How do metals interact with periphytic biofilms?

Extracellular matrix of periphyton has complex structural and chemical composition regulating metal transfer within biofilms with consequences for metal transfer to aquatic food webs. We investigated which metal species were retained in the loosely (LB) and the tightly bound (TB) fractions of the periphyton matrix from three pristine lakes at different growth stages. We measured the fluorescent dissolved organic matter (FDOM) composition with parallel factor anal-ysis (PARAFAC) and the co-occurrence of essential and non-essential metals with FDOM in the two matrix fractions. The LB and TB fractions of periphyton had distinct fluorescence composition from the water column. The PARAFAC model identified five components, including two (C2 and C4) appearing to be of periphytic origin. The humic-like C2 was almost exclusive to periphyton and the tryptophan-like C4, associated to biofilm phototrophy, represented up to 47.0 +/- 7.3 % of total fluorescence in the LB fraction. Most metals had significant positive relationships with four FDOM components in the LB fraction while C2 was the only component in the TB fraction to show such significant relationships. Components in the LB fraction seemed to act as scavengers for metals, preventing them from reaching the cellular fraction, while C2 from the TB fraction was likely promoting the bioavailability of essential metals for mi-croorganisms inside periphyton. This study highlights the contrasting roles of the extracellular matrix on metal mobil-ity beyond the usually proposed protection mechanisms. We suggest an experimental model for the study of metal regulation processes of the periphytic extracellular polymeric substances with a focus on the components produced by microorganisms within periphyton and their distribution in the different matrix fractions.