This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K2HPO4 and FePO4 center dot 2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Sicontaining ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K2HPO4 and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO4 center dot 2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO4 center dot 2H(2)O confirmed the findings from P Ledge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 pm): whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P Kedge method is 51.1m and that of P L-edge and Fe M-edge methods is 50 nm. (C) 2011 Elsevier Inc. All rights reserved.