This paper investigates the use of Fourier transform infrared (FTIR) attenuated total reflectance (ATR) spectroscopy as a fast and simple way for direct determination of nitrate concentration in soil pastes, which would assist precision fertilizer placement and reduce nitrate pollution. Eight types of soils are investigated, with nitrate concentrations ranging from 0 to 1000 ppm-N. The spectral region around the nitrate band (1300-1550 cm(-1)) is analyzed by (1) principal component regression (PCR), (2) partial least squares (PLS), and (3) cross-correlation with reference libraries that include spectra of pure ions and/or soils. The main obstacle to accurate nitrate measurement appears to be an interfering band present in calcareous soils. This band, which may be due to carbonate, is located around 1450 cm(-1) and overlaps with the nitrate band centered around 1370 cm(-1). For non-calcareous soils, and in particular for light sandy agricultural soils, PLS and cross-correlation with a reference library containing only spectra of ions in water give similar results (about 8 ppm-N on dry soil basis), while PCR leads to slightly poorer results. When calcareous soils are included in the analysis, the prediction errors are about twice as large. In this case, the best results are obtained using PLS, followed by PCR, while cross-correlation with reference libraries leads to poorer results.
The development of silver halide fibers that transmit with minimal loss into the mid-IR (MIR) paved the way to their successful utilization as effective ATR (Attenuated Total Reflectance) elements, promoting the implementation of Fiberoptic Evanescent Wave Spectroscopy (FEWS) for direct monitoring of nitrate in environmental systems. Samples containing nitrate in water, soil extracts, and pastes were used for the determination of nitrate concentration with a common ATR ZnSe crystal and with silver halide fibers (FEWS). Spectra of soil pastes and suspensions and those of phosphate, carbonate, sulfate, ammonium, and soil organic constituents were collected to study possible interference with nitrate determination. The standard error of estimate (SEE) and R2 values obtained with flat fibers, using the simple single-point correlation method, were superior to those obtained for cylindrical FEWS and ZnSe ATR crystals in pure water. A significant improvement in the SEE and R2 was achieved in most soil pastes by applying the simple mode of the Cross Correlation method. Direct transmission of MIR radiation through ion-exchange membranes, partially loaded with nitrate or carbonate, was found an effective alternative for MIR-FTIR determination of these ions. Further development and modification of the FEWS devices should allow in-situ and online determination of nitrate in soil and environmental systems.
Acoustic wave propagation in a three-layer waveguiding configuration is analyzed. Considering an adhesive layer as a waveguide structure, it is shown that the propagation of guided modes is affected by the bonding quality. A comprehensive study demonstrates the possibility of utilizing measurements on guided wave propagation to detect interfacial weakness between an adhesive and adherend.
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