The permanent ice cover of Lake Vida (Antarctica) encapsulates an extreme cryogenic brine ecosystem (−13°C; salinity, 200). This aphotic ecosystem is anoxic and consists of a slightly acidic (pH 6.2) sodium chloride-dominated brine. Expeditions in 2005 and 2010 were conducted to investigate the biogeochemistry of Lake Vida's brine system. A phylogenetically diverse and metabolically active Bacteria dominated microbial assemblage was observed in the brine. These bacteria live under very high levels of reduced metals, ammonia, molecular hydrogen (H 2 ), and dissolved organic carbon, as well as high concentrations of oxidized species of nitrogen (i.e., supersaturated nitrous oxide and ∼1 mmol·L −1 nitrate) and sulfur (as sulfate). The existence of this system, with active biota, and a suite of reduced as well as oxidized compounds, is unusual given the millennial scale of its isolation from external sources of energy. The geochemistry of the brine suggests that abiotic brine-rock reactions may occur in this system and that the rich sources of dissolved electron acceptors prevent sulfate reduction and methanogenesis from being energetically favorable. The discovery of this ecosystem and the in situ biotic and abiotic processes occurring at low temperature provides a tractable system to study habitability of isolated terrestrial cryoenvironments (e.g., permafrost cryopegs and subglacial ecosystems), and is a potential analog for habitats on other icy worlds where water-rock reactions may cooccur with saline deposits and subsurface oceans.astrobiology | geomicrobiology | microbial ecology | extreme environment T he observation of microbes surviving and growing in a variety of icy systems on Earth has expanded our understanding of how life pervades, functions, and persists under challenging conditions (e.g., refs. 1-3). Studies of the physical characteristics, the geochemical properties, and microbes in ice (triple point junctions, brine channels, gas bubbles) have also changed our perceptions of the environments that may contain traces of, or even sustain, life beyond Earth [e.g., Mars (4), Europa (5), and Enceladus (6)].Solute depression of ice crystal formation or solar radiation melting of water ice are key processes that provide liquid waterthe key solvent that makes life possible-within icy systems. Microbial communities in these conditions are often sustained by a supply of energy that ultimately derives from photosynthesis (present or past). The understanding of ecosystems based on energy sources other than the Sun comes mainly from realms where hydrothermal processes have provided reduced compounds necessary to fuel chemosynthetically driven ecosystems. Methane derived from thermogenic or biogenic sources can also support microbial communities in deep sea (7) and high arctic cold saline seeps (8). More recently, discoveries of life and associated processes in deep terrestrial subsurface ecosystems (9) provide compelling evidence of subsurface life that in some cases is fueled by nonphotosynthetic processes. Ou...

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Wetlands provide quintessential ecosystem services such as maintenance of water quality, water supply and biodiversity, among others; however, wetlands are also among the most threatened ecosystems worldwide. Natural dissolved organic matter (DOM) is an abundant and critical component in wetland biogeochemistry. This study describes the first detailed, comparative, molecular characterization of DOM in subtropical, pulsed, wetlands, namely the Everglades (USA), the Pantanal (Brazil) and the Okavango Delta (Botswana), using optical properties, high-field nuclear magnetic resonance (NMR) and ultrahigh-resolution mass spectrometry (FT-ICRMS), and compares compositional features to variations in organic matter sources and flooding characteristics (i.e., differences in hydroperiod). While optical properties showed a high degree of variability within and between the three wetlands, analogies in DOM fluorescence properties were such that an established excitation emission matrix fluorescence parallel factor analysis (EEM-PARAFAC) model for the Everglades was perfectly applicable to the other two wetlands. Area-normalized 1 H NMR spectra of selected samples revealed clear distinctions of samples while a pronounced congruence within the three pairs of wetland DOM readily suggested the presence of an individual wetland-specific molecular signature. Within sample pairs (long-vs. short-hydroperiod sites), internal differences mainly referred to intensity variations (denoting variable abundance) rather than to alterations of NMR resonances positioning (denoting diversity of molecules). The relative disparity was largest between the Everglades longand short-hydroperiod samples, whereas Pantanal and Okavango samples were more alike among themselves. Otherwise, molecular divergence was most obvious in the case of unsaturated protons (δ H > 5 ppm). 2-D NMR spectroscopy for a particular sample revealed a large richness of aliphatic and unsaturated substructures, likely derived from microbial sources such as periphyton in the Everglades. In contrast, the chemical diversity of aromatic wetland DOM likely originates from a combination of higher plant sources, progressive microbial and photochemical oxidation, and contributions from combustion-derived products (e.g., black carbon). FT-ICRMS spectra of both Okavango and Pantanal showed near 57 ± 2 % CHO, 8 ± 2 % CHOS, 33 ± 2 % CHNO and < 1 % CHNOS molecules, whereas those of Everglades samples were markedly enriched in CHOS and CHNOS at the expense of CHO and CHNO compounds. In particular, the Everglades short-hydroperiod site showed a large set of aromatic and oxygen-deficient "black sulfur" compounds whereas the long-hydroperiod site contained oxygenated sulfur attached to fused-ring polyphenols. The elevated abundance of CHOS compounds for the Everglades samples likely results from higher inputs of agriculture-derived and sea-spray-derived sulfate. Although wetland DOM samples were found to share many molecular features, each sample was unique in its composition, which reflected spec...

The direct and indirect photolysis of bisphenol A (BPA) was investigated using a solar simulator in the absence and presence of dissolved organic matter (DOM). BPA degradation by direct photolysis was significantly slower than its rate in the presence of DOM. In natural waters, the direct photolytic pathway would be even less important due to light screening effects. Surprisingly, differences in the rate of indirect BPA photolysis were relatively small between DOM samples. Two of the DOM samples represented terrestrial (Suwannee River fulvic acid) and autochthonous (Lake Fryxell) geochemical endmembers. The third DOM (Fulton County, Ohio) was derived from a temperate artificial wetland. We were unable to correlate BPA photoreactivity to the structural components of DOM or its extinction coefficient at 280 nm. The addition of methanol, a hydroxyl radical scavenger, to reaction solutions slowed but did not completely quench the indirect photolysis of BPA. This observation suggests that BPA photodegrades via multiple pathways involving other transients formed by the photolysis of DOM. Competitive experiments using 2,4,6-trimethylphenol also reduce the reaction rate of BPA by DOM and implythat other DOM-derived phototransients (e.g., excited triplet state DOM) are involved in the reaction. The reaction rate coefficients reported under solar-simulated irradiance in the presence of DOM are significantly faster than those reported for the microbial degradation of BPA. Thus, in natural surface waters photosensitized transformation of BPA by dissolved organic matter may be as important as biodegradation.

Abstract. Many alpine areas are experiencing deglaciation, biogeochemical changes driven by temperature rise, and changes in atmospheric deposition. There is mounting evidence that the water quality of alpine streams may be related to these changes, including rising atmospheric deposition of carbon (C) and nutrients. Given that barren alpine soils can be severely C limited, atmospheric deposition sources may be an important source of C and nutrients for these environments. We evaluated the magnitude of atmospheric deposition of C and nutrients to an alpine site, the Green Lake 4 catchment in the Colorado Rocky Mountains. Using a long-term dataset (2002)(2003)(2004)(2005)(2006)(2007)(2008)(2009)(2010) of weekly atmospheric wet deposition and snowpack chemistry, we found that volume weighted mean dissolved organic carbon (DOC) concentrations were 1.12 ± 0.19 mg l −1 , and weekly concentrations reached peaks as high at 6-10 mg l −1 every summer. Total dissolved nitrogen concentration also peaked in the summer, whereas total dissolved phosphorus and calcium concentrations were highest in the spring. To investigate potential sources of C in atmospheric deposition, we evaluated the chemical quality of dissolved organic matter (DOM) and relationships between DOM and other solutes in wet deposition. Relationships between DOC concentration, fluorescence, and nitrate and sulfate concentrations suggest that pollutants from nearby urban and agricultural sources and organic aerosols derived from sub-alpine vegetation may influence high summer DOC wet deposition concentrations. Interestingly, high DOC concentrations were also recorded during "dust-in-snow" events in the spring, which may reflect an association of DOM with dust. Detailed chemical and spectroscopic analyses conducted for samples collected in 2010 revealed that the DOM in many late spring and summer samples was less aromatic and polydisperse and of lower molecular weight than that of winter and fall samples. Our C budget estimates for the Green Lake 4 catchment illustrated that wet deposition (9.9 kg C ha −1 yr −1 ) and dry deposition (6.9 kg C ha −1 yr −1 ) were a combined input of approximately 17 kg C ha −1 yr −1 , which could be as high as 24 kg C ha −1 yr −1 in high dust years. This atmospheric C input approached the C input from microbial autotrophic production in barren soils. Atmospheric wet and dry deposition also contributed 4.3 kg N ha −1 yr −1 , 0.15 kg P ha −1 yr −1 , and 2.7 kg Ca 2+ ha −1 yr −1 to this alpine catchment.

To characterize the effects of thermal-alteration on water extractable organic matter (WEOM), soil samples were heated in a laboratory at 225, 350, and 500 °C. Next, heated and unheated soils were leached, filtered, and analyzed for dissolved organic carbon (DOC) concentration, optical properties, molecular size distribution, molecular composition, and disinfection byproduct (DBP) formation following the addition of chlorine. The soils heated to 225 °C leached the greatest DOC and had the highest C- and N-DBP precursor reactivity per unit carbon compared to the unheated material or soils heated to 350 or 500 °C. The molecular weight of the soluble compounds decreased with increasing heating temperature. Compared to the unheated soil leachates, all DBP yields were higher for the leachates of soils heated to 225 °C. However, only haloacetonitrile yields (μg/mg) were higher for leachates of the soils heated to 350 °C, whereas trihalomethane, haloacetic acid and chloropicrin yields were lower compared to unheated soil leachates. Soluble N-containing compounds comprised a high number of molecular formulas for leachates of heated soils, which may explain the higher yield of haloacetonitriles for heated soil leachates. Overall, heating soils altered the quantity, quality, and reactivity of the WEOM pool. These results may be useful for inferring how thermal alteration of soil by wildfire can affect water quality.

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