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.