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.

Natural levels and photo-production rates of hydrogen peroxide (H2O2) in Andean Patagonian aquatic systems: Influence of the dissolved organic matter pool.

In aquatic environments the reactive oxygen species hydrogen peroxide (H2O2) is produced through photochemical reactions involving chromophoric dissolved organic matter (CDOM). Andean Patagonian freshwaters experience challenging underwater UV levels, which promote high levels of photochemical weathering. In this investigation, we study natural H2O2 levels and experimentally address the photochemical formation of H2O2 in stream and lake water with a range of dissolved organic matter (DOM) concentrations and quality. The screening of different pristine aquatic systems of Patagonia revealed that H2O2 concentration fluctuates between 8 and 60 nM. Laboratory incubation of different water types in PAR + UV showed photo-production of H2O2. The H2O2 formation rate increased linearly with dissolved organic carbon (DOC) in streams (13.5-20.5 nM h-1) and shallow lakes (25.7-37.8 nM h-1). In contrast, the H2O2 formation rate in deep lakes was much lower (2.1-7.1 nM h-1), and decreased with DOC. The natural potential for H2O2 formation was related to the concentration and quality of the DOM pool. At higher DOC levels, such as those present in shallow lakes, H2O2 production was directly related to DOC, whereas at low DOC levels in deep lakes and streams, two patterns were distinguished in relation to their DOM pool quality. Stream DOM, composed of high molecular weight/size humic compounds, proved to be a reactive substrate, as reflected by their high H2O2 formation rates. On the other hand, deep lake DOM, with its higher relative contribution of small and more processed compounds, was found to be a less reactive substrate, affording lower H2O2 formation rates.

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.

Climate-driven terrestrial inputs in ultraoligotrophic mountain streams of Andean Patagonia revealed through chromophoric and fluorescent dissolved organic matter.

Fluvial networks transport a substantial fraction of the terrestrial production, contributing to the global carbon cycle and being shaped by hydrologic, natural and anthropogenic factors. In this investigation, four Andean Patagonian oligotrophic streams connecting a forested catchment (~125km(2)) and draining to a double-basin large and deep lake (Lake Moreno complex, Northwestern Patagonia), were surveyed to analyze the dynamics of the allochthonous subsidy. The results of a 30month survey showed that the catchment supplies nutrients and dissolved organic matter (DOM) to the streams. The eruption of the Puyehue-Cordón Caulle at the beginning of the study overlapped with seasonal precipitation events. The largest terrestrial input was timed with precipitation which increased particulate materials, nutrients and DOM through enhanced runoff. Baseline suspended solids and nutrients were very low in all the streams (suspended solids: ~1mg/L; total nitrogen: ~0.02mg/L; total phosphorus: ~5µg/L), increasing several fold with runoff. Baseline dissolved organic carbon concentrations (DOC) ranged between 0.15 and 1mg/L peaking up to three-fold. Chromophoric and fluorescent analyses characterized the DOM as of large molecular weight and high aromaticity. Parallel factor modeling (PARAFAC) of DOM fluorescence matrices revealed three components of terrestrial origin, with certain degree of microbial processing: C1 and C2 (terrestrial humic-like compounds) and C3 (protein-like and pigment derived compounds). Seasonal changes in MOD quality represent different breakdown stages of the allochthonous DOM. Our survey allowed us to record and discuss the effects of the Puyehue-Cordón Caulle eruption, showing that due to the high slopes, high current and discharge of the streams the volcanic material was rapidly exported to the Moreno Lake complex. Overall, this survey underscores the magnitude and timing of the allochthonous input revealing the terrestrial subsidy to food webs in Patagonian freshwaters, which are among the most oligotrophic systems of the world.

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.

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms: an experimental study using oligotrophic water from Patagonian lakes.

Ligands present in dissolved organic matter (DOM) form complexes with inorganic divalent mercury (Hg2+) affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg2+ (the prevailing mercury species in the water column of these lakes) by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg2+ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended witht'97Hg2+. The bioavailability of Hg2+ was affected by the concentration and character of DOM. The entrance of Hg2+ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg2+ by Cryptomonas, up to 27% of the Hg2+ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg2+ in the dissolved phase, resulting in the lowest Hg2+ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg2+ amended. The dietary incorporation of Hg2+ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg2+ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg2+ by algae through competitive binding, while the incorporation of Hg2+ into the zooplankton was dominated by trophic or dietary transfer.

Influence of precipitation, landscape and hydrogeomorphic lake features on pelagic allochthonous indicators in two connected ultraoligotrophic lakes of North Patagonia.

We investigated the terrestrial influence on two chained deep ultraoligotrophic lakes of North Patagonia (Argentina) through the seasonal analysis of two pelagic allochthonous indicators: i) water color, as a proxy of allochthonous dissolved organic matter in lakes; and ii) the color to chlorophyll a ratio (Color:Chla), as an indicator of the relationship between allochthonous and autochthonous carbon pools. We also evaluated the potential transfer pathways of the allochthonous dissolved organic matter into the pelagic food webs of these deep lakes, including the natural zooplankton δ(13)C in the analysis. The dynamics of the allochthonous indicators were related to the precipitation regime, water level fluctuations, and hydrogeomorphic and catchment features of lakes Moreno East and Moreno West. The water color (absorbance at 440 nm) was extremely low (<0.28 m(-1)) in both lakes regardless of the season. However, precipitation and snowmelt regimes drove the increase and decrease of water color, respectively. A significant positive relationship between the zooplankton bulk δ(13)C with the water color would suggest an input of allochthonous organic carbon into the pelagic consumers. The incorporation of the dissolved allochthonous material into higher trophic levels is likely favored by the bacterivorous behavior of planktonic organisms, mixotrophic flagellates and ciliates, which dominate the pelagic food webs of these Patagonian lakes. Morphometric aspects, mainly the higher water residence time, led to lower values of allochthony in Moreno East compared to Moreno West, probably accentuated by its upper position in the lake chain. Overall, our results suggest that these allochthonous signals can bring insight into the magnitude of the interaction between terrestrial environments and lake ecosystems, even in extremely clear and ultraoligotrophic systems, such as the Andean Patagonian lakes.

Mercury in an ultraoligotrophic North Patagonian Andean lake (Argentina): concentration patterns in different components of the water column.

The deep, ultraoligotrophic piedmont lakes of Northern Patagonia (Argentina) are located in pristine and barely impacted areas, along a wide latitudinal range. Several studies have reported moderate to high total mercury (Hg) concentrations and contrasting methylmercury (CH3Hg+) production in different lake compartments. Sources of Hg for western Patagonian terrestrial and aquatic ecosystems are still not clear; while point sources can be ruled out and atmospheric deposition is a plausible source, along with contribution from active volcanic areas of the Andes. In this investigation, we reported a noticeably seasonal, spatial (between lake branches), and vertical (between water column strata) heterogeneity in the total Hg concentrations found in the pelagic zone of Lake Moreno. Sterile water samples taken in a depth profile of the lake showed moderate to high concentrations of CH3Hg+ in autumn with a decreasing trend with depth. Our results indicated that Hg is largely allocated in the plankton fraction between 10-53 microm; which dominated within the euphotic (epilimnetic) zone of the lake due to the high densities attained by two species of the dinoflagellate Gymnodinium. The 53-200 microm planktonic size fraction (comprising rotifers, ciliates and immature stages of crustaceans) and the > 200 microm fraction (calanoid copepods and cladocerans) were found to bear strikingly lower total Hg concentrations, suggesting that the magnification of Hg at the planktonic consumer level is negligible.

Methylmercury production in the water column of an ultraoligotrophic lake of Northern Patagonia, Argentina.

Methyl-mercury (CH3Hg+) production was studied in freshwaters from lake Moreno, an ultraoligotrophic system belonging to Northern Patagonia. Hg2+ labelled with high specific activity 197Hg was spiked to water samples in concentrations of 10 ng l(-1), and incubated in laboratory for 3d time trends under different conditions. Experimental water was sampled daily to evaluate CH3(197)Hg+ production. Lake water used in the experiments was sampled just below the upper limit of the metalimnion ( approximately 30 m depth), where maximum values of chlorophyll a have been measured previously. Sampling was performed in late autumn, when the plankton fraction <50 microm exhibited mercury concentrations up to 260 microg g(-1) dry weight. The experiments analysed lake water filtered through 50, 20, and 0.2 microm (filter-sterilized) mesh nets. ASTM grade 1 water was also incubated for control. All the experiments were run in an environmental chamber under controlled temperature and light regime. High Hg2+ conversion to CH3Hg+, up to 50%, was measured in lake water, in a process stimulated by light. CH3Hg+ production was two-fold higher after 3d of incubation with illumination compared to total darkness. Sterile lake water showed conversions up to 30%, while the planktonic components seem to enhance the CH3Hg+ production. Overall, our results provide evidence that lake Moreno waters favour CH3Hg+ production in processes stimulated by light. Although biotic components certainly contribute to enhance mercury methylation, water chemistry plays a key role in this process. We hypothesize that dissolved organic matter, particularly its quality, could be decisive.