Pyrite Oxidation Halts Migration of a Phosphorus Plume.

We have established a monitoring record of phosphate (PO ) migration in the Long Point, ON campground septic system plume that now spans 26 years. Previously, at year 16 (2006), a P plume 16 m in length was documented and provided a good fit with an analytical advection dispersion model when a P migration velocity of 0.8 m/yr was used (retardation factor of 37) and when P behaved in an otherwise conservative manner (sorption only). However, between years 16 and 26 (2016), the P plume length expanded by only 2 m (0.2 m/yr) and increased in depth by only 0.5 m. The zone of abrupt P depletion at depth occurs close to the zone where SO concentrations increase in response to NO oxidation of pyrite. Scanning electron microscope images of sand grains from the nose of the P plume reveal abundant authigenic mineral coatings of considerable thickness (∼5 to 20 μm), with Fe as the dominant cation and containing 1 to 3 wt % P. This evidence suggests that P is now being attenuated along a reaction front that coincides with the zone where pyrite oxidation is occurring. P migration may now be controlled by the rate of migration of the pyrite oxidation front and this is several times slower than the previously indicated rate in the shallower, sorption-controlled portion of the plume. Monitoring at Long Point has demonstrated the danger of embracing an overly simplistic conceptual model when attempting to predict wastewater P migration in groundwater and also highlights the unique insight provided by a long-term monitoring record.