Pyrite Oxidation Halts Migration of a Phosphorus Plume

We have established a monitoring record of phosphate (PO₄ ^3- ) 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 SO₄ ^2- concentrations increase in response to NO₃ ^- 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.