Natural levels of hydrogen peroxide (H2O2) in deep clear South temperate lakes: Field and laboratory evidence of photo- and biotic production.

Hydrogen peroxide (H2O2) is a ubiquitous reactive oxygen species (ROS) in aquatic systems and is produced mainly in surface water by the interaction of ultraviolet radiation (UVR) and natural dissolved organic carbon (DOC). Andean Patagonian lakes are ultraoligotrophic, clear systems with extended photic zones (~40 m), and are exposed to challenging UVR levels due to their lati-altitudinal situation and extremely low DOC levels. This investigation describes the seasonal levels of H2O2 in relation to DOC quality in the water column of lakes Moreno East (ME) and Moreno West (MW), two deep (ca. 100 m), ultraoligotrophic, low-DOC (<0.7 mg L-1) systems of Andean Patagonia. H2O2 concentrations recorded in the lakes were below 60 nM, ranging from ~3 to ~60 nM in Lake ME and from ~5 to ~35 nM in Lake MW. In most of the samples of both lakes, the H2O2 levels were higher in the photic zone (surface to 30-40 m) than the aphotic zone (from 30-40 m to 90-100 m), particularly in summer samples. Laboratory experiments evaluated the abiotic (photochemical) and biotic (microbial) production of H2O2 in seasonal (summer, autumn) samples which varied DOM quality due to lake (ME, MW) and depth (photic and aphotic lake layers) provenance. Abiotic and biotic production of H2O2 attained higher levels in summer samples from the photic zones of both lakes. Humic DOM from deep layers (particularly from summer samples) was more susceptible to both photo- and bio-degradation than DOM from upper lake layers, which was characterized by stronger signs of degradation and progress in diagenesis.

Linking landscape heterogeneity with lake dissolved organic matter properties assessed through absorbance and fluorescence spectroscopy: Spatial and seasonal patterns in temperate lakes of Southern Andes (Patagonia, Argentina).

Hydrological connectivity between terrestrial and aquatic systems is influenced by landscape features. Topography, vegetation cover and type, lake morphometry and climate (seasonality, precipitation) drive the timing, concentration and quality of allochthonous dissolved organic matter (DOM) inputs to lakes, influencing lake metabolism. The impact of climate changes on terrestrial-aquatic linkages depends on regional trends and ecosystems properties. We examined how landscape heterogeneity affects lake DOM in pristine temperate headwater lakes located in sharp bioclimatic gradients at the leeward side of the southern Andes (Patagonia, Argentina), and predicted their potential responses to forecasted changes in regional climate. We assessed DOM properties of deep and shallow lakes spotted along precipitation and altitudinal gradients which reflect on vegetation heterogeneity. Lake DOM (concentration, and chromophoric and fluorescent properties) was related to terrestrial bioclimatic conditions, addressing also DOM bio- and photodegradation processes. Co-effects of climate and vegetation determined the quantity and quality of allochthonous DOM inputs. Higher terrestrial signs showed up at the wettest extreme of the gradient and during the rainy season, being attributable to higher hydrological land-water connectivity, and dense vegetation cover. Under drier conditions, DOM displayed higher photobleaching signs at spatial and temporal scales. The ratio between non-humic and terrestrial humic substances indicated that DOM biodegradation dominates in shallow forested lakes and photodegradation prevails in deep ones, whereas coupled photo- and biological processing shaped the DOM pool of high altitude lakes. Overall, DOM optical metrics captured landscape heterogeneity. Under the forecasted climate changes for Patagonia (decreasing precipitation and increasing temperature), piedmont lakes may experience lower hydrological connectivity, lower terrestrial inputs and, enhanced photobleaching usually associated with longer water residence time. In high altitude lakes, terrestrial DOM inputs are expected to increase due to the upward expansion of native deciduous forests, thus becoming more similar to lakes located lower in the landscape.

The microbial mercury link in oligotrophic lakes: Bioaccumulation by picocyanobacteria in natural gradients of dissolved organic matter.

Andean Patagonian lakes are oligotrophic systems characterized by low dissolved organic carbon (DOC) levels and moderate to high Hg concentration that determine naturally high Hg/DOC ratios and bioavailability. In these lakes, microbial food webs are extremely important in Hg trophodynamics, being that the picophytoplankton fraction is a major entrance path of Hg2+ into pelagic food webs. This study analyzed the bioaccumulation of Hg2+ by the picocyanobacteria Synechococcus sp. using the radiotracer 197Hg2+ and water from four Andean Patagonian lakes presenting a natural gradient of DOM concentration and quality. Hg2+ bioaccumulation by Synechococcus was calculated as the uptake of Hg2+ per biovolume unit (volume concentration factor VCF; pL µm-3). Hg uptake showed a wide variation (13 < VCF< 300 pL µm-3) in the natural DOC gradient tested (0.7-4 mg L-1; Hg2+/DOC ratio: 1.8-14 ng mg-1). The bioaccumulation of Hg2+ in Synechococcus decreased exponentially with DOC concentration. Differences in the quality of dissolved organic matter (DOM) among lake water influenced also Hg2+ bioaccumulation. Naturally degraded DOM, with low molecular weight/size, promoted higher Hg uptakes in Synechococcus compared to humic DOM, rich in high molecular weight/size aromatic compounds, that retained Hg in the dissolved phase. In Andean Patagonian lakes picocyanobacteria are pivotal organisms in the Hg cycling, taking dissolved Hg2+ and transferring it to pelagic food webs, as well as fueling the benthic Hg pathway through sedimentation.

Inorganic mercury (Hg2+) accumulation in autotrophic and mixotrophic planktonic protists: Implications for Hg trophodynamics in ultraoligotrophic Andean Patagonian lakes.

Microbial assemblages are typical of deep ultraoligotrophic Andean Patagonian lakes and comprise picoplankton and protists (phytoflagellates and mixotrophic ciliates), having a central role in the C cycle, primary production and in the incorporation of dissolved inorganic mercury (Hg2+) into lake food webs. In this study we evaluated the mechanisms of Hg2+ incorporation in hetero- and autotrophic bacteria, in the autotrophic dinoflagellate (Gymnodinium paradoxum) and in two mixotrophic ciliates (Stentor araucanus and Ophrydium naumanni) dominating the planktonic microbial assemblage. The radioisotope 197Hg was used to trace the Hg2+ incorporation in microbiota. Hg uptake was analyzed as a function of cell abundance (BCF: bioconcentration factor), cell surface (SCF: surface concentration factor) and cell volume (VCF: volume concentration factor). Overall, the results obtained showed that these organisms incorporate substantial amounts of dissolved Hg2+ passively (adsorption) and actively (bacteria consumption or attachment), displaying different Hg internalization and therefore, varying potential for Hg transfer. Surface area and quality, and surface:volume ratio (S:V) control the passive uptake in all the organisms. Active incorporation depends on bacteria consumption in the mixotrophic ciliates, or on bacteria association to surface in the autotrophic dinoflagellate. Hg bioaccumulated by pelagic protists can be transferred to higher trophic levels through plankton and fish feeding, regenerated to the dissolved phase by excretion, and/or transferred to the sediments by particle sinking. In ultraoligotrophic Andean Patagonian lakes, picoplankton and planktonic protists are key components of lake food webs, linking the pelagic and benthic Hg pathways, and thereby playing a central role in Hg trophodynamics.