A comparative discrimination spectral detection (CDSD) system for the identification of chemicals with overlapping spectral signatures, including: a radiation source for delivering radiation to a sample; a radiation collector for collecting radiation from the sample; a plurality of beam splitters for splitting the radiation collected from the sample into a plurality of radiation beams; a plurality of low-resolution optical filters for filtering the plurality of radiation beams; a plurality of radiation detectors for detecting the plurality filtered radiation beams; and a processor for: receiving a set of reference spectra related to a set of target chemicals and generating a set of base vectors for the set of target chemicals from the set of reference spectra, wherein the set of base vectors define a geometrical shape in a configuration space; receiving a set of filtered test spectra from the plurality of radiation detectors and generating a set of test vectors in the configuration space from the set of filtered test spectra; assessing a geometrical relationship of the set of test vectors and the geometrical shape defined by the set of base vectors in the configuration space; and based on the assessed geometrical relationship, establishing a probability that a given test spectrum or spectra matches a given reference spectrum or spectra.
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