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The influence of hyporheic exchange on selenium (Se) biogeochemistry and mobility in sediments is unknown. A multiscale investigation of Se biogeochemistry in the hyporheic zone of East Mill Creek (EMC), southeastern Idaho, USA, was performed using in situ surface water and pore water geochemical measurements, a field-based stream tracer test, and energy-dependent micro synchrotron X-ray fluorescence (mu-SXRF) measurements of Se speciation in sediments. The active hyporheic zone was determined to be 12 +/- 3 cm. Pore water redox profiles indicated that a transition to suboxic conditions begins at approximately 6 cm. Modeling pore water Se and solid phase analysis suggested Se uptake is occurring. Micro-SXRF analysis of sediments showed reduced elemental Se or selenides throughout the profile and selenite in surface sediments. Field geochemical measurements and microscale analysis both support the hypothesis that reduction in the hyporheic zone promotes sequestration of surface water Se.

The transport and bioavailability of selenium in the environment is controlled by its chemical speciation. However, knowledge of the biogeochemistry and speciation of Se in streambed sediment is limited. We investigated the speciation of Se in sediment cores from the Blackfoot River (BFR), Idaho using sequential extractions and synchrotron-based micro-X-ray fluorescence (micro-SXRF). We collected micro-SXRF oxidation state maps of Se in sediments, which had not been done on natural sediment samples. Selective extractions showed that most Se in the sediments is present as either (1) nonextractable Se or (2) base extractable Se. Results from micro-SXRF showed three defined species of Se were present in all four samples: Se(-II,O), Se(IV), and Se(VI). Se(-II,O) was the predominant species in samples from one location, and Se(IV) was the predominant species in samples from a second location. Results from both techniques were consistent, and suggested that the predominant species were Se(-II) species associated with recalcitrant organic matter, and Se(IV) species tightly bound to organic materials. This information can be used to predict the biogeochemical cycling and bioavailability of Se in streambed sediment environments.