Total and extractable elemental composition of the intertidal estuarine biofilm of the Río de la Plata: Disentangling natural and anthropogenic influences

Estuarine transitional waters constitute regions affected by or at risk of anthropogenic impact due to urbanization and industrial development. The elemental composition of the intertidal biofilm sediment is an excellent marker for the detection of any impact, and may exert a bottom-up influence by natural concatenation to higher organization levels (e.g. molecules, cells, organisms, communities). The distribution pattern of elemental composition (total and bioavailable fraction) along the estuary axes was analyzed, disentangling potential shifts produced by human activities. We predict that most abundant elements in the Rio de la Plata estuary are the natural earth-crust components and that these will not show any evident gradient along the estuarine axis. Elements involved in human related processes will shape concentration gradients from the most probable source (i.e. cities) indicating estuarine pollution. The research strategy involved the sampling of intertidal biofilm along the entire estuary and the registration of environmental variables and the total and bioavailable elemental composition. Sampling sites represent pristine, agricultural, and urbanized areas along a 428-km-long coastline comprising the inner, middle and outer Río de la Plata estuarine zones and a coastal fringe of oceanic beaches of Uruguay (South America). Biofilm sediment samples were collected in Autumn 2011 and digested for total and extractable (bioavailable) elements quantification measured by ICP-OES. Mercury (Hg) sediments were digested with aqua regia and quantified by cold vapor atomic absorption (CVAAS). The most abundant elements measured were Al, Fe, and Ca in all sampling. Anthropogenic marker elements such as Hg, Cr, Pb, Zn, and Cu were found, even at potentially toxic levels, at urban beaches at the city of Montevideo. The ordination of samples highlights the distinctive characteristics of urban beaches, placed in a particular location along the first principal component. This position is mainly driven by human impact marker metals and C/N ratios. The results highlight the value of bioavailable elemental composition analyses of benthic biofilm as a tool for detecting shifts in estuarine systems.