Photo-lability of deep ocean dissolved black carbon

Dissolved black carbon (DBC), defined here as condensed aromatics isolated from seawater via PPL solid phase extraction and quantified as benzenepolycarboxylic acid (BPCA) oxidation products, is a significant component of the oceanic dissolved organic carbon (DOC) pool. These condensed aromatics are widely distributed in the open ocean and appear to be tens of thousands of years old. As such DBC is regarded as highly refractory. In the current study, the photo-lability of DBC, DOC and coloured dissolved organic matter (CDOM; ultraviolet-visible absorbance) were determined over the course of a 28 day irradiation of North Atlantic Deep Water under a solar simulator. During the irradiation DBC fell from 1044 ± 164 nM-C to 55 ± 15 nM-C, a 20-fold decrease in concentration. Dissolved black carbon photo-degradation was more rapid and more extensive than for bulk CDOM and DOC. The concentration of DBC correlated with CDOM absorbance and the quality of DBC indicated by the ratios of different BPCAs correlated with CDOM absorbance spectral slope, suggesting the optical properties of CDOM may provide a proxy for both DBC concentrations and quality in natural waters. Further, the photo-lability of components of the DBC pool increased with their degree of aromatic condensation. These trends indicate that a continuum of compounds of varying photo-lability exists within the marine DOC pool. In this continuum, photo-lability scales with aromatic character, specifically the degree of condensation. Scaling the rapid photo-degradation of DBC to rates of DOC photo-mineralisation for the global ocean leads to an estimated photo-chemical half-life for oceanic DBC of less than 800 years. This is more than an order of magnitude shorter than the apparent age of DBC in the ocean. Consequently, photo-degradation is posited as the primary sink for oceanic DBC and the apparent survival of DBC molecules in the oceans for millennia appears to be facilitated not by their inherent inertness but by the rate at which they are cycled through the surface ocean's photic zone

Evidence of complex involvement of serotonergic genes with restrictive and binge purge subtypes of anorexia nervosa

Peer reviewedPreprin

Characterization and Photodegradation of Dissolved Organic Matter (DOM) From a Tropical Lake and Its Dominant Primary Producer, the cyanobacteria Microcystis aeruginosa

This study investigates optical and high-resolution molecular signatures and photochemical degradation of DOM from the Barra Bonita Reservoir (BB-DOM), a tropical eutrophic lake, as well as from its dominant phytoplankton species, the cyanobacteria Microcystis aeruginosa (Microcystis-DOM). Consistent with a predominantly autotrophic source, BB-DOM and Microcystis-DOM exhibited high protein-like fluorescence and contained a large number of aliphatics. Microcystis-DOM was enriched in peptide-like formulae, while BB-DOM had higher chromophoric and fluorescent DOM(CDOM and FDOM) and was enriched in moderately unsaturated formulae, indicating additions of terrigenous DOM and/or in situ processing of autochthonous material in the lake. Consistent with its higher CDOM content, BB-DOM was more photoreactive than Microcystis-DOM. For both types of DOM, photodegradation resulted in loss of CDOM, FDOM, moderately unsaturated structures, high O/C and low H/C formulae, and preservation of aliphatics. The majority of photoproducts of 0.5 d irradiation were subsequently removed by day 7, and photoproducts represented a minor fraction of the photo-irradiated DOM. For BB-DOM, molecular formula photolability increased with increasing aromaticity index values, while for Microcystis-DOM, molecular formula photolability increased with molecular mass. Photodegradation increased the proportion of molecular formulae containing N (CHO + N) in BB-DOM, while the molecular mass and the proportion of CHO + N formulae decreased upon photo-irradiation of Microcystis-DOM. In concert, these molecular shifts due to photodegradation decreased the diversity of and increased the similarity between BB-DOM and Microcystis-DOM, suggesting the selective pressure exerted by photochemistry selects for the survival of similar compounds in both samples

Contextualizing Wetlands Within a River Network to Assess Nitrate Removal and Inform Watershed Management

Aquatic nitrate removal depends on interactions throughout an interconnected network of lakes, wetlands, and river channels. Herein, we present a network‐based model that quantifies nitrate‐nitrogen and organic carbon concentrations through a wetland‐river network and estimates nitrate export from the watershed. This model dynamically accounts for multiple competing limitations on nitrate removal, explicitly incorporates wetlands in the network, and captures hierarchical network effects and spatial interactions. We apply the model to the Le Sueur Basin, a data‐rich 2,880 km2 agricultural landscape in southern Minnesota and validate the model using synoptic field measurements during June for years 2013–2015. Using the model, we show that the overall limits to nitrate removal rate via denitrification shift between nitrate concentration, organic carbon availability, and residence time depending on discharge, characteristics of the waterbody, and location in the network. Our model results show that the spatial context of wetland restorations is an important but often overlooked factor because nonlinearities in the system, e.g., deriving from switching of resource limitation on denitrification rate, can lead to unexpected changes in downstream biogeochemistry. Our results demonstrate that reduction of watershed‐scale nitrate concentrations and downstream loads in the Le Sueur Basin can be most effectively achieved by increasing water residence time (by slowing the flow) rather than by increasing organic carbon concentrations (which may limit denitrification). This framework can be used toward assessing where and how to restore wetlands for reducing nitrate concentrations and loads from agricultural watersheds.This research was funded by NSF grant EAR-1209402 under the Water Sustainability and Climate Program (WSC): REACH (REsilience under Accelerated CHange)NSF grant EAR-1242458 under Science Across Virtual Institutes (SAVI): LIFE (Linked Institutions for Future EarthA.T.H. acknowledges support provided by NSF grant EAR- 1415206 under the Science, Engineering and Education for Sustainability (SEES

Does Photomineralization of Dissolved Organics Matter in Temperate Rivers?

Sunlight can oxidize dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in freshwaters. The importance of complete photooxidation, or photomineralization, as a sink for DOC remains unclear in temperate rivers, as most estimates are restricted to lakes, high latitude rivers, and coastal river plumes. In this study, we construct a model representing over 75,000 river reaches in the Connecticut River Watershed (CRW), USA, to calculate spectrally resolved photomineralization. We test the hypothesis that photomineralization is a negligible DOC sink across all reaches and flow conditions relative to DOC fluxes. Our model quantifies reaction rates and transport drivers within the river reaches for the ranges of flow conditions, incoming solar irradiance, and canopy cover shading observed throughout the year. Our model predicts average daily areal photomineralization rates ranging from 1.16 mg-C m−2 day−1 in low flow river reaches in the winter, to 18.33 mg-C m−2 day−1 in high flow river reaches during the summer. Even for high photomineralization fluxes, corresponding photomineralization uptake velocities are typically at least an order of magnitude smaller than those reported for other instream processes. We calculate DOC elimination by photomineralization relative to DOC fluxes through individual stream reaches as well as the entire riverine portion of the CRW. We find that relative photomineralization fluxes are highest in summer drought conditions in low order streams. In median flows and mean light intensities, for an average watershed travel distance, 3%–5% of the DOC fluxes are eliminated, indicating that photomineralization is a minor DOC sink in temperate rivers

High--order connected moments expansion for the Rabi Hamiltonian

We analyze the convergence properties of the connected moments expansion (CMX) for the Rabi Hamiltonian. To this end we calculate the moments and connected moments of the Hamiltonian operator to a sufficiently large order. Our large--order results suggest that the CMX is not reliable for most practical purposes because the expansion exhibits considerable oscillations.Comment: 12 pages, 5 figures, 1 tabl

Controls on the composition and lability of dissolved organic matter in Siberia's Kolyma River basin

High-latitude northern rivers export globally significant quantities of dissolved organic carbon (DOC) to the Arctic Ocean. Climate change, and its associated impacts on hydrology and potential mobilization of ancient organic matter from permafrost, is likely to modify the flux, composition, and thus biogeochemical cycling and fate of exported DOC in the Arctic. This study examined DOC concentration and the composition of dissolved organic matter (DOM) across the hydrograph in Siberia's Kolyma River, with a particular focus on the spring freshet period when the majority of the annual DOC load is exported. The composition of DOM within the Kolyma basin was characterized using absorbance-derived measurements (absorbance coefficienta330, specific UV absorbance (SUVA254), and spectral slope ratio SR) and fluorescence spectroscopy (fluorescence index and excitation-emission matrices (EEMs)), including parallel factor analyses of EEMs. Increased surface runoff during the spring freshet led to DOM optical properties indicative of terrestrial soil inputs with high humic-like fluorescence, SUVA254, and low SRand fluorescence index (FI). Under-ice waters, in contrast, displayed opposing trends in optical properties representing less aromatic, lower molecular weight DOM. We demonstrate that substantial losses of DOC can occur via biological (∼30% over 28 days) and photochemical pathways (>29% over 14 days), particularly in samples collected during the spring freshet. The emerging view is therefore that of a more dynamic and labile carbon pool than previously thought, where DOM composition plays a fundamental role in controlling the fate and removal of DOC at a pan-Arctic scale

Differential susceptibility to obesity between male, female and ovariectomized female mice

All authors are with the Department of Nutritional Sciences, University of Texas at Austin, Austin, Texas, USABackground: The prevalence of obesity has increased dramatically. A direct comparison in the predisposition to obesity between males, premenopausal females, and postmenopausal females with various caloric intakes has not been made. To determine the effects of sex and ovarian hormones on the susceptibility to obesity, we conducted laboratory studies with mice. To eliminate confounders that can alter body weight gain, such as age and food consumption; we used mice with the same age and controlled the amount of calories they consumed. -- Methods: We determined sex-specific susceptibility to obesity between male, non-ovariectomized female, and ovariectomized female mice. To compare susceptibility to gaining body weight between males and females, animals from each sex were exposed to either a 30% calorie-restricted, low-fat (5% fat), or high-fat (35% fat) diet regimen. To establish the role of ovarian hormones in weight gain, the ovaries were surgically removed from additional female mice, and then were exposed to the diets described above. Percent body fat and percent lean mass in the mice were determined by dual energy x-ray absorptiometry (DEXA). -- Results: In all three diet categories, male mice had a greater propensity of gaining body weight than female mice. However, ovariectomy eliminated the protection of female mice to gaining weight; in fact, ovariectomized female mice mimicked male mice in their susceptibility to weight gain. In summary, results show that male mice are more likely to become obese than female mice and that the protection against obesity in female mice is eliminated by ovariectomy. -- Conclusion: Understanding metabolic differences between males and females may allow the discovery of better preventive and treatment strategies for diseases associated with body weight such as cancer and cardiovascular disease.Nutritional [email protected]