectra, and models using DRIFT spectra plus analytical pH values (DRIFT + pH), were compared with predicted log K(d + 1) values. Apart from selenate (R(2)  = 0.43), the DRIFT + pH calibrations resulted in marginally better models to predict log K(d + 1) values (R(2)  = 0.62-0.79), compared with those from PSLR-DRIFT (R(2)  = 0.61-0.72) and MLR (R(2)  = 0.54-0.79). The DRIFT + pH calibrations were applied to the prediction of log K(d + 1) values in the remaining 4313 soils. An example map of predicted log K(d + 1) values for added soluble MoO4(2-) in soils across Europe is presented. The DRIFT + pH PLSR models provided a rapid and inexpensive tool to assess the risk of mobility and potential availability of boric acid and selected oxoanions in European soils. For these models to be used in the prediction of log K(d + 1) values in soils globally, additional research will be needed to determine if soil variability is accounted on the calibration.
authors.affiliation: Contaminant Chemistry and Ecotoxicology Program, Sustainable Agriculture Flagship Program, Waite Campus, CSIRO Land and Water, South Australia, Australia.
authors.forename: Leslie J
authors.initials: LJ
authors.lastname: Janik
authors.forename: Sean T
authors.initials: ST
authors.lastname: Forrester
authors.forename: José M
authors.initials: JM
authors.lastname: Soriano-Disla
authors.forename: Jason K
authors.initials: JK
authors.lastname: Kirby
authors.forename: Michael J
authors.initials: MJ
authors.lastname: McLaughlin
authors.forename: Clemens
authors.initials: C
authors.lastname: Reimann
mesh_terms: D000383:Agriculture; D000838:Anions / Q000032:analysis*; D001888:Boric Acids / Q000032:analysis*; D002138:Calibration; D005060:Europe; D005843:Geography; D006863:Hydrogen-Ion Concentration; D016018:Least-Squares Analysis; D016014:Linear Models; D008962:Models, Theoretical; D012987:Soil / Q000737:chemistry*; D012989:Soil Pollutants / Q000032:analysis; D012996:Solutions; D013055:Spectrophotometry, Infrared / Q000379:methods*
chemical_list: D000838:Anions; D001888:Boric Acids; D012987:Soil; D012989:Soil Pollutants; D012996:Solutions; C032688:boric acid
keywords: Anions; Metal/metalloid; Mid-infrared spectroscopy; Partial least squares regression; Soil; Solid-solution partitioning coefficients (Kd)