We determined the concentrations and compositions of coarse particulate (Ͼ63 m), fine particulate (0.1-63 m), and dissolved (0.001-0.1 m) organic matter collected along a river reach extending from a first-order stream in the Bolivian Andes, through the Beni River system, to the lower Madeira and Amazon Rivers. Dissolved organic carbon (DOC) concentrations increased down the total reach from ϳ80 to 350 M. The percentage of total DOC with a molecular weight greater than ϳ1,000 atomic mass units that could be isolated by ultrafiltration also increased downstream from 40 to 80%. Weight percentages of organic carbon in the ultrafiltered isolates also grew downstream from 5% at the uppermost station to 37% in the Amazon mainstem. Organic carbon composed only 0.4-1.2 weight percentage of the total mass of the fine particulate fraction, which accounted for 70-80% of the total organic carbon (TOC) in transport through the highly turbid (ϳ600-2000 mg L Ϫ1 ) Beni sequence. Observed compositional differences were related primarily to the size fractions in which the organic matter occurred. On average, coarse particulate organic material exhibited an atomic C : N of 24, whereas ultrafiltered DOM was nitrogen poor, (C : N)a ϭ 34, and fine particulate material was nitrogen rich, (C : N)a ϭ 15. The lignin and stable-carbon isotopic compositions of these fractions indicate tree leaves and other nonwoody tissues from C3 land plants as predominant sources. Three molecular parameters demonstrate that the coarse, fine, and dissolved fractions of individual water samples are increasingly degraded downstream. Elemental nitrogen, amino acids, and basic amino acids are all preferentially associated with fine minerals. Observed geographical patterns included more positive ␦ 13 C values in particulate organic matter from high altitude sites and an increase in the abundance and degradation of ultrafiltered dissolved organic matter down the drainage system. Many of these compositional patterns are imprinted within materials carried by low-order, high-altitude tributaries and appear to reflect processes occurring on the landscape.

Methylation and demethylation represent major transformation pathways regulating the net production of methylmercury (MMHg). Very few studies have documented Hg reactivity and transformation in extreme high-altitude lake ecosystems. Mercury (Hg) species concentrations (IHg, MMHg, Hg°, and DMHg) and in situ Hg methylation (M) and MMHg demethylation (D) potentials were determined in water, sediment, floating organic aggregates, and periphyton compartments of a shallow productive Lake of the Bolivian Altiplano (Uru Uru Lake, 3686 m). Samples were collected during late dry season (October 2010) and late wet season (May 2011) at a north (NS) and a south (SS) site of the lake, respectively. Mercury species concentrations exhibited significant diurnal variability as influenced by the strong diurnal biogeochemical gradients. Particularly high methylated mercury concentrations (0.2 to 4.5 ng L(-1) for MMHgT) were determined in the water column evidencing important Hg methylation in this ecosystem. Methylation and D potentials range were, respectively, <0.1-16.5 and <0.2-68.3 % day(-1) and were highly variable among compartments of the lake, but always higher during the dry season. Net Hg M indicates that the influence of urban and mining effluent (NS) promotes MMHg production in both water (up to 0.45 ng MMHg L(-1) day(-1)) and sediment compartments (2.0 to 19.7 ng MMHg g(-1) day(-1)). While the sediment compartment appears to represent a major source of MMHg in this shallow ecosystem, floating organic aggregates (dry season, SS) and Totora's periphyton (wet season, NS) were found to act as a significant source (5.8 ng MMHg g(-1) day(-1)) and a sink (-2.1 ng MMHg g(-1) day(-1)) of MMHg, respectively. This work demonstrates that high-altitude productive lake ecosystems can promote MMHg formation in various compartments supporting recent observations of high Hg contents in fish and water birds.

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