Synergistic adsorption of phosphorus by iron in lanthanum modified bentonite (Phoslock®): New insight into sediment phosphorus immobilization.

Iron redox cycle plays a primary role in controlling the mobility of P in sediments. It is crucial to better understand how lanthanum (La) modified bentonite (LMB, Phoslock®), an increasingly employed capping agent, immobilizes P from sediments by altering Fe redox-coupled P cycling. Batch adsorption experiments found that LMB effectively adsorbed Fe(II) with a capacity of 8.51 mg g-1. Fe(II)-preloaded LMB effectively retained P during a 518-hour equilibration, while up to 16.7% of adsorbed P was release-sensitive in LMB without Fe(II) preloading. A 60-day incubation experiment was performed using sediment cores, with an LMB amendment dosage of up to 200 LMB/Pmob (w/w, Pmob denotes the amount of mobile P in the surface 40 mm sediment layer). The concentrations of pore water soluble reactive P (SRP) and labile P were measured by high resolution dialysis (HR-Peeper) and by diffusive gradient in thin films (DGT), respectively, at a vertical millimeter scale. They stratified into static layers with extremely low concentration distribution in the top 16-22 mm sediments (mean SRP ≤ 0.28 mg L-1 and mean DGT-labile P ≤ 0.051 mg L-1) and active layers with decreased upward diffusion potential (≤5.85 for SRP and ≤12.7 for DGT-labile P) below the static layer, when the applied dosage reached 60 LMB/Pmob. The LMB amendment reduced the pore water Fe and DGT-labile Fe in sediments, while considerable amounts of Fe and Fe-bound P existed in the LMB binding layer (25% of the total P in 200 LMB/Pmob treatment). These findings show that the adsorption of Fe by LMB plays a significant role in the stabilization of LMB-bound P, possibly by adsorbing release-sensitive P initially bound to the rhabdophane surface. LMB adsorbed Fe and P were not released until the redox potential decreased to extremely reductive conditions (-150 mV to -300 mV), possibly due to the re-adsorption of Fe and P by LMB. This study reveals synergistic effects of Fe adsorption and provides new insight into the immobilization mechanisms of P by LMB application.