Phosphorus K-edge X-ray absorption fine structure (XAFS) was explored as a means to distinguish between aqueous and solid phosphates and to detect changes in phosphate protonation state. Data were collected for H(3)PO(4), KH(2)PO(4), K(2)HPO(4) and K(3)PO(4) solids and solutions and for the more complex phosphates, hydroxylapatite (HAP) and struvite (MAP). The X-ray absorption near-edge structure (XANES) spectra for solid samples are distinguishable from those of solutions by a shoulder at approximately 4.5 eV above the edge, caused by scattering from cation sites. For phosphate species, the intensity of the white line peak increased for solid and decreased for aqueous samples, respectively, with phosphate deprotonation. This was assigned to increasing charge delocalization in solid samples, and the effect of solvating water molecules on charge for aqueous samples. In the extended X-ray absorption fine structure (EXAFS), backscattering from first-shell O atoms dominated the chi(k) spectra. Multiple scattering (MS) via a four-legged P-O(1)-P-O(1)-P collinear path was localized in the lower k region at approximately 3.5 A(-1) and contributed significantly to the beat pattern of the first oscillation. For EXAFS analysis, increasing Debye-Waller factors suggest more disorder in the P-O shell with addition of protons to the crystal structure due to the lengthening effects of P-OH bonds. This disorder produces splitting in the hybridized P 3p-O 2p band in the density of states. For aqueous samples, however, increased protonation reduced the structural disorder within this shell. This was linked to a change from kosmotropic to chaotropic behavior of the phosphate species, with reduced effects of H bonding on structural distortion. The intensity of MS is correlated to the degree of disorder in the P-O shell, with more ordered structures exhibiting enhanced MS. The observed trends in the XAFS data can be used to distinguish between phosphate species in both solid and aqueous samples. This is applicable to many chemical, geochemical and biological systems, and may be an important tool for determining the behavior of phosphate during the hydrothermal gasification of biomass.