Rapid estimation of soil engineering properties using diffuse reflectance near infrared spectroscopyWaruru BK, Shepherd KD, Ndegwa GM, Kamoni PT, Sila AM. 2014. Rapid estimation of soil engineering properties using diffuse reflectance near infrared spectroscopy. Biosystems Engineering 121:177-185. , 2014-05 [+]
Materials testing involve complex reference methods and several soil tests have been used for indexing material functional attributes for civil engineering applications. However, conventional laboratory methods are expensive, slow and often imprecise. The potential of soil diffuse reflectance near infrared (NIR) spectroscopy for the rapid estimation of selected key engineering soil properties was investigated. Two samples sets representing different soils from across the Lake Victoria basin of Kenya were used for the study: A model calibration set (n = 136) was obtained using a conditioned Latin hypercube sampling, and a validation set (n = 120) using a spatially stratified random sampling strategy. Spectral measurements were obtained for air-dried (<2 mm) soil sub-samples using a Fourier-transform diffuse reflectance near infrared (NIR) spectrometer. Soil laboratory reference data were also obtained for liquid limit (LL), plastic limit (PL), plasticity index (PI), linear shrinkage (LS), coefficient of linear extensibility (COLE), volumetric shrinkage (VS), clay activity number (Ac), total clay content, air-dried moisture content, and cation exchange capacity (CEC). Soil reference data were calibrated to smoothed first derivative NIR spectra using partial least squares (PLS) regression. At the calibration stage, coefficient of determination for full cross-validation (R2) of ≥0.70 was obtained for CEC, mc, LL, PI, LS, COLE and VS. Further independent validation gave R2 ≥ 0.70 and RPD (ratio of reference data SD and root mean square error of prediction) 1.7–2.2 for LL, PI, mc and CEC. The results suggested that NIR–PLS has potential for the rapid estimation of several key soil engineering properties. Further work should focus on extending calibration libraries using more diverse soil types and testing alternative infrared diffuse reflectance based methods.
Quantification of total element concentrations in soils using total X-ray fluorescence spectroscopy (TXRF)Towett, E.K., Shepherd, K.D, Cadisch, G. 2013. Quantification of total element concentrations in soils using total X-ray fluorescence spectroscopy (TXRF). Science of the Total Environment 463–464: 374–388 http://www.sciencedirect.com/science/article/pii/S, 2013-10-01 [+]
Total X-ray fluorescence spectroscopy (TXRF) determines concentrations of major and trace elements in multiple media. We developed and tested a method for the use of TXRF for direct quantification of total element concentrations in soils using an S2 PICOFOX™ spectrometer (Bruker AXS Microanalysis GmbH, Germany). We selected 15 contrasting soil samples from across sub-Saharan Africa for element analysis to calibrate the instrument against concentrations determined using the inductively coupled plasma-mass spectroscopy (ICP-MS) standard method. A consistent underestimation of element concentrations using TXRF compared to ICP-MS reference analysis occurred, indicating that spectrometer recalibration was required. Single-element recalibration improved the TXRF spectrometer's sensitivity curve. Subsequent analysis revealed that TXRF determined total element concentrations of Al, K, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, and Ga accurately (model efficacy/slope close to 1:1 line, and R2 > 0.80) over a wide range of soil samples. Other elements that could be estimated with an acceptable precision (R2 > 0.60) compared with ICP-MS although generally somewhat under- or overestimated were P, Ca, As, Rb, Sr, Y, Pr, Ta and Pb. Even after recalibration, compared to ICP-MS the TXRF spectrometer produced underestimations for elements Na, Mg, Ba, Ce, Hf, La, Nd, W and Sm and overestimations for elements Bi, Tl and Zr. We validated the degree of accuracy of the TXRF analytical method after recalibration using an independent set of 20 soil samples. We also tested the accuracy of the analysis using 2 multi-element standards as well as the method repeatability on replicate samples. The resulting total element concentration repeatability for all elements analyzed were within 10% coefficient of variability after the instrument recalibration except for Cd and Tl. Our findings demonstrate that TXRF could be used as a rapid screening tool for total element concentrations in soils assuming that sufficient calibration measures are followed.