Spectroscopy apparatuses oriented to the critical angle of the sample are described that detecting the spectral characteristics of a sample wherein the apparatus consists of an electromagnetic radiation source adapted to excite a sample with electromagnetic radiation introduced to the sample at a location at an angle of incidence at or near a critical angle of the sample; a transmitting crystal in communication with the electromagnetic radiation source and the sample, the transmitting crystal having a high refractive index adapted to reflect the electromagnetic radiation internally; a reflector adapted to introduce the electromagnetic radiation to the sample at or near an angle of incidence near the critical angle between the transmitting crystal and sample; and a detector for detecting the electromagnetic radiation from the sample. Also, provided herein are methods, systems, and kits incorporating the peri-critical reflection spectroscopy apparatus.