Wavelength Dispersive X-Ray Fluorescence Spectrometry (WD-XRF)

Wavelength Dispersive X-Ray Fluorescence Spectrometry (WD-XRF) is the oldest method of measurement of X-rays, introduced commercially in the 1950’s. This name is descriptive in that the radiation emitted from the sample is collimated with a Soller collimator, and then impinges upon an analyzing crystal. The crystal diffracts the radiation to different extents, according to Bragg’s law, depending upon the wavelength or energy of the X radiation.

This angular dispersion of the radiation permits the sequential or simultaneous detection of X-rays emitted by elements in the sample. Simultaneous instruments normally contain several sets of analyzing crystals and detectors; one is adjusted for each desired analyte in the sample. These instruments tend to be very expensive, but efficient for the routine determination or preselected elements.

WD-XRF spectrometers are usually larger and more expensive than other spectrometers. Because the analyzing crystal d-spacing determines wavelength sensitivity, they are usually more sensitive than other spectrometers. To overcome losses in X-ray optics of the WD-XRF spectrometers and to maximize primary radiation intensity, X-ray tubes are usually employed. The sample is usually held under vacuum to reduce contamination and avoid absorption of light element characteristic radiation in air.

Typical uses of WD-XRF include the analysis of oils and fuel, plastics, rubber and textiles, pharmaceutical products, foodstuffs, cosmetics and body care products, fertilizers, minerals, ores, rocks, sands, slags, cements, heat-resistant materials glass, ceramics, semiconductor wafers; the determination of coatings on paper, film, polyester and metals; the sorting or compositional analysis of metal alloys, glass and polymeric materials; and the monitoring of soil contamination, solid waste, effluent, cleaning fluids, sediments and air filters.


WD-XRF spectrometers measure X-ray intensity as a function of wavelength. This is done by passing radiation emanating from the specimen through an analyzing diffraction crystal mounted on a 2θ goniometer. By Bragg’s Law, the angle between the sample and detector yields the wavelength of the radiation:

2d sin θ = nλ ;

d is the d-spacing of the analyzing crystal,
θ is half the angle between the detector and the sample,
n is the order of diffraction.


The analyzing crystal must be oriented so that the crystal diffraction plane is directed in the appropriate direction. Figure shows a simplified schematic of the WD-XRF spectrometer. A scintillation or flow-proportional detector usually measures the fluoresced radiation. The heights of the resulting pulses are proportional to energy so using a pulse height analyzer (PHA), scattered or undesired diffraction-order X-rays can be ejected. The X-ray beam is usually collimated before and after the analyzing crystal. Each of the components showed in the below (Figure 1) were be described in the following sections.