Iron-sulphur-phosphorus interactions: implications for sediment buffering capacity in a mediterranean eutrophic lagoon (Sacca di Goro, Italy)

The interactions among sedimentary cycles of sulphur, iron and phosphorus were investigated in the eutrophic Sacca di Goro lagoon (Northern Adriatic coast, Italy) in order to assess the iron buffering capacity of the sediment. Three stations were chosen, which represented different primary producer communities, hydrodynamics and sediment characteristics. Station G was close to the outlet of the Po di Volano river, station 4 was in the central part of the lagoon under tidal influence and station 17, in the sheltered zone, was affected by macroalgal blooms. From January 1997 to January 1998, sediment cores were sampled approximately every 2 months. In parallel, temperature, salinity and dissolved oxygen were determined in the water column. Sedimentary profiles of Eh, pH, dissolved sulphide (DS), acid volatile sulphide (AVS), chromium reducible sulphur (CRS), iron and phosphorus pools were determined in the 0-10 cm sediment horizon. Bacterial sulphate reduction rates were measured only at station 17. Iron pools, AVS and CRS followed similar patterns at all the considered stations, with lower values in the 0-2 cm sediment horizon and peaks in the deepest sediment layer (5-10 cm horizon). Overall, the labile Fe accounted for an annual average of 115.6 +/- 3.0 mu mol cm(-3), with peaks of labile ferric iron up to 40 mu mol cm-3. The great iron availability and reactivity accounted for an efficient buffering capacity against sulphides, with the accumulation of AVS and CRS, specially at station G where the iron buffer was replenished by iron-rich freshwaters. At station 17, in spite of a great iron availability the buffering capacity was less efficient due to macroalgal blooms and accumulation of labile organic matter, whose decomposition stimulated bacterial sulfate reduction and the inherent sulphide production both in the pore-water (DS: 4.0 +/- 3.7 mM) and in the deepest water column (DS: 85 mu M). The iron and sulphur interactions had also implications for P cycling, since in summer the ferric iron reduction was accompanied by a significant increase of pore-water and exchangeable phosphates. The AVS to labile Fe and AVS to TRIS (AVS + CRS) ratios were used to assess the sediment capacity of precipitating and retaining sulphides. These ratios were then compared with the chemical buffer capacity, demonstrating their suitability as indicators of buffering capacity towards sulphides.