A first estimation of the role of penguin guano on copper cycling and organic speciation in Antarctic coastal waters.

Cu is a vital micronutrient, but free Cu ions (Cu2+) in seawater, even at subnanomolar concentrations, can impede phytoplankton growth. Natural Cu complexation with organic ligands regulates Cu acquisition and, in most instances, reduces Cu2+ concentrations below toxic thresholds. Along the Antarctic coast, the sources and sinks of Cu and its associated ligands remain poorly defined. Despite the high productivity in the area, there are no studies on the role of trophic transfer in Cu cycling. This study explores penguin guano release of Cu and Cu ligands and its potential in neutralizing copper toxicity along the Antarctic coast. We collected guano in a Chinstrap penguin nesting location in the West coast of Deception Island and extracted its components into aqueous solution imitating natural processes. Copper concentration in guano was 0.4 mg (dry weight g)-1 constituting a potential toxic threat and showed biomagnification with respect to krill. Surface seawater samples collected from various locations varying in penguin activity, were analyzed to assess the potential influence of guano on the area. Visual examination and elevated levels of Al suggested that a substantial portion of guano was lithogenic. Consequently, only a modest 16 % of the total Cu present in guano could be extracted using mechanical methods. Notably, the concentrations of the extracted organic ligands were approximately 23 times higher than the concentrations of the extracted Cu. This significant presence of ligands effectively nullifies any potential toxicity that could have arisen from free Cu2+ ions. Guano ligands' conditional stability constants were lower than those in surface seawater suggesting phytoplankton exudation was the main ligand source in the area. Overall, guano acts as a key node for Cu cycling in coastal Antarctic waters but its deleterious potential is neutralized by ligands from krill digestion and the high background concentration of phytoplankton exudates.

Macronutrients, iron and humic substances summer cycling over the extended continental shelf of the South Brazil Bight.

We surveyed macronutrients and dissolved iron (DFe) concentrations and speciation in a transect over the shelf of the South Brazil Bight (SBB) at Santa Marta Grande Cape (SE Brazil) during a coastal downwelling episode. Driven by dominant NE winds, coastal downwelling is a common feature during the austral summer and force after water convergence, with contribution of internal wave breaking at the shelf edge, upwelling of macronutrients into the nutrient-depleted waters of the southbound Brazil Current at ~100 km from the coastline. As a result, we found a plume of high turbidity that reached the euphotic layer, a deepening of the silicate, nitrate, and phosphate isolines over the shelf and a bulging of the nitrate and phosphate isolines over the shelf edge and the slope. Our first measurements of DFe concentration and speciation in the area revealed that against prior findings in other coastal areas, macronutrients, DFe, and iron ligand cycles were disentangled. Higher DFe concentrations were often found at the surface indicating aerial deposition. Secondary DFe maxima over the sediment-water interface and in the upwelled plume indicated DFe fluxes from the sediment and from resuspended instable colloids. Iron ligand concentrations were higher than DFe concentrations in most stations with a clear land-to-ocean gradient. Subtraction of HS iron ligands revealed that except in upwelled water, the bulk of surface ligands was the result of local biological processes. The analysis of the concentrations of Fe-HS complexes showed that the contribution of HS to DFe was dominant in upwelled waters, significant in waters close to the coast, but nearly negligible in the rest of the studied area. We hypothesize that the injection of iron-humic complexes into the euphotic layer during summer upwelling episodes is the key to understanding the persistent high chlorophyll meanders found over the shelf edge of the SBB coast.