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.

Mercury in a stream-lake network of Andean Patagonia (Southern Volcanic Zone): Partitioning and interaction with dissolved organic matter.

Lake Nahuel Huapi (NH) is a large, ultraoligotrophic deep system located in Nahuel Huapi National Park (NHNP) and collecting a major headwater network of Northwestern Patagonia (Argentina). Brazo Rincón (BR), the westernmost branch of NH, is close to the active volcanic formation Puyehue-Cordón Caulle. In BR, aquatic biota and sediments display high levels of total Hg (THg), ranging in contamination levels although it is an unpolluted region. In this survey, Hg species and fractionation were assessed in association with dissolved organic matter (DOM) in several aquatic systems draining to BR. THg varied between 16.8 and 363 ng L-1, with inorganic Hg (Hg2+) contributing up to 99.8% and methyl mercury (MeHg) up to 2.10%. DOC levels were low (0.31-1.02 mg L-1) resulting in high THg:DOC and reflecting in high Hg2+ availability for binding particles (partitioning coefficient log Kd up to 6.03). In streams, Hg fractionation and speciation related directly with DOM terrestrial prints, indicating coupled Hg-DOM inputs from the catchment. In the lake, DOM quality and photochemical and biological processing drive Hg fractionation, speciation and vertical levels. Dissolved gaseous Hg (Hg0) reached higher values in BR (up to 3.8%), particularly in upper lake layers where solar radiation enhances the photoreduction of Hg2+ and Hg-DOM complexes. The environmental conditions in BR catchment promote Hg2+ binding to abiotic particles and bioaccumulation and the production of Hg0, features enhancing Hg mobilization among ecosystem compartments. Overall, the aquatic network studied can be considered a "natural Hg hotspot" within NHNP.

Incorporation of inorganic mercury (Hg²âº) in pelagic food webs of ultraoligotrophic and oligotrophic lakes: the role of different plankton size fractions and species assemblages.

In lake food webs, pelagic basal organisms such as bacteria and phytoplankton incorporate mercury (Hg(2+)) from the dissolved phase and pass the adsorbed and internalized Hg to higher trophic levels. This experimental investigation addresses the incorporation of dissolved Hg(2+) by four plankton fractions (picoplankton: 0.2-2.7 µm; pico+nanoplankton: 0.2-20 µm; microplankton: 20-50 µm; and mesoplankton: 50-200 µm) obtained from four Andean Patagonian lakes, using the radioisotope (197)Hg(2+). Species composition and abundance were determined in each plankton fraction. In addition, morphometric parameters such as surface and biovolume were calculated using standard geometric models. The incorporation of Hg(2+) in each plankton fraction was analyzed through three concentration factors: BCF (bioconcentration factor) as a function of cell or individual abundance, SCF (surface concentration factor) and VCF (volume concentration factor) as functions of individual exposed surface and biovolume, respectively. Overall, this investigation showed that through adsorption and internalization, pico+nanoplankton play a central role leading the incorporation of Hg(2+) in pelagic food webs of Andean lakes. Larger planktonic organisms included in the micro- and mesoplankton fractions incorporate Hg(2+) by surface adsorption, although at a lesser extent. Mixotrophic bacterivorous organisms dominate the different plankton fractions of the lakes connecting trophic levels through microbial loops (e.g., bacteria-nanoflagellates-crustaceans; bacteria-ciliates-crustaceans; endosymbiotic algae-ciliates). These bacterivorous organisms, which incorporate Hg from the dissolved phase and through their prey, appear to explain the high incorporation of Hg(2+) observed in all the plankton fractions.