The Differential Geochemical Behavior of Arsenic and Phosphorus in the Water Column and Sediments of the Saguenay Fjord Estuary, Canada

The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.