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Sample records for modelling dissolved organic

  1. Mathematical modeling of wastewater-derived biodegradable dissolved organic nitrogen.

    PubMed

    Simsek, Halis

    2016-11-01

    Wastewater-derived dissolved organic nitrogen (DON) typically constitutes the majority of total dissolved nitrogen (TDN) discharged to surface waters from advanced wastewater treatment plants (WWTPs). When considering the stringent regulations on nitrogen discharge limits in sensitive receiving waters, DON becomes problematic and needs to be reduced. Biodegradable DON (BDON) is a portion of DON that is biologically degradable by bacteria when the optimum environmental conditions are met. BDON in a two-stage trickling filter WWTP was estimated using artificial intelligence techniques, such as adaptive neuro-fuzzy inference systems, multilayer perceptron, radial basis neural networks (RBNN), and generalized regression neural networks. Nitrite, nitrate, ammonium, TDN, and DON data were used as input neurons. Wastewater samples were collected from four different locations in the plant. Model performances were evaluated using root mean square error, mean absolute error, mean bias error, and coefficient of determination statistics. Modeling results showed that the R(2) values were higher than 0.85 in all four models for all wastewater samples, except only R(2) in the final effluent sample for RBNN modeling was low (0.52). Overall, it was found that all four computing techniques could be employed successfully to predict BDON.

  2. THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

    EPA Science Inventory

    Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

    The key properties of solu...

  3. Three-phase modeling of polycyclic aromatic hydrocarbon association with pore-water-dissolved organic carbon

    SciTech Connect

    Mitra, S. ); Dickhut, R.M. )

    1999-06-01

    Log-log plots of measured organic carbon-normalized sediment pore-water distribution coefficients (K[prime][sub OC]s) for several polycyclic aromatic hydrocarbons (PAHs) versus their octanol-water partition coefficients (K[prime][sub OW]s) at two sites in the Elizabeth River, Virginia, show large deviations from linearity. Organic-carbon normalized distribution coefficients for these PAHs between sediments and pore waters decreased by more than two orders of magnitude with depth as well. To determine to what extent pore water dissolved and colloidal organic carbon (DOC) was responsible for the observed nonlinearity and decrease in K[prime][sub OC], a three-phase model was used to estimate pore-water PAH-DOC binding coefficients (K[sub DOC]). Partitioning of PAHs to pore-water DOC (i.e., K[sub DOC])enhances the observed dissolved phase PAH concentration, especially for high-K[sub OW] compounds, contributing to the nonlinearity in K[prime][sub OC]-K[sub OW] plots. However, the application of the three-phase partitioning model to these data indicate that, at most, pore-water PAH-DOC binding accounts for one order of magnitude of the observed decrease in K[prime][sub OC] with depth in the sediment bed. The results of this study are consistent with three-phase partitioning theory for hydrophobic organic compounds between sediment organic matter, pore-water DOC, and freely dissolved aqueous phases in natural systems.

  4. Variable C : N : P stoichiometry of dissolved organic matter cycling in the Community Earth System Model

    DOE PAGES

    Letscher, R. T.; Moore, J. K.; Teng, Y. -C.; ...

    2015-01-12

    Dissolved organic matter (DOM) plays an important role in the ocean's biological carbon pump by providing an advective/mixing pathway for ~ 20% of export production. DOM is known to have a stoichiometry depleted in nitrogen (N) and phosphorus (P) compared to the particulate organic matter pool, a fact that is often omitted from biogeochemical ocean general circulation models. However the variable C : N : P stoichiometry of DOM becomes important when quantifying carbon export from the upper ocean and linking the nutrient cycles of N and P with that of carbon. Here we utilize recent advances in DOM observationalmore » data coverage and offline tracer-modeling techniques to objectively constrain the variable production and remineralization rates of the DOM C : N : P pools in a simple biogeochemical-ocean model of DOM cycling. The optimized DOM cycling parameters are then incorporated within the Biogeochemical Elemental Cycling (BEC) component of the Community Earth System Model (CESM) and validated against the compilation of marine DOM observations. The optimized BEC simulation including variable DOM C : N : P cycling was found to better reproduce the observed DOM spatial gradients than simulations that used the canonical Redfield ratio. Global annual average export of dissolved organic C, N, and P below 100 m was found to be 2.28 Pg C yr-1 (143 Tmol C yr-1, 16.4 Tmol N yr-1, and 1 Tmol P yr-1, respectively, with an average export C : N : P stoichiometry of 225 : 19 : 1 for the semilabile (degradable) DOM pool. Dissolved organic carbon (DOC) export contributed ~ 25% of the combined organic C export to depths greater than 100 m.« less

  5. Dynamics of dissolved organic carbon in hillslope discharge: Modeling and challenges

    NASA Astrophysics Data System (ADS)

    Dusek, Jaromir; Vogel, Tomas; Dohnal, Michal; Barth, Johannes A. C.; Sanda, Martin; Marx, Anne; Jankovec, Jakub

    2017-03-01

    Reliable quantitative prediction of water movement and fluxes of dissolved substances - specifically organic carbon - at both the hillslope and the catchment scales remains a challenge due to complex boundary conditions and soil spatial heterogeneity. In addition, microbially mediated transformations of dissolved organic carbon (DOC) are recognized to determine the balance of DOC in soils. So far, only few studies utilized stable water isotope information in modeling and even fewer linked dissolved carbon fluxes to mixing and/or transport models. In this study, stormflow dynamics of 18O/16O ratios in the water molecules (expressed as δ18O) and DOC were analyzed using a physically-based modeling approach. A one-dimensional dual-continuum vertical flow and transport model was used to simulate the subsurface transport processes in a forest hillslope soil over a period of 2.5 years. The model was applied to describe the transformation of input signals of δ18O and DOC into output signals observed in the hillslope stormflow. To quantify uncertainty associated with the model parameterization, Monte Carlo analysis in conjunction with Latin hypercube sampling was applied. δ18O variations in hillslope discharge and in soil pore water were predicted reasonably well. Despite the complex nature of microbial transformations that caused uncertainty in model parameters and subsequent prediction of DOC transport, the simulated temporal patterns of DOC concentration in stormflow showed similar behavior to that reflected in the observed DOC fluxes. Due to preferential flow, the contribution of the hillslope DOC export was higher than the amounts that are usually found in the available literature.

  6. Modeling studies of dissolved organic matter cycling in Santa Barbara Basin (CA, USA) sediments

    NASA Astrophysics Data System (ADS)

    Burdige, David J.; Komada, Tomoko; Magen, Cédric; Chanton, Jeffrey P.

    2016-12-01

    Here we describe new reaction-transport models for the cycling of dissolved organic matter (DOM, both dissolved organic carbon [DOC] and dissolved organic nitrogen [DON]) in anoxic marine sediments, and apply these models to data from Santa Barbara Basin sediment cores (maximum depth of 4.6 m). Model results show that most organic carbon (and nitrogen) flow in the sediments occurs through reactive DOM intermediates that turn over rapidly to produce inorganic remineralization end-products. Refractory DOM is also produced, and the vast majority of this refractory DOM is not remineralized and either escapes as a benthic flux across the sediment-water interface or is buried. Except near the sediment surface, refractory DOM represents >95% of the total pore water DOM. Pore water DOM appears to be consistently depleted in nitrogen as compared to its source organic matter, which may be the result of differential production of carbon- versus nitrogen-containing refractory DOM during remineralization. Refractory DOC (DOCr) in Santa Barbara Basin sediment pore waters is largely produced from degradation of sediment particulate organic carbon (POC). In addition, there is an upward basal flux of DOCr that is strongly depleted in 14C (-810‰). The Δ14C value of DOCr varies according to its source, ranging from +60‰ (a component of surface sediment POC enriched with radiocarbon from nuclear weapons testing in the 1960's) to -810‰ (the basal DOC flux). Each contributes to the DOCr benthic flux, which has a weighted-average Δ14C value of -40‰. The model-determined DOCr benthic flux is roughly half of the total DOC benthic flux, consistent with observations in the literature that sediments are a source of both labile and refractory DOC to bottom waters. These results support previous arguments that sediment benthic fluxes represent an important source of refractory DOC to the oceans. The benthic flux of refractory DOC from these sediments may also contribute pre-aged DOC

  7. Variable C : N : P stoichiometry of dissolved organic matter cycling in the Community Earth System Model

    DOE PAGES

    Letscher, R. T.; Moore, J. K.; Teng, Y. -C.; ...

    2014-06-16

    Dissolved organic matter (DOM) plays an important role in the ocean's biological carbon pump by providing an advective/mixing pathway for ~ 20% of export production. DOM is known to have a stoichiometry depleted in nitrogen (N) and phosphorus (P) compared to the particulate organic matter pool, a~fact that is often omitted from biogeochemical-ocean general circulation models. However the variable C : N : P stoichiometry of DOM becomes important when quantifying carbon export from the upper ocean and linking the nutrient cycles of N and P with that of carbon. Here we utilize recent advances in DOM observational data coveragemore » and offline tracer-modeling techniques to objectively constrain the variable production and remineralization rates of the DOM C / N / P pools in a simple biogeochemical-ocean model of DOM cycling. The optimized DOM cycling parameters are then incorporated within the Biogeochemical Elemental Cycling (BEC) component of the Community Earth System Model and validated against the compilation of marine DOM observations. The optimized BEC simulation including variable DOM C : N : P cycling was found to better reproduce the observed DOM spatial gradients than simulations that used the canonical Redfield ratio. Global annual average export of dissolved organic C, N, and P below 100 m was found to be 2.28 Pg C yr-1 (143 Tmol C yr-1), 16.4 Tmol N yr-1, and 1 Tmol P yr-1, respectively with an average export C : N : P stoichiometry of 225 : 19 : 1 for the semilabile (degradable) DOM pool. DOC export contributed ~ 25% of the combined organic C export to depths greater than 100 m.« less

  8. Influence of dissolved organic carbon content on modelling natural organic matter acid-base properties.

    PubMed

    Garnier, Cédric; Mounier, Stéphane; Benaïm, Jean Yves

    2004-10-01

    Natural organic matter (NOM) behaviour towards proton is an important parameter to understand NOM fate in the environment. Moreover, it is necessary to determine NOM acid-base properties before investigating trace metals complexation by natural organic matter. This work focuses on the possibility to determine these acid-base properties by accurate and simple titrations, even at low organic matter concentrations. So, the experiments were conducted on concentrated and diluted solutions of extracted humic and fulvic acid from Laurentian River, on concentrated and diluted model solutions of well-known simple molecules (acetic and phenolic acids), and on natural samples from the Seine river (France) which are not pre-concentrated. Titration experiments were modelled by a 6 acidic-sites discrete model, except for the model solutions. The modelling software used, called PROSECE (Programme d'Optimisation et de SpEciation Chimique dans l'Environnement), has been developed in our laboratory, is based on the mass balance equilibrium resolution. The results obtained on extracted organic matter and model solutions point out a threshold value for a confident determination of the studied organic matter acid-base properties. They also show an aberrant decreasing carboxylic/phenolic ratio with increasing sample dilution. This shift is neither due to any conformational effect, since it is also observed on model solutions, nor to ionic strength variations which is controlled during all experiments. On the other hand, it could be the result of an electrode troubleshooting occurring at basic pH values, which effect is amplified at low total concentration of acidic sites. So, in our conditions, the limit for a correct modelling of NOM acid-base properties is defined as 0.04 meq of total analysed acidic sites concentration. As for the analysed natural samples, due to their high acidic sites content, it is possible to model their behaviour despite the low organic carbon concentration.

  9. Experimental investigation and modeling of dissolved organic carbon removal by coagulation from seawater.

    PubMed

    Jeong, Sanghyun; Sathasivan, Arumugam; Kastl, George; Shim, Wang Geun; Vigneswaran, Saravanamuthu

    2014-01-01

    Coagulation removes colloidal matters and dissolved organic carbon (DOC) which can cause irreversible membrane fouling. However, how DOC is removed by coagulant is not well-known. Jar test was used to study the removal of hydrophobic and hydrophilic DOC fractions at various doses (0.5-8.0 mg-Fe(+3) L(-1)) of ferric chloride (FeCl3) and pH (5.0-9.0). Natural organic matter (NOM) in seawater and treated seawater were fractionated by liquid chromatography-organic carbon detector (LC-OCD). Compared to surface water, the removal of DOC in seawater by coagulation was remarkably different. Majority of DOC could be easily removed with very low coagulant dose (<5.0 mg-Fe(+3) L(-1)) and the removal efficiency did not vary with pH, but the DOC composition in treated water had significantly changed. Hydrophobic fraction (HB) was better removed at high pH while hydrophilic fraction (HF) was better removed at low pH. A modified model of Kastl et al. (2004) which assumed that the removal occurred by adsorption of un-dissociated compounds onto ferric hydroxide was formulated and successfully validated against the jar test data.

  10. Copper(II) binding by dissolved organic matter: importance of the copper-to-dissolved organic matter ratio and implications for the biotic ligand model.

    PubMed

    Craven, Alison M; Aiken, George R; Ryan, Joseph N

    2012-09-18

    The ratio of copper to dissolved organic matter (DOM) is known to affect the strength of copper binding by DOM, but previous methods to determine the Cu(2+)-DOM binding strength have generally not measured binding constants over the same Cu:DOM ratios. In this study, we used a competitive ligand exchange-solid-phase extraction (CLE-SPE) method to determine conditional stability constants for Cu(2+)-DOM binding at pH 6.6 and 0.01 M ionic strength over a range of Cu:DOM ratios that bridge the detection windows of copper-ion-selective electrode and voltammetry measurements. As the Cu:DOM ratio increased from 0.0005 to 0.1 mg of Cu/mg of DOM, the measured conditional binding constant ((c)K(CuDOM)) decreased from 10(11.5) to 10(5.6) M(-1). A comparison of the binding constants measured by CLE-SPE with those measured by copper-ion-selective electrode and voltammetry demonstrates that the Cu:DOM ratio is an important factor controlling Cu(2+)-DOM binding strength even for DOM isolates of different types and different sources and for whole water samples. The results were modeled with Visual MINTEQ and compared to results from the biotic ligand model (BLM). The BLM was found to over-estimate Cu(2+) at low total copper concentrations and under-estimate Cu(2+) at high total copper concentrations.

  11. Comparing Modeled and Measured Mercury Speciation in Contaminated Groundwater: Importance of Dissolved Organic Matter Composition.

    PubMed

    Richard, Jan-Helge; Bischoff, Cornelia; Biester, Harald

    2016-07-19

    In addition to analytical speciation, reliable Hg species modeling is crucial for predicting the mobility and toxicity of Hg, but geochemical speciation codes have not yet been tested for their prediction accuracy. Our study compares analyses of Hg species in highly Hg-contaminated groundwater (Hgtot: 0.02-4 μmol·L(-1)) at three sites with predictions of Hg speciation obtained from three geochemical codes (WHAM, Visual MINTEQ, PHREEQC) with and without implementation of Hg complexation by dissolved organic matter (DOM). Samples were analyzed for chemical composition, elemental, inorganic, and DOM-bound Hg (Hg(0), Hginorg, HgDOM). Hg-DOM complexation was modeled using three approaches: binding to humic/fulvic acids, binding to thiol-groups, or a combination of both. Results of Hg(0) modeling were poor in all scenarios. Prediction accuracy for Hginorg and HgDOM strongly depended on the assumed DOM composition. Best results were achieved when weaker binding sites, simulated by WHAMs DOM submodel, were combined with strongly binding thiol groups. Indications were found that thiol-DOM ratios in groundwater are likely to be lower than in surface water, highlighting the need for analytical thiol quantification in groundwater DOM. This study shows that DOM quality is a crucial parameter for prediction of Hg speciation in groundwater by means of geochemical modeling.

  12. pH modeling for maximum dissolved organic matter removal by enhanced coagulation.

    PubMed

    Xie, Jiankun; Wang, Dongsheng; van Leeuwen, John; Zhao, Yanmei; Xing, Linan; Chow, Christopher W K

    2012-01-01

    Correlations between raw water characteristics and pH after enhanced coagulation to maximize dissolved organic matter (DOM) removal using four typical coagulants (FeCl3, Al2(SO4)3, polyaluminum chloride (PACl) and high performance polyaluminum chloride (HPAC)) without pH control were investigated. These correlations were analyzed on the basis of the raw water quality and the chemical and physical fractionations of DOM of thirteen Chinese source waters over three seasons. It was found that the final pH after enhanced coagulation for each of the four coagulants was influenced by the content of removable DOM (i.e. hydrophobic and higher apparent molecular weight (AMW) DOM), the alkalinity and the initial pH of raw water. A set of feed-forward semi-empirical models relating the final pH after enhanced coagulation for each of the four coagulants with the raw water characteristics were developed and optimized based on correlation analysis. The established models were preliminarily validated for prediction purposes, and it was found that the deviation between the predicted data and actual data was low. This result demonstrated the potential for the application of these models in practical operation of drinking water treatment plants.

  13. Effects of asynchronous snowmelt on flushing of dissolved organic carbon: A mixing model approach

    USGS Publications Warehouse

    Boyer, E.W.; Hornberger, G.M.; Bencala, K.E.; McKnight, Diane M.

    2000-01-01

    In many snowmelt-dominated catchments, stream dissolved organic carbon (DOC) levels typically increase rapidly as spring melt commences, peak before maximum discharge, and decrease quickly as melting continues. We present data from Deer Creek (Summit County, CO) that shows this distinctive flushing response of DOC during snowmelt runoff, with DOC stored in landscape soils flushed to the stream in response to infiltrating melt waters. Our prior studies show that asynchronous melting of the snowpack across the landscape causes the spring DOC flush to be initiated at different times throughout the catchment. In this study we quantify characteristics of the asynchronous melt and its effect on DOC flushing. We investigated whether a simple mixing model can be used to capture the essentials of the asynchronous melting of a seasonal snowpack and its controls on DOC transport. We divided the catchment into zones of aspect and elevation, which largely determine spatial and temporal variations in the distribution of snow. TOPMODEL was used to simulate the hydrology in each zone, and the simulated flow paths were routed through a simple DOC mixing model to predict contributions of DOC to the stream. The zonal responses were aggregated to give a predicted response of hydrology and DOC fluxes for the entire catchment. Our results indicate that asynchronous melting-which determines the timing of contributions of discharge and DOC to streamflow from different areas of the landscape-can be quantified using a simple modeling approach. Copyright ?? 2000 John Wiley & Sons, Ltd.

  14. Modeling the Dynamics and Export of Dissolved Organic Matter in the Northeastern U.S. Continental Shelf

    NASA Technical Reports Server (NTRS)

    Druon, J.N.; Mannino, A.; Signorini, Sergio R.; McClain, Charles R.; Friedrichs, M.; Wilkin, J.; Fennel, K.

    2009-01-01

    Continental shelves are believed to play a major role in carbon cycling due to their high productivity. Particulate organic carbon (POC) burial has been included in models as a carbon sink, but we show here that seasonally produced dissolved organic carbon (DOC) on the shelf can be exported to the open ocean by horizontal transport at similar rates (1-2 mol C/sq m/yr) in the southern U.S. Mid-Atlantic Bight (MAB). The dissolved organic matter (DOM) model imbedded in a coupled circulation-biogeochemical model reveals a double dynamics: the progressive release of dissolved organic nitrogen (DON) in the upper layer during summer increases the regenerated primary production by 30 to 300%, which, in turns ; enhances the DOC production mainly from phytoplankton exudation in the upper layer and solubilization of particulate organic matter (POM) deeper in the water column. This analysis suggests that DOM is a key element for better representing the ecosystem functioning and organic fluxes in models because DOM (1) is a major organic pool directly related to primary production, (2) decouples partially the carbon and nitrogen cycles (through carbon excess uptake, POM solubilization and DOM mineralization) and (3) is intimately linked to the residence time of water masses for its distribution and export.

  15. Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM).

    PubMed

    Clark, Catherine D; de Bruyn, Warren; Jones, Joshua G

    2014-02-15

    To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H2O2) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H2O2 with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h(-1)); values ranged from 6.99 to 0.137 mM h(-1) for quinones. Apparent quantum yields (Θ app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation-emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM.

  16. Riverine Dissolved Organic Matter Degradation Modeled Through Microbial Incubations of Vascular Plant Leachates

    NASA Astrophysics Data System (ADS)

    Harfmann, J.; Hernes, P.; Chuang, C. Y.

    2015-12-01

    Dissolved organic matter (DOM) contains as much carbon as is in the atmosphere, provides the main link between terrestrial and marine carbon reservoirs, and fuels the microbial food web. The fate and removal of DOM is a result of several complex conditions and processes, including photodegradation, sorption/desorption, dominant vascular plant sources, and microbial abundance. In order to better constrain factors affecting microbial degradation, laboratory incubations were performed using Sacramento River water for microbial inoculums and vascular plant leachates. Four vascular plant sources were chosen based on their dominance in the Sacramento River Valley: gymnosperm needles from Pinus sabiniana (foothill pine), angiosperm dicot leaves from Quercus douglassi (blue oak), angiosperm monocot mixed annual grasses, and angiosperm monocot mixed Schoenoplectus acutus (tule) and Typha spp. (cattails). Three concentrations of microbial inoculum were used for each plant material, ranging from 0.2% to 10%. Degradation was monitored as a function of time using dissolved organic carbon (DOC), UV-Vis absorbance, and fluorescent dissolved organic matter (fDOM), and was compared across vascular plant type and inoculum concentration.

  17. Modeling the production, decomposition, and transport of dissolved organic carbon in boreal soils

    USGS Publications Warehouse

    Fan, Zhaosheng; Neff, Jason C.; Wickland, Kimberly P.

    2010-01-01

    The movement of dissolved organic carbon (DOC) through boreal ecosystems has drawn increased attention because of its potential impact on the feedback of OC stocks to global environmental change in this region. Few models of boreal DOC exist. Here we present a one-dimensional model with simultaneous production, decomposition, sorption/desorption, and transport of DOC to describe the behavior of DOC in the OC layers above the mineral soils. The field-observed concentration profiles of DOC in two moderately well-drained black spruce forest sites (one with permafrost and one without permafrost), coupled with hourly measured soil temperature and moisture, were used to inversely estimate the unknown parameters associated with the sorption/desorption kinetics using a global optimization strategy. The model, along with the estimated parameters, reasonably reproduces the concentration profiles of DOC and highlights some important potential controls over DOC production and cycling in boreal settings. The values of estimated parameters suggest that humic OC has a larger potential production capacity for DOC than fine OC, and most of the DOC produced from fine OC was associated with instantaneous sorption/desorption whereas most of the DOC produced from humic OC was associated with time-dependent sorption/desorption. The simulated DOC efflux at the bottom of soil OC layers was highly dependent on the component and structure of the OC layers. The DOC efflux was controlled by advection at the site with no humic OC and moist conditions and controlled by diffusion at the site with the presence of humic OC and dry conditions.

  18. A variable reaction rate model for chlorine decay in drinking water due to the reaction with dissolved organic matter.

    PubMed

    Hua, Pei; Vasyukova, Ekaterina; Uhl, Wolfgang

    2015-05-15

    A second order kinetic model for simulating chlorine decay in bulk water due to the reaction with dissolved organic matter (DOM) was developed. It takes into account the decreasing reactivity of dissolved organic matter using a variable reaction rate coefficient (VRRC) which decreases with an increasing conversion. The concentration of reducing species is surrogated by the maximum chlorine demand. Temperature dependency, respectively, is described by the Arrhenius-relationship. The accuracy and adequacy of the proposed model to describe chlorine decay in bulk water were evaluated and shown for very different waters and different conditions such as water mixing or rechlorination by applying statistical tests. It is thus very well suited for application in water quality modeling for distribution systems.

  19. Understanding and modelling the variability in Dissolved Organic Carbon concentrations in catchment drainage

    NASA Astrophysics Data System (ADS)

    Coleman, Martin; Waldron, Susan; Scott, Marian; Drew, Simon

    2013-04-01

    Our knowledge of dynamic natural habitats could be improved through the deployment of automated sensor technology. Dissolved organic carbon concentrations, [DOC], are of interest to water companies as purification removes this pool and currently in environmental science, due in part to rising DOC levels and also as respiration of this C pool can lead to an increased CO2 efflux. Manual sampling of catchment drainage systems has revealed seasonal patterns in DOC (Williams, P.J.L., 1995) and that hydrological events export most DOC(Raymond, P.A. and J.E. Saiers, 2010). However, manual sampling precludes detailed characterisation of the dynamic fluctuation of DOC over shorter but important time periods e.g. immediately prior to an event; the transition from base flow to a surface run-off dominated system as surface flow pathways defrost. Such insight is only gained through deployment of continuous-monitoring equipment. Since autumn 2010 we have deployed an S::CAN Spectrolyser (which from absorbance gives a measurement of [DOC]) in a 7.5 kilometre squared peaty catchment draining Europe's largest windfarm, Whitelee. Since autumn 2011, we have an almost complete time series of [DOC] every 30. Here [DOC] has ranged from 12.2 to 58.4 mg/l C and during event flow DOC had a maximum variation of 23.5 mg/l within a single day. Simultaneously with the Spectrolyser, we have logged stage height, pH and conductivity using an In-Situ Inc MD Troll 9000. Generally there is an inverse relationship between [DOC] and both pH and conductivity, but a positive relationship (albeit with seasonal differences) with [DOC] and stage height, from which we can infer hydrological changes in the source of the DOC. Here, in addition to presenting the time series of the data, and a more accurate export budget estimate, I will explore statistical methods for the handling of large datasets. Trends in the data of such large and dynamic data sets are challenging to model. Simple relationships with stage

  20. Uranium isotopes and dissolved organic carbon in loess permafrost: Modeling the age of ancient ice

    USGS Publications Warehouse

    Ewing, Stephanie A.; Paces, James B.; O'Donnell, J.A.; Jorgenson, M.T.; Kanevskiy, M.Z.; Aiken, George R.; Shur, Y.; Harden, Jennifer W.; Striegl, Robert G.

    2015-01-01

    fluctuations in climate, fire disturbance and vegetation. Radiocarbon (14C) analysis of dissolved organic carbon (DOC) in thaw waters supports ages greater than ∼40 ky BP below 10 m. DOC concentrations in thaw waters increased with depth to maxima of >1000 ppm, despite little change in ice content or cryostructures. These relations suggest time-dependent production of old DOC that will be released upon permafrost thaw at a rate that is mediated by sediment transport, among other factors.

  1. Uranium isotopes and dissolved organic carbon in loess permafrost: Modeling the age of ancient ice

    NASA Astrophysics Data System (ADS)

    Ewing, S. A.; Paces, J. B.; O'Donnell, J. A.; Jorgenson, M. T.; Kanevskiy, M. Z.; Aiken, G. R.; Shur, Y.; Harden, J. W.; Striegl, R.

    2015-03-01

    climate, fire disturbance and vegetation. Radiocarbon (14C) analysis of dissolved organic carbon (DOC) in thaw waters supports ages greater than ∼40 ky BP below 10 m. DOC concentrations in thaw waters increased with depth to maxima of >1000 ppm, despite little change in ice content or cryostructures. These relations suggest time-dependent production of old DOC that will be released upon permafrost thaw at a rate that is mediated by sediment transport, among other factors.

  2. Recalcitrant dissolved organic carbon fractions.

    PubMed

    Hansell, Dennis A

    2013-01-01

    Marine dissolved organic carbon (DOC) exhibits a spectrum of reactivity, from very fast turnover of the most bioavailable forms in the surface ocean to long-lived materials circulating within the ocean abyss. These disparate reactivities group DOC by fractions with distinctive functions in the cycling of carbon, ranging from support of the microbial loop to involvement in the biological pump to a hypothesized major source/sink of atmospheric CO(2) driving paleoclimate variability. Here, the major fractions constituting the global ocean's recalcitrant DOC pool are quantitatively and qualitatively characterized with reference to their roles in carbon biogeochemistry. A nomenclature for the fractions is proposed based on those roles.

  3. Dissolved organic C export is highly dynamic - capturing this variability and challenges in modelling

    NASA Astrophysics Data System (ADS)

    Waldron, S.; Coleman, M.; Scott, E. M.; Drew, S.

    2013-12-01

    High resolution, field-deployable sensors offer opportunities to deepen our understanding of natural environmental systems, and measure the ';riverine pulse'. Studies utilising high-resolution equipment have demonstrated that sampling hydrological variables on traditional low frequency rates (such as once a week) creates a simplified picture of conditions that does not capture a true reflection of how fluvial systems operate. Dissolved organic carbon (DOC) represents a large and diverse mixture of compounds (including sugars, amino acids and humic substances) and concentration and composition of this pool varies globally. Understanding transport of this C pool in fluvial systems is important as it 1) represents the lateral export of C no longer sequestered in the terrestrial system, 2) surface water concentrations have been observed to have increased globally and we need to know if this trend is continuing and 3) when water is abstracted the purification processes removing DOC from the water, can create harmful by-products and so prior knowledge of inflow loading is valuable. Traditionally [DOC] has been measured using manual sampling methods, where a water sample would be collected in the field and returned to the lab. This approach can provide reliable data but the resource required to sustain this make it nearly impossible to measure the ';riverine pulse' through the information in long and detailed time series. In recent years new technology designed to estimate [DOC] in-situ has been developed. We have used one of these devices, which measures absorption in both the visible and UV wavelength regions of the electromagnetic spectrum and from this absorbance profile an algorithm estimates [DOC]. We have deployed this system in the field environment and after overcoming initial challenges have an almost continuous time series of [DOC], measured at 30 minute intervals, since May 2012. The logger has been functioning over a temperature range of 0.5 - 23 °C and a

  4. Degradation dynamics and bioavailability of land-based dissolved organic nitrogen in the Bohai Sea: Linking experiment with modeling.

    PubMed

    Li, Keqiang; Ma, Yunpeng; Dai, Aiquan; Wang, Xiulin

    2017-02-24

    Dissolved organic nitrogen (DON) is the major nitrogen form in the Bohai Sea. Land-based DON is released into the nitrogen pool and degraded by planktonic microbiota in coastal ocean. In this study, we evaluated the degradation of land-based DON, particularly its dynamics and bioavailability, in coastal water by linking experiment and modeling. Results showed that the degradation rate constant of DON from sewage treatment plant was significantly faster than those of other land-based sources (P<0.05). DON was classified into three categories based on dynamics and bioavailability. The supply of dissolved inorganic nitrogen (DIN) pool from the DON pool of Liao River, Hai River, and Yellow River was explored using a 3D hydrodynamic multi-DON biogeochemical model in the Bohai Sea. In the model, large amounts of DIN were supplied from DON of Liao River than the other rivers because of prolonged flushing time in Liaodong Bay.

  5. Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

    NASA Astrophysics Data System (ADS)

    Tang, Jianwu; Johannesson, Karen H.

    2003-07-01

    Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., p KMHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. p KMHA values were further refined by comparison of calculated Model V "fits" to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl -, F -, OH -, SO 42-, CO 32-, PO 43-), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V's ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to "speciation" data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5

  6. PATTERNS AND CONTROLS OF DISSOLVED ORGANIC MATTER EXPORT BY MAJOR RIVERS: A NEW SEASONAL, SPATIALLY EXPLICIT, GLOBAL MODEL

    EPA Science Inventory

    River-derived dissolved organic matter (DOM) influences metabolism, light attenuation, and bioavailability of metals and nutrients in coastal ecosystems. Recent work suggests that DOM concentrations in surface waters vary seasonally because different organic matter pools are mobi...

  7. Modeling nonequilibrium adsorption of MIB and sulfamethoxazole by powdered activated carbon and the role of dissolved organic matter competition.

    PubMed

    Shimabuku, Kyle K; Cho, Hyukjin; Townsend, Eli B; Rosario-Ortiz, Fernando L; Summers, R Scott

    2014-12-02

    This study demonstrates that the ideal adsorbed solution theory-equivalent background compound (IAST-EBC) as a stand-alone model can simulate and predict the powdered activated carbon (PAC) adsorption of organic micropollutants found in drinking water sources in the presence of background dissolved organic matter (DOM) under nonequilibrium conditions. The IAST-EBC represents the DOM competitive effect as an equivalent background compound (EBC). When adsorbing 2-methylisoborneol (MIB) with PAC, the EBC initial concentration was a similar percentage, on average 0.51%, of the dissolved organic carbon in eight nonwastewater impacted surface waters. Using this average percentage in the IAST-EBC model yielded good predictions for MIB removal in two nonwastewater impacted waters. The percentage of competitive DOM was significantly greater in wastewater impacted surface waters, and varied markedly in DOM size fractions. Fluorescence parameters exhibited a strong correlation with the percentage of competitive DOM in these waters. Utilizing such correlations in the IAST-EBC successfully modeled MIB and sulfamethoxazole adsorption by three different PACs in the presence of DOM that varied in competitive effect. The influence of simultaneous coagulant addition on PAC adsorption of micropollutants was also investigated. Coagulation caused the DOM competitive effect to increase and decrease with MIB and sulfamethoxazole, respectively.

  8. Understanding drivers of the export of dissolved organic carbon from a German headwater catchment using Generalised Additive Models

    NASA Astrophysics Data System (ADS)

    Selle, Benny; Musolff, Andreas; Tittel, Jörg

    2016-04-01

    In the literature, several causes of recently increasing concentrations of dissolved organic carbon (DOC) in headwaters across eastern North America and northern and central Europe have been debated. One likely driver of the widespread increase of DOC concentrations since the early 1990s are decreasing depositions of acid rain resulting in an increased solubility of organic carbon compounds including humic acids. Here, we tested the hypothesis if the reduced availability of nitrate stimulated the microbial reduction of ferric iron soil minerals and the mobilisation of DOC. Forested catchments are relatively unaffected by agricultural and urban nitrate inputs. In these catchments, decreasing depositions often resulted in a reduced availability of nitrate, which are preferred electron acceptors in microbial decomposition processes. As ferric iron minerals act as efficient sorbents of organic compounds in soils its reduction may cause a release of humic substances and hence an export of DOC. To test this hypothesis, time series of DOC, dissolved iron and nitrate from a forested headwater catchment in Germany were examined using Generalised Additive Models. We found that rising DOC concentrations most likely resulted from a reductive dissolution of iron(III) minerals in soils and the associated mobilisation of adsorbed organic carbon. Phosphate, which can trigger undesired algal growth and is also known to be adsorbed by particulate iron(III), was released as well.

  9. Understanding drivers of the export of dissolved organic carbon from headwater catchments in Germany using Generalised Additive Models

    NASA Astrophysics Data System (ADS)

    Selle, Benny; Tittel, Jörg; Musolff, Andreas

    2015-04-01

    In the literature, several causes of recently increasing concentrations of dissolved organic carbon (DOC) in headwaters across eastern North America and northern and central Europe have been debated. One likely driver of the widespread increase of DOC concentrations since the early to mid 1990s are decreasing depositions of acid rain resulting in an increased solubility of organic carbon compounds including humic acids. Here, we tested the hypothesis if the reduced availability of both nitrate and sulfate stimulated the reduction of ferric iron soil minerals and the mobilisation of DOC. Decreasing depositions often resulted in a reduced availability of both nitrate and sulphate, which are preferred electron acceptors in microbial decomposition processes. As iron minerals act as efficient sorbents of organic compounds in soils its reduction may have caused a release of humic substances and hence an increasing export of DOC from headwater catchments. To test this hypothesis, time series of DOC, dissolved iron, sulfate and nitrate from several German headwater catchments were examined using Generalised Additive Models. Using this modelling technique, discharge corrected time series of concentrations were represented as a sum of a seasonal and a non-linear trend component. Both, the computed trends and seasonalities supported the redox hypothesis.

  10. First dynamic model of dissolved organic carbon derived directly from high-frequency observations through contiguous storms.

    PubMed

    Jones, Timothy D; Chappell, Nick A; Tych, Wlodek

    2014-11-18

    The first dynamic model of dissolved organic carbon (DOC) export in streams derived directly from high frequency (subhourly) observations sampled at a regular interval through contiguous storms is presented. The optimal model, identified using the recently developed RIVC algorithm, captured the rapid dynamics of DOC load from 15 min monitored rainfall with high simulation efficiencies and constrained uncertainty with a second-order (two-pathway) structure. Most of the DOC export in the four headwater basins studied was associated with the faster hydrometric pathway (also modeled in parallel), and was soon exhausted in the slower pathway. A delay in the DOC mobilization became apparent as the ambient temperatures increased. These features of the component pathways were quantified in the dynamic response characteristics (DRCs) identified by RIVC. The model and associated DRCs are intended as a foundation for a better understanding of storm-related DOC dynamics and predictability, given the increasing availability of subhourly DOC concentration data.

  11. Experimental and modeling approach to study sorption of dissolved hydrophobic organic contaminants to microbial biofilms.

    PubMed

    Wicke, Daniel; Böckelmann, Uta; Reemtsma, Thorsten

    2007-05-01

    A biofilm reactor was developed to investigate the sorption of polycyclic aromatic hydrocarbons (PAH) as model compounds for hydrophobic organic contaminants (HOC) to intact microbial biofilms at environmentally realistic concentrations. When operated as a differential column batch reactor, the system can be used to study the thermodynamics as well as the kinetics of the exchange of HOC between an aqueous phase and microbial biofilms. Organic carbon normalized partition coefficients (K(oc)) for phenanthrene, fluoranthene and pyrene were at the lower end of those known for other organic sorbents. Intra-biofilm diffusion coefficients (D) were calculated from decrease in solute concentration over time using a model for diffusion through a plane sheet and ranged from 0.23 to 0.45x10(-9)cm(2)s(-1) for the three PAH. These diffusion coefficients are about four orders of magnitude lower than those reported in literature for free aqueous solution. These data and the experimental approach presented here are useful to assess the importance of microbial biofilms for exchange processes of HOC in heterogeneous systems such as water distribution systems, membranes and aquifers, sewer systems or surface soils.

  12. Simple model of dissolved oxygen consumption in a bay within high organic loading: an applied remediation tool.

    PubMed

    Ahumada, Ramón; Vargas, José; Pagliero, Liliana

    2006-07-01

    San Vicente Bay is a coastal shallow embayment in Central Chile with multiple uses, one of which is receiving wastewater from industrial fisheries, steel mill effluents, and domestic sewage. A simulation model was developed and applied to dissolved oxygen consumption by organic residues released into this embayment. Three compartments were established as function of: depth, circulation and outfall location. The model compartments had different volumes, and their oxygen saturation value was used as baseline. The parameters: (a) BOD5 of the industrial and urban effluents, (b) oxygen demand by organic sediments, (c) respiration, (d) photosynthesis and (e) re-aeration were included in the model. Iteration results of the model showed severe alterations in Compartment 1, with a decrease of 65% in the oxygen below saturation. Compartment 2 showed a small decline (10%) and compartment 3 did not show apparent changes in oxygen values. Measures recommended for remediation were to decrease the BOD5 loading by 30% in the affected sector. Iteration of the model for 200 h following recommendations derived from the preceding results produced an increase in saturation of 60% (5 ml O2 L(-1)), which suggested an improvement of the environmental conditions.

  13. Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

    PubMed

    Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

    2016-06-01

    Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies.

  14. Kinetics of peat soil dissolved organic carbon release to surface water. Part 2. A chemodynamic process model.

    PubMed

    Thibodeaux, L J; Aguilar, L

    2005-09-01

    Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper contains a process-based mathematical model that quantifies the DOC release from the bed and its build-up in the water column. The model elements are based on microbial DOC production rates and bed sediment transport kinetics describing its' release from the organic soil systems. It relies on laboratory data obtained from an experimental study, Part 1, designed to simulate the DOC chemodynamics of aquatic reservoirs built upon peat soils. A two-step DOC release process was structured based on the experimental findings. The model mechanism assumes a quick release fraction that characterizes the upper soil surface layers as a "tea bag" type release process. This is followed by a fraction that is continuously produced and then released at a constant rate overtime by on-going microbial processes within the upper soil layers. The depth of the active layer, selected as h* = 0.3 cm, is the single adjustable parameter in the model. Concentration predictions of the are consistent with the laboratory simulations and field observations. Measured vs. model-calculated DOC concentrations for both in the microcosm bed and water column are used to test critical features of the proposed model. As conceived and structured it appears to be a realistic first step in quantifying the DOC release consequences for the water column of a reservoir sited upon a peat-soil bed. The development ends with an application to a hypothetical reservoir in order to illustrate model strengths and uncertainties.

  15. Effect of chemical oxidation on the sorption tendency of dissolved organic matter to a model hydrophobic surface.

    PubMed

    Zeng, Teng; Wilson, Corey J; Mitch, William A

    2014-05-06

    The application of chemical oxidants may alter the sorption properties of dissolved organic matter (DOM), such as humic and fulvic acids, proteins, polysaccharides, and lipids, affecting their fate in water treatment processes, including attachment to other organic components, activated carbon, and membranes (e.g., organic fouling). Similar reactions with chlorine (HOCl) and bromine (HOBr) produced at inflammatory sites in vivo affect the fate of biomolecules (e.g., protein aggregation). In this study, quartz crystal microbalance with dissipation monitoring (QCM-D) was used to evaluate changes in the noncovalent interactions of proteins, polysaccharides, fatty acids, and humic and fulvic acids with a model hydrophobic surface as a function of increasing doses of HOCl, HOBr, and ozone (O3). All three oxidants enhanced the sorption tendency of proteins to the hydrophobic surface at low doses but reduced their sorption tendency at high doses. All three oxidants reduced the sorption tendency of polysaccharides and fatty acids to the hydrophobic surface. HOCl and HOBr increased the sorption tendency of humic and fulvic acids to the hydrophobic surface with maxima at moderate doses, while O3 decreased their sorption tendency. The behavior observed with two water samples was similar to that observed with humic and fulvic acids, pointing to the importance of these constituents. For chlorination, the highest sorption tendency to the hydrophobic surface was observed within the range of doses typically applied during water treatment. These results suggest that ozone pretreatment would minimize membrane fouling by DOM, while chlorine pretreatment would promote DOM removal by activated carbon.

  16. Temperature Dependence of Photodegradation of Dissolved Organic Matter to Dissolved Inorganic Carbon and Particulate Organic Carbon

    PubMed Central

    Porcal, Petr; Dillon, Peter J.; Molot, Lewis A.

    2015-01-01

    Photochemical transformation of dissolved organic matter (DOM) has been studied for more than two decades. Usually, laboratory or “in-situ” experiments are used to determine photodegradation variables. A common problem with these experiments is that the photodegradation experiments are done at higher than ambient temperature. Five laboratory experiments were done to determine the effect of temperature on photochemical degradation of DOM. Experimental results showed strong dependence of photodegradation on temperature. Mathematical modeling of processes revealed that two different pathways engaged in photochemical transformation of DOM to dissolved inorganic carbon (DIC) strongly depend on temperature. Direct oxidation of DOM to DIC dominated at low temperatures while conversion of DOM to intermediate particulate organic carbon (POC) prior to oxidation to DIC dominated at high temperatures. It is necessary to consider this strong dependence when the results of laboratory experiments are interpreted in regard to natural processes. Photodegradation experiments done at higher than ambient temperature will necessitate correction of rate constants. PMID:26106898

  17. Associations Between the Molecular and Optical Properties of Dissolved Organic Matter in the Florida Everglades, a Model Coastal Wetland System

    PubMed Central

    Wagner, Sasha; Jaffé, Rudolf; Cawley, Kaelin; Dittmar, Thorsten; Stubbins, Aron

    2015-01-01

    Optical properties are easy-to-measure proxies for dissolved organic matter (DOM) composition, source, and reactivity. However, the molecular signature of DOM associated with such optical parameters remains poorly defined. The Florida coastal Everglades is a subtropical wetland with diverse vegetation (e.g., sawgrass prairies, mangrove forests, seagrass meadows) and DOM sources (e.g., terrestrial, microbial, and marine). As such, the Everglades is an excellent model system from which to draw samples of diverse origin and composition to allow classically-defined optical properties to be linked to molecular properties of the DOM pool. We characterized a suite of seasonally- and spatially-collected DOM samples using optical measurements (EEM-PARAFAC, SUVA254, S275−295, S350−400, SR, FI, freshness index, and HIX) and ultrahigh resolution mass spectrometry (FTICR-MS). Spearman's rank correlations between FTICR-MS signal intensities of individual molecular formulae and optical properties determined which molecular formulae were associated with each PARAFAC component and optical index. The molecular families that tracked with the optical indices were generally in agreement with conventional biogeochemical interpretations. Therefore, although they represent only a small portion of the bulk DOM pool, absorbance, and fluorescence measurements appear to be appropriate proxies for the aquatic cycling of both optically-active and associated optically-inactive DOM in coastal wetlands. PMID:26636070

  18. Associations between the molecular and optical properties of dissolved organic matter in the Florida Everglades, a model coastal wetland system

    NASA Astrophysics Data System (ADS)

    Wagner, Sasha; Jaffe, Rudolf; Cawley, Kaelin; Dittmar, Thorsten; Stubbins, Aron

    2015-11-01

    Optical properties are easy-to-measure proxies for dissolved organic matter (DOM) composition, source and reactivity. However, the molecular signature of DOM associated with such optical parameters remains poorly defined. The Florida coastal Everglades is a subtropical wetland with diverse vegetation (e.g., sawgrass prairies, mangrove forests, seagrass meadows) and DOM sources (e.g., terrestrial, microbial and marine). As such, the Everglades is an excellent model system from which to draw samples of diverse origin and composition to allow classically-defined optical properties to be linked to molecular properties of the DOM pool. We characterized a suite of seasonally- and spatially-collected DOM samples using optical measurements (EEM-PARAFAC, SUVA254, S275-295, S350-400, SR, FI, freshness index and HIX) and ultrahigh resolution mass spectrometry (FTICR-MS). Spearman’s rank correlations between FTICR-MS signal intensities of individual molecular formulae and optical properties determined which molecular formulae were associated with each PARAFAC component and optical index. The molecular families that tracked with the optical indices were generally in agreement with conventional biogeochemical interpretations. Therefore, although they represent only a small portion of the bulk DOM pool, absorbance and fluorescence measurements appear to be appropriate proxies for the aquatic cycling of both optically-active and associated optically-inactive DOM in coastal wetlands.

  19. Peer reviewed: Characterizing aquatic dissolved organic matter

    USGS Publications Warehouse

    Leenheer, Jerry A.; Croué, Jean-Philippe

    2003-01-01

    Whether it causes aesthetic concerns such as color, taste, and odor; leads to the binding and transport of organic and inorganic contaminants; produces undesirable disinfection byproducts; provides sources and sinks for carbon; or mediates photochemical processes, the nature and properties of dissolved organic matter (DOM) in water are topics of significant environmental interest. DOM is also a major reactant in and product of biogeochemical processes in which the material serves as a carbon and energy source for biota and controls levels of dissolved oxygen, nitrogen, phosphorus, sulfur, numerous trace metals, and acidity.

  20. Response surface modeling for optimization heterocatalytic Fenton oxidation of persistence organic pollution in high total dissolved solid containing wastewater.

    PubMed

    Sekaran, G; Karthikeyan, S; Boopathy, R; Maharaja, P; Gupta, V K; Anandan, C

    2014-01-01

    The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N2 adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, (29)Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H2O2 (4 mmol/L), FeSO4[Symbol: see text]7H2O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90%, respectively.

  1. An integrated Dissolved Organic Carbon Dynamics Model (DOCDM 1.0): model development and a case study in the Alaskan Yukon River Basin

    NASA Astrophysics Data System (ADS)

    Lu, X.; Zhuang, Q.

    2015-12-01

    Quantitative understanding of the variation in dissolved organic carbon (DOC) is important to studying the terrestrial ecosystem carbon cycle. This study presents a process-based, dissolved organic carbon dynamics model (DOCDM 1.0) that couples the soil heat conduction, water flow, DOC production, mineralization and transport in both surface and subsurface of soil profile to quantify DOC dynamics in boreal terrestrial ecosystems. The model is first evaluated and then applied for a watershed in Alaska to investigate its DOC production and transport. We find that 42 and 27 % of precipitation infiltrates to soils in 2004, a warmer year, and in 1976, a colder year, respectively. Under warming conditions, DOC transported via overland flow does not show the expected decrease trend while the overland DOC yield shows a 4 % increase. The horizontal subsurface flow only accounts for 1-2 % of total water flux, but transports 30-50 % of DOC into rivers. Water flush due to water infiltration controls DOC transport. Snowmelt plays a noticeable role in DOC flush-out and DOC transport significantly depends on flowpaths in the study region. High soil temperature stimulates DOC production. The overland DOC export does not necessarily follow the DOC downward trend in surface water transport. Overall, this study shows that DOC export behavior is complex under changing temperature and hydrological conditions in cold-region watersheds. To adequately quantify DOC dynamics in northern high latitudes, more DOC and hydrological data are needed to better parameterize and test the developed model before extrapolating it to the region.

  2. ESTIMATING DISSOLVED ORGANIC CARBON PARTITION COEFFICIENTS FOR NONIONIC ORGANIC CHEMICALS

    EPA Science Inventory

    A literature search was performed for dissolved organic carbon/water partition coefficients for nonionic chemicals (Kdoc) and Kdoc data was taken from more than sixty references. The Kdoc data were evaluated as a function of the n-octanol/water partition coefficients (Kow). A pre...

  3. Application of Bayesian belief net in modelling the origin and effects of terrigenous dissolved organic matter in a boreal aquatic ecosystem

    NASA Astrophysics Data System (ADS)

    Rahikainen, Mika; Hoikkala, Laura; Soinne, Helena

    2013-04-01

    models of different environmental compartments (soil chemistry, agricultural management practices, aquatic processes, costs and benefits for society) with explicit treatment of uncertainty. In order to achieve policy relevance, these models have to be integrated into resource management. We use a Bayesian belief net to describe the probabilistic dependencies among the driving forces, processes, and impacts relevant to dissolved organic matter in boreal waterways.

  4. Hydrological mobilization of mercury and dissolved organic carbon in a snow-dominated, forested watershed: Conceptualization and modeling

    USGS Publications Warehouse

    Schelker, J.; Burns, Douglas A.; Weiler, M.; Laudon, H.

    2011-01-01

    The mobilization of mercury and dissolved organic carbon (DOC) during snowmelt often accounts for a major fraction of the annual loads. We studied the role of hydrological connectivity of riparian wetlands and upland/wetland transition zones to surface waters on the mobilization of Hg and DOC in Fishing Brook, a headwater of the Adirondack Mountains, New York. Stream water total mercury (THg) concentrations varied strongly (mean = 2.25 ?? 0.5 ng L -1), and the two snowmelt seasons contributed 40% (2007) and 48% (2008) of the annual load. Methyl mercury (MeHg) concentrations ranged up to 0.26 ng L-1, and showed an inverse log relationship with discharge. TOPMODEL-simulated saturated area corresponded well with wetland areas, and the application of a flow algorithm based elevation-above-creek approach suggests that most wetlands become well connected during high flow. The dynamics of simulated saturated area and soil storage deficit were able to explain a large part of the variation of THg concentrations (r2 = 0.53 to 0.72). In contrast, the simulations were not able to explain DOC variations and DOC and THg concentrations were not correlated. These results indicate that all three constituents, THg, MeHg, and DOC, follow different patterns at the outlet: (1) the mobilization of THg is primarily controlled by the saturation state of the catchment, (2) the dilution of MeHg suggests flushing from a supply limited pool, and (3) DOC dynamics follow a pattern different from THg dynamics, which likely results from differing gain and/or loss processes for THg and/or DOC within the Fishing Brook catchment. Copyright 2011 by the American Geophysical Union.

  5. Isolation and chemical characterization of dissolved and colloidal organic matter

    USGS Publications Warehouse

    Aiken, G.; Leenheer, J.

    1993-01-01

    Commonly used techniques for the concentration and isolation of organic matter from water, such as preparative chromatography, ultrafiltration and reverse osmosis, and the methods used to analyze the organic matter obtained by these methods are reviewed. The development of methods to obtain organic matter that is associated with fractions of the dissolved organic carbon other than humic substances, such as organic bases, hydrophilic organic acids and colloidal organic matter are discussed. Methods specifically used to study dissolved organic nitrogen and dissolved organic phosphorous are also discussed. -from Authors

  6. Evaluation and modelling of dissolved organic matter reactivity toward As(III) and As(V) – implication in environmental arsenic speciation.

    PubMed

    Lenoble, V; Dang, D H; Loustau Cazalet, M; Mounier, S; Pfeifer, H-R; Garnier, C

    2015-03-01

    Many studies have been carried out to identify dissolved organic matter-trace metals interactions, as organic matter (OM) was demonstrated to be a governing parameter of metals speciation. Concerning arsenic (As), such OM-As studies are scarce and concluded that, when As binding occurred, it was probably through cationic bridges or, in some cases, directly. Yet, analytical proofs remained complex to obtain. In this work, As binding with Suwanee River Humic Acid (SRHA), as an example of dissolved organic matter, was studied, considering both As(III) and As(V), at various pH and in absence/presence of Na and Ca. Dialysis, fluorescence measurements and PHREEQC modelling were performed to identify and characterize the mechanisms at work for the various performed experiments. It was observed that As(III) binding on SRHA occurred through direct SRHA-As(III) binding and that neither Na nor Ca presence modify this mechanism. As(V) appeared to be also bound by SRHA through direct interaction, but suffered from the competition of Na for the SRHA binding sites. Oppositely, in presence of Ca, the overall As(V)-SRHA binding was significantly enhanced, Ca acting as an efficient cationic bridge through the formation of an SRHA-Ca-As(V) ternary complex. All the obtained data were satisfactorily simulated using a unique set of binding parameters which can therefore be implemented in any speciation code to better address As behaviour in environmental conditions.

  7. Relating dissolved organic matter fluorescence to functional properties

    NASA Astrophysics Data System (ADS)

    Tipping, E.; Baker, A.; Thacker, S.; Gondar, D.

    2007-12-01

    The fluorescence excitation emission matrix properties of dissolved organic matter from three rivers and one lake in NW England are analysed. Sites are sampled in duplicate and for some sites seasonally to cover variations in dissolved organic matter composition, river flow, and carbon isotopic (13C, 14C) variability. Results are compared to the functional properties of the dissolved organic matter, the functional assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Fluorescence characterization of the dissolved organic matter samples demonstrates that peak C fluorescence emission wavelength, the ratio of peak T to peak C fluorescence intensity, and the fluorescence : absorbance ratio best differentiate different dissolved organic matter samples. These parameters correspond to dissolved organic matter aromaticity, the ratio of labile to recalcitrant organic matter, and dissolved organic matter molecular weight. Peak C fluorescence emission wavelength, the ratio of peak T to peak C fluorescence intensity, and the fluorescence : absorbance ratio fluorescence parameters also have strong correlations with several of the functional assays, in particular the extinction coefficients, benzo(a)pyrene binding and alumina adsorption, and buffering capacity. In many cases, regression equations with a correlation coefficient >0.9 are obtained, suggesting that dissolved organic matter functional character can be predicted from DOM fluorescence properties. For one site, the relationship between dissolved organic matter source, fluorescence, function and carbon isotopic composition is discussed.

  8. Composition of dissolved organic matter in groundwater

    NASA Astrophysics Data System (ADS)

    Longnecker, Krista; Kujawinski, Elizabeth B.

    2011-05-01

    Groundwater constitutes a globally important source of freshwater for drinking water and other agricultural and industrial purposes, and is a prominent source of freshwater flowing into the coastal ocean. Therefore, understanding the chemical components of groundwater is relevant to both coastal and inland communities. We used electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to examine dissolved organic compounds in groundwater prior to and after passage through a sediment-filled column containing microorganisms. The data revealed that an unexpectedly high proportion of organic compounds contained nitrogen and sulfur, possibly due to transport of surface waters from septic systems and rain events. We matched 292 chemical features, based on measured mass:charge ( m/z) values, to compounds stored in the Kyoto Encyclopedia of Genes and Genomes (KEGG). A subset of these compounds (88) had only one structural isomer in KEGG, thus supporting tentative identification. Most identified elemental formulas were linked with metabolic pathways that produce polyketides or with secondary metabolites produced by plants. The presence of polyketides in groundwater is notable because of their anti-bacterial and anti-cancer properties. However, their relative abundance must be quantified with appropriate analyses to assess any implications for public health.

  9. Utilization of PARAFAC-Modeled Excitation-Emission Matrix (EEM) Fluorescence Spectroscopy to Identify Biogeochemical Processing of Dissolved Organic Matter in a Northern Peatland.

    PubMed

    Tfaily, Malak M; Corbett, Jane E; Wilson, Rachel; Chanton, Jeffrey P; Glaser, Paul H; Cawley, Kaelin M; Jaffé, Rudolf; Cooper, William T

    2015-01-01

    In this study, we contrast the fluorescent properties of dissolved organic matter (DOM) in fens and bogs in a Northern Minnesota peatland using excitation emission matrix fluorescence spectroscopy with parallel factor analysis (EEM-PARAFAC). EEM-PARAFAC identified four humic-like components and one protein-like component and the dynamics of each were evaluated based on their distribution with depth as well as across sites differing in hydrology and major biological species. The PARAFAC-EEM experiments were supported by dissolved organic carbon measurements (DOC), optical spectroscopy (UV-Vis), and compositional characterization by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). The FT-ICR MS data indicate that metabolism in peatlands reduces the molecular weights of individual components of DOM, and oxygen-rich less aromatic molecules are selectively biodegraded. Our data suggest that different hydrologic and biological conditions within the larger peat ecosystem drive molecular changes in DOM, resulting in distinctly different chemical compositions and unique fluorescent fingerprints. PARAFAC modeling of EEM data coupled with ultrahigh resolution FT-ICR MS has the potential to provide significant molecular-based information on DOM composition that will support efforts to better understand the composition, sources, and diagenetic status of DOM from different terrestrial and aquatic systems.

  10. Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

    NASA Technical Reports Server (NTRS)

    Mannino, Antonio; Harvey, H. Rodger

    2003-01-01

    Analysis of high-molecular-weight dissolved organic matter (DOM) from two estuaries in the northwest Atlantic Ocean reveals that black carbon (BC) is a significant component of previously uncharacterized DOM, suggesting that river-estuary systems are important exporters of recalcitrant dissolved organic carbon to the ocean.

  11. Bioavailability and characterization of dissolved organic nitrogen and dissolved organic phosphorus in wastewater effluents.

    PubMed

    Qin, Chao; Liu, Haizhou; Liu, Lei; Smith, Scott; Sedlak, David L; Gu, April Z

    2015-04-01

    There is still a great knowledge gap in the understanding of characteristics and bioavailability of dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) in wastewater effluents, which surmise implications related to both discharge regulation and treatment practice. In this study, we simultaneously investigated the characteristics and bioavailability of both DON and DOP, with separated hydrophilic versus hydrophobic fractions, in highly-treated wastewater effluents for the first time. The tertiary effluents from two wastewater treatment plants were separated into two fractions by XAD-8 resin coupled with anion exchange resin based on the hydrophobicity. Results showed that the majority of DON was present in hydrophilic forms while more DOP existed in hydrophobic forms. Hydrophilic DON contributed to 64.0%-72.2% of whole DON, while hydrophobic DOP accounted for 61.4%-80.7% of total DOP for the two plants evaluated. The effluents and their fractions were then subject to bioavailability assay based on 14-day algae growth. The results indicated that majority (~73-75%) of the effluent DOP, particularly the hydrophobic fraction with lower C/P ratio was more likely to be bioavailable for algal growth. The bioavailable fraction of DON varied widely (28%-61%) for the two plants studied and the hydrophilic fraction with lower C/N ratio seemed to exhibit higher bioavailability than the hydrophobic portion. The differences in bioavailable DON and DOP distributions of effluents from those two plants could be attributed to different receiving effluent compositions and wastewater treatment processes. In addition, fluorescence excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were used to characterize the dissolved organic matter (DOM) in wastewater effluent, which provided insights into the nature of organic matter in wastewater samples with different characteristics and originating sources.

  12. Dissolved organic carbon release by marine macrophytes

    NASA Astrophysics Data System (ADS)

    Barrón, C.; Apostolaki, E. T.; Duarte, C. M.

    2012-02-01

    Estimates of dissolved organic carbon (DOC) release by marine macrophyte communities (seagrass meadows and macroalgal beds) were obtained experimentally using in situ benthic chambers. The effect of light availability on DOC release by macrophyte communities was examined in two communities both by comparing net DOC release under light and dark, and by examining the response of net DOC release to longer-term (days) experimental shading of the communities. All most 85% of the seagrass communities and almost all of macroalgal communities examined acted as net sources of DOC. There was a weak tendency for higher DOC fluxes under light than under dark conditions in seagrass meadow. There is no relationship between net DOC fluxes and gross primary production (GPP) and net community production (NCP), however, this relationship is positive between net DOC fluxes and community respiration. Net DOC fluxes were not affected by shading of a T. testudinum community in Florida for 5 days, however, shading of a mixed seagrass meadow in the Philippines led to a significant reduction on the net DOC release when shading was maintained for 6 days compared to only 2 days of shading. Based on published and unpublished results we also estimate the global net DOC production by marine macrophytes. The estimated global net DOC flux, and hence export, from marine macrophyte is about 0.197 ± 0.015 Pg C yr-1 or 0.212 ± 0.016 Pg C yr-1 depending if net DOC flux by seagrass meadows was estimated by taking into account the low or high global seagrass area, respectively.

  13. Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA

    USGS Publications Warehouse

    Spencer, Robert G.M.; Butler, Kenna D.; Aiken, George R.

    2012-01-01

    Dissolved organic carbon (DOC) concentration and chromophoric dissolved organic matter (CDOM) parameters were measured over a range of discharge in 30 U.S. rivers, covering a diverse assortment of fluvial ecosystems in terms of watershed size and landscape drained. Relationships between CDOM absorption at a range of wavelengths (a254, a350, a440) and DOC in the 30 watersheds were found to correlate strongly and positively for the majority of U.S. rivers. However, four rivers (Colorado, Colombia, Rio Grande and St. Lawrence) exhibited statistically weak relationships between CDOM absorption and DOC. These four rivers are atypical, as they either drain from the Great Lakes or experience significant impoundment of water within their watersheds, and they exhibited values for dissolved organic matter (DOM) parameters indicative of autochthonous or anthropogenic sources or photochemically degraded allochthonous DOM and thus a decoupling between CDOM and DOC. CDOM quality parameters in the 30 rivers were found to be strongly correlated to DOM compositional metrics derived via XAD fractionation, highlighting the potential for examining DOM biochemical quality from CDOM measurements. This study establishes the ability to derive DOC concentration from CDOM absorption for the majority of U.S. rivers, describes characteristics of riverine systems where such an approach is not valid, and emphasizes the possibility of examining DOM composition and thus biogeochemical function via CDOM parameters. Therefore, the usefulness of CDOM measurements, both laboratory-based analyses and in situ instrumentation, for improving spatial and temporal resolution of DOC fluxes and DOM dynamics in future studies is considerable in a range of biogeochemical studies.

  14. Production of fluorescent dissolved organic matter in Arctic Ocean sediments

    NASA Astrophysics Data System (ADS)

    Chen, Meilian; Kim, Ji-Hoon; Nam, Seung-Il; Niessen, Frank; Hong, Wei-Li; Kang, Moo-Hee; Hur, Jin

    2016-12-01

    Little is known about the production of fluorescent dissolved organic matter (FDOM) in the anoxic oceanic sediments. In this study, sediment pore waters were sampled from four different sites in the Chukchi-East Siberian Seas area to examine the bulk dissolved organic carbon (DOC) and their optical properties. The production of FDOM, coupled with the increase of nutrients, was observed above the sulfate-methane-transition-zone (SMTZ). The presence of FDOM was concurrent with sulfate reduction and increased alkalinity (R2 > 0.96, p < 0.0001), suggesting a link to organic matter degradation. This inference was supported by the positive correlation (R2 > 0.95, p < 0.0001) between the net production of FDOM and the modeled degradation rates of particulate organic carbon sulfate reduction. The production of FDOM was more pronounced in a shallow shelf site S1 with a total net production ranging from 17.9 to 62.3 RU for different FDOM components above the SMTZ depth of ca. 4.1 mbsf, which presumably underwent more accumulation of particulate organic matter than the other three deeper sites. The sediments were generally found to be the sources of CDOM and FDOM to the overlying water column, unearthing a channel of generally bio-refractory and pre-aged DOM to the oceans.

  15. Production of fluorescent dissolved organic matter in Arctic Ocean sediments

    PubMed Central

    Chen, Meilian; Kim, Ji-Hoon; Nam, Seung-Il; Niessen, Frank; Hong, Wei-Li; Kang, Moo-Hee; Hur, Jin

    2016-01-01

    Little is known about the production of fluorescent dissolved organic matter (FDOM) in the anoxic oceanic sediments. In this study, sediment pore waters were sampled from four different sites in the Chukchi-East Siberian Seas area to examine the bulk dissolved organic carbon (DOC) and their optical properties. The production of FDOM, coupled with the increase of nutrients, was observed above the sulfate-methane-transition-zone (SMTZ). The presence of FDOM was concurrent with sulfate reduction and increased alkalinity (R2 > 0.96, p < 0.0001), suggesting a link to organic matter degradation. This inference was supported by the positive correlation (R2 > 0.95, p < 0.0001) between the net production of FDOM and the modeled degradation rates of particulate organic carbon sulfate reduction. The production of FDOM was more pronounced in a shallow shelf site S1 with a total net production ranging from 17.9 to 62.3 RU for different FDOM components above the SMTZ depth of ca. 4.1 mbsf, which presumably underwent more accumulation of particulate organic matter than the other three deeper sites. The sediments were generally found to be the sources of CDOM and FDOM to the overlying water column, unearthing a channel of generally bio-refractory and pre-aged DOM to the oceans. PMID:27982085

  16. Possible method for dissolved organic carbon speciation in forest soils

    NASA Astrophysics Data System (ADS)

    Drabek, O.; Tejnecký, V.; Ash, C.; Hubova, P.; Boruvka, L.

    2013-12-01

    Dissolved organic carbon (DOC) is a natural part of dissolved organic matter and it plays an important role in the biogeochemistry of soil processes. Low Molecular Mass Organic Acids (LMMOA) are an essential part of DOC. These acids play a key role in chemical processes that affect the entire soil environment. Knowing the amount of DOC and the speciation of LMMOA is required for realistic equilibrium modelling of soil chemical processes and transport mechanisms. There have been a number of proposed methods for the quantitative analysis of DOC and for speciation of LMMOA. The first aim of this contribution is to introduce and test a modified spectroscopic method for the determination of water-extractable organic carbon (WEOC) from forest soils. In general this method is based on the oxidization of WEOC by chromium-sulphuric acid. The presented method can be used as an economical alternative to the classical, more financially demanding elemental analysis. However, the main aim is to test the reliability of the method for LMMOA speciation. Ion exchange chromatography (IC) with hydroxide elution has proven to be a useful tool for the determination of LMMOA in many different water-based samples. However, the influence of multivalent cations (often present in environmental samples) on IC results has not yet been sufficiently studied. In order to assess the influence of Al, Fe, Mn, Mg and Ca on the amount of LMMOA determined by IC, an extensive set of model solutions was prepared and immediately analysed by means of IC. Moreover, the influence of pH on determined amounts of LMMOA in model solutions and representative soil aqueous extracts was investigated. These experimental results were compared to expected values and also to results provided by the chemical equilibrium model - PHREEQC. Based on the above listed research, some modifications to the common IC method for LMMOA speciation are presented.

  17. Modelling seasonal and long-term patterns in stream dissolved organic carbon concentration in mire and forest dominated landscape elements at Svartberget, Sweden using INCA-C

    NASA Astrophysics Data System (ADS)

    Futter, M.; Koehler, S. J.; Bishop, K. H.

    2009-04-01

    We present an application of the INCA-C (Integrated Catchments model for Carbon) to the Svartberget catchment in central Sweden. The INCA-C model is a catchment-scale, semi-distributed, process-based model of dissolved organic carbon (DOC) that has been used previously to simulate intra- and inter-annual patterns in surface water DOC concentration and flux in boreal and temperate forested catchments (Futter et al. 2007). The 50 ha Svartberget catchment provides an ideal location for evaluating the performance of INCA-C as it contains two mire and upland landscape elements, where the output from each element has been monitored separately for a decade. Previous work has shown that these two landscape elements have markedly different intra-annual patterns of DOC concentration and export as well as the importance of the riparian zone in controlling surface water DOC concentration from the forested sub-catchment (Köhler et al. 2008). The 19 ha mire sub-catchment is dominated by bog communities with Scots pine in the upland areas. The 13 ha forested sub-catchment stream joins the main stem of the stream just above the confluence. It is dominated by Scots pine and Norway spruce. A third sub-catchment between the mire and the catchment outflow has a similar vegetation cover to that of the forested sub-catchment. INCA is designed to model different landscape elements, and combine them to simulate downstream locations. Like most complex, process-based models, however, INCA-C is over-determined. Insufficient data are available to constrain all processes and pool-sizes. As a result, similar in-stream DOC concentrations may be obtained by varying either aquatic or terrestrial rate parameters. The Svartberget catchment provides an opportunity to constrain the model parameter space for the entire catchment as there is information for the two major constituent elements, forest and mire. Additionally soil solution data from the riparian zone in the forest area together with a

  18. The combined effects of hardness, pH, and dissolved organic carbon on the chronic toxicity of Zn to D. magna: development of a surface response model.

    PubMed

    Heijerick, D G; Janssen, C R; De Coen, W M

    2003-02-01

    The effect of changes in pH, hardness, and dissolved organic carbon (DOC) and the possible interactions among these parameters on the chronic toxicity of zinc to D. magna were investigated. Based on a Central Composite Design, models were developed that can explain the observed variation in EC(10) and EC(50) as a function of these toxicity modifying factors. All three parameters significantly altered the observed effect concentrations based on net reproductive rate. The largest differences in 21-day EC(10)s and EC(50)s caused by these factors were 10.1 and 4.9, respectively. An increase in pH and/or DOC decreased zinc toxicity. The significant interaction between pH and DOC on observed chronic Zn toxicity is in accordance with earlier reported increased sorption efficiency of Zn to humic substances at higher pH levels. Lowest Zn toxicity was observed in tests performed with moderately hard test media (between 200 and 300 mg/L as CaCO(3)). Lower or higher hardness of the test medium resulted in lower effect concentrations. Based on physico-chemical characteristics of the test media, developed models can be used to explain the variation between reported NOECs for Zn and may improve current environmental risk assessment procedures of metals.

  19. Dissolved Organic Matter and Emerging Contaminants in Urban Stream Ecosystems

    NASA Astrophysics Data System (ADS)

    Kaushal, S. S.; Findlay, S.; Groffman, P.; Belt, K.; Delaney, K.; Sides, A.; Walbridge, M.; Mayer, P.

    2009-05-01

    We investigated the effects of urbanization on the sources, bioavailability and forms of natural and anthropogenic organic matter found in streams located in Maryland, U.S.A. We found that the abundance, biaoavailability, and enzymatic breakdown of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and dissolved organic phosphorus (DOP) increased in streams with increasing watershed urbanization suggesting that organic nutrients may represent a growing form of nutrient loading to coastal waters associated with land use change. Organic carbon, nitrogen, and phosphorus in urban streams were elevated several-fold compared to forest and agricultural streams. Enzymatic activities of stream microbes in organic matter decomposition were also significantly altered across watershed land use. Chemical characterization suggested that organic matter in urban streams originated from a variety of sources including terrestrial, sewage, and in-stream transformation. In addition, a characterization of emerging organic contaminants (polyaromatic cyclic hydrocarbons, organochlorine pesticides, and polybrominated diphenyl ether flame retardents), showed that organic contaminants and dissolved organic matter increase with watershed urbanization and fluctuate substantially with changing climatic conditions. Elucidating the emerging influence of urbanization on sources, transport, and in-stream transformation of organic nutrients and contaminants will be critical in unraveling the changing role of organic matter in urban degraded and restored stream ecosystems.

  20. Carbon cycle: Ocean dissolved organics matter

    NASA Astrophysics Data System (ADS)

    Amon, Rainer M. W.

    2016-12-01

    Large quantities of organic carbon are stored in the ocean, but its biogeochemical behaviour is elusive. Size-age-composition relations now quantify the production of tiny organic molecules as a major pathway for carbon sequestration.

  1. The composition and degradability of upland dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Moody, Catherine; Worrall, Fred; Clay, Gareth

    2016-04-01

    In order to assess controls on the degradability of DOM in stream water, samples of dissolved organic matter (DOM) and particulate organic matter (POM) were collected every month for a period of 24 months from an upland, peat-covered catchment in northern England. Each month the degradability of the DOM was assessed by exposing river water to light for up to 24 hours, and the change in the dissolved organic carbon (DOC) concentration in the water was measured. To provide context for the analysis of DOM and its degradability, samples of peat, vegetation, and litter were also taken from the same catchment and analysed. The organic matter samples were analysed by several methods including: elemental analysis (CHN and O), bomb calorimetry, thermogravimetric analysis, pyrolysis GC/MS, ICP-OES, stable isotope analysis (13C and 15N) and 13C solid state nuclear magnetic resonance (NMR). The water samples were analysed for pH, conductivity, absorbance at 400nm, anions, cations, particulate organic carbon (POC) and DOC concentrations. River flow conditions and meteorology were also recorded at the site and included in the analysis of the composition and degradability of DOM. The results of multiple regression models showed that the rates of DOC degradation were affected by the N-alkyl, O-alkyl, aldehyde and aromatic relative intensities, gross heat, OR and C:N. Of these, the N-alkyl relative intensity had the greatest influence, and this in turn was found to be dependent on the rainfall and soil temperature in the week before sampling.

  2. Simulating dissolved organic carbon dynamics at the swedish integrated monitoring sites with the integrated catchments model for carbon, INCA-C.

    PubMed

    Futter, M N; Löfgren, S; Köhler, S J; Lundin, L; Moldan, F; Bringmark, L

    2011-12-01

    Surface water concentrations of dissolved organic carbon ([DOC]) are changing throughout the northern hemisphere due to changes in climate, land use and acid deposition. However, the relative importance of these drivers is unclear. Here, we use the Integrated Catchments model for Carbon (INCA-C) to simulate long-term (1996-2008) streamwater [DOC] at the four Swedish integrated monitoring (IM) sites. These are unmanaged headwater catchments with old-growth forests and no major changes in land use. Daily, seasonal and long-term variations in streamwater [DOC] driven by runoff, seasonal temperature and atmospheric sulfate (SO₄(2-)) deposition were observed at all sites. Using INCA-C, it was possible to reproduce observed patterns of variability in streamwater [DOC] at the four IM sites. Runoff was found to be the main short-term control on [DOC]. Seasonal patterns in [DOC] were controlled primarily by soil temperature. Measured SO₄(2-) deposition explained some of the long-term [DOC] variability at all sites.

  3. Snowball Earth prevention by dissolved organic carbon remineralization.

    PubMed

    Peltier, W Richard; Liu, Yonggang; Crowley, John W

    2007-12-06

    The 'snowball Earth' hypothesis posits the occurrence of a sequence of glaciations in the Earth's history sufficiently deep that photosynthetic activity was essentially arrested. Because the time interval during which these events are believed to have occurred immediately preceded the Cambrian explosion of life, the issue as to whether such snowball states actually developed has important implications for our understanding of evolutionary biology. Here we couple an explicit model of the Neoproterozoic carbon cycle to a model of the physical climate system. We show that the drawdown of atmospheric oxygen into the ocean, as surface temperatures decline, operates so as to increase the rate of remineralization of a massive pool of dissolved organic carbon. This leads directly to an increase of atmospheric carbon dioxide, enhanced greenhouse warming of the surface of the Earth, and the prevention of a snowball state.

  4. Ocean metabolism and dissolved organic matter: How do small dissolved molecules persist in the ocean?

    NASA Astrophysics Data System (ADS)

    Benner, Ronald

    2010-05-01

    The ocean reservoir of dissolved organic matter (DOM) is among the largest global reservoirs (~700 Pg C) of reactive organic carbon. Marine primary production (~50 Pg C/yr) by photosynthetic microalgae and cyanobacteria is the major source of organic matter to the ocean and the principal substrate supporting marine food webs. The direct release of DOM from phytoplankton and other organisms as well as a variety of other processes, such as predation and viral lysis, contribute to the ocean DOM reservoir. Continental runoff and atmospheric deposition are relatively minor sources of DOM to the ocean, but some components of this material appear to be resistant to decomposition and to have a long residence time in the ocean. Concentrations of DOM are highest in surface waters and decrease with depth, a pattern that reflects the sources and diagenesis of DOM in the upper ocean. Most (70-80%) marine DOM exists as small molecules of low molecular weight (<1 kDalton). Surprisingly, high-molecular-weight (>1 kDalton) DOM is relatively enriched in major biochemicals, such as combined neutral sugars and amino acids, and is more bioavailable than low-molecular-weight DOM. The observed relationships among the size, composition, and reactivity of DOM have led to the size-reactivity continuum model, which postulates that diagenetic processes lead to the production of smaller molecules that are structurally altered and resistant to microbial degradation. The radiocarbon content of these small dissolved molecules also indicates these are the most highly aged components of DOM. Chemical signatures of bacteria are abundant in DOM and increase during diagenesis, indicating bacteria are an important source of slowly cycling biochemicals. Recent analyses of DOM isolates by ultrahigh-resolution mass spectrometry have revealed an incredibly diverse mixture of molecules. Carboxyl-rich alicyclic molecules are abundant in DOM, and they appear to be derived from diagenetically

  5. Measurement and Modeling of Optical, Physical, and Photochemical Processes in the Open-Ocean Mixed Layer: Peroxide and Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Sikorski, Richard J.

    The goals of this work were to model H _2O_2 cycling in aquatic systems, and to study the photoproperties of bulk dissolved organic matter (DOM). H_2O _2 is produced photochemically from DOM with an "apparent" quantum yield (AQY; normalized to DOM absorbance) which decreases exponentially as wavelength increases. The primary task of this project was to develop a vertical-flux model of undersea irradiance (300-500 nm). The model varied the path-length and geometry of undersea light with solar zenith angle according to scattering in the atmosphere and water column, and according to the ratio of collimated light to diffuse light. This optical model was then combined with a one-dimensional model of marine surface mixing, which derived structure and dynamics by applying empirically determined stability limits to calculated bulk turbulent kinetic energy and shear turbulence. Using data collected in the eastern Caribbean during 1988, modeled H_2O _2 mixed-layer depth and diel distributions were controlled by mixing dynamics. Preliminary model results made it possible to identify two classes of photoproductive waters, based on the ratio of UV DOM absorption, 330 nm, to visible absorption, 460 nm. H_2O _2 photoproduction was primarily due to 320-360 nm irradiance in the model, while a surprisingly significant fraction of total production occurred at wavelengths greater than 400 nm at depth and at zenith angles greater than 15 degrees. The diel photoproduction of H _2O_2 was notably deeper at midday than would be predicted in a simple non -scattering optical model. DOM fluorescence decayed with irradiation above 330 nm, and intensified with irradiation below 330 nm. The processes were partially photo-reversible, and also reversed slowly in the dark. For new river input, irradiation at 296.7 nm initially bleached fluorescence, with re-intensification occurring upon longer irradiation at the same wavelength. Full -spectral solar irradiation bleached fluorescence. The rates of

  6. Removal of dissolved organic matter by anion exchange: Effect of dissolved organic matter properties

    USGS Publications Warehouse

    Boyer, T.H.; Singer, P.C.; Aiken, G.R.

    2008-01-01

    Ten isolates of aquatic dissolved organic matter (DOM) were evaluated to determine the effect that chemical properties of the DOM, such as charge density, aromaticity, and molecular weight, have on DOM removal by anion exchange. The DOM isolates were characterized asterrestrial, microbial, or intermediate humic substances or transphilic acids. All anion exchange experiments were conducted using a magnetic ion exchange (MIEX) resin. The charge density of the DOM isolates, determined by direct potentiometric titration, was fundamental to quantifying the stoichiometry of the anion exchange mechanism. The results clearly show that all DOM isolates were removed by anion exchange; however, differences among the DOM isolates did influence their removal by MIEX resin. In particular, MIEX resin had the greatest affinity for DOM with high charge density and the least affinity for DOM with low charge density and low aromaticity. This work illustrates that the chemical characteristics of DOM and solution conditions must be considered when evaluating anion exchange treatment for the removal of DOM. ?? 2008 American Chemical Society.

  7. PHOTOCHEMICAL TRANSFORMATIONS OF DISSOLVED ORGANIC MATTER IN A BLACKWATER RIVER

    EPA Science Inventory

    We examined photochemical alterations of dissolved organic matter (DOM) from the Satilla River, a high DOC (10-40 mg/liter) blackwater river of southeast Georgia. Water samples were filtered to remove most organisms, placed in quartz tubes, and incubated under natural sunlight a...

  8. Spectral Characterization of Plant-Derived Dissolved Organic Matter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic matter (DOM) derived from fresh or early-stage decomposing soil amendment materials may play an important role in the process of organic matter accumulation. The DOM can influence many chemical processes, due to its reactivity with both soil solution components and soil surfaces. W...

  9. Do soils loose phosphorus with dissolved organic matter?

    NASA Astrophysics Data System (ADS)

    Kaiser, K.; Brödlin, D.; Hagedorn, F.

    2014-12-01

    During ecosystem development and soil formation, primary mineral sources of phosphorus are becoming increasingly depleted. Inorganic phosphorus forms tend to be bound strongly to or within secondary minerals, thus, are hardly available to plants and are not leached from soil. What about organic forms of phosphorus? Since rarely studied, little is known on the composition, mobility, and bioavailability of dissolved organic phosphorus. There is some evidence that plant-derived compounds, such as phytate, bind strongly to minerals as well, while microbial compounds, such as nucleotides and nucleic acids, may represent more mobile fractions of soil phosphorus. In some weakly developed, shallow soils, leaching losses of phosphorus seem to be governed by mobile organic forms. Consequently, much of the phosphorus losses observed during initial stages of ecosystem development may be due to the leaching of dissolved organic matter. However, the potentially mobile microbial compounds are enzymatically hydrolysable. Forest ecosystems on developed soils already depleted in easily available inorganic phosphorus are characterized by rapid recycling of organic phosphors. That can reduce the production of soluble forms of organic phosphorus as well as increase the enzymatic hydrolysis and subsequent plant uptake of phosphorus bound within dissolved organic matter. This work aims at giving an outlook to the potential role of dissolved organic matter in the cycling of phosphorus within developing forest ecosystems, based on literature evidence and first results of ongoing research.

  10. The Biogeochemistry of Chromophoric Dissolved Organic Matter in Coastal Waters

    DTIC Science & Technology

    2016-06-07

    97-1-0720 LONG-TERM GOAL The long-term goal of this research is to better understand the biogeochemical cycling of dissolved organic matter (DOM) in...are analyzed for particulate organic carbon and nitrogen , chlorophyll a, total suspended matter, DO13C, and fluorescence lifetime. These samples have

  11. Modeling Fish Growth in Low Dissolved Oxygen

    ERIC Educational Resources Information Center

    Neilan, Rachael Miller

    2013-01-01

    This article describes a computational project designed for undergraduate students as an introduction to mathematical modeling. Students use an ordinary differential equation to describe fish weight and assume the instantaneous growth rate depends on the concentration of dissolved oxygen. Published laboratory experiments suggest that continuous…

  12. [Dissolved organic matter (DOM) dynamics in karst aquifer systems].

    PubMed

    Yao, Xin; Zou, Sheng-Zhang; Xia, Ri-Yuan; Xu, Dan-Dan; Yao, Min

    2014-05-01

    Dissolved organic matter (DOM) and nutrients have a unique way of producing, decomposing and storing in southwest karst water systems. To understand the biogeochemical cycle of DOM in karst aquifer systems, we investigated the behavioral changes of DOM fluorescence components in Zhaidi karst river system. Two humic-like components (C1 and C2), and one autochthonous tyrosine-like component (C4) were identified using the parallel factor analysis (PARAFAC) model. Compared with the traditional physical and chemical indicators, spatial heterogeneity of DOM was more obvious, which can reflect the subtle changes in groundwater system. Traditional indicators mainly reflect the regional characteristics of karst river system, while DOM fluorescence components reflect the attribute gaps of sampling types.

  13. Effects of dissolved organic matter from a eutrophic lake on the freely dissolved concentrations of emerging organic contaminants.

    PubMed

    Xiao, Yi-Hua; Huang, Qing-Hui; Vähätalo, Anssi V; Li, Fei-Peng; Chen, Ling

    2014-08-01

    The authors studied the effects of dissolved organic matter (DOM) on the bioavailability of bisphenol A (BPA) and chloramphenicol by measuring the freely dissolved concentrations of the contaminants in solutions containing DOM that had been isolated from a mesocosm in a eutrophic lake. The abundance and aromaticity of the chromophoric DOM increased over the 25-d mesocosm experiment. The BPA freely dissolved concentration was 72.3% lower and the chloramphenicol freely dissolved concentration was 56.2% lower using DOM collected on day 25 than using DOM collected on day 1 of the mesocosm experiment. The freely dissolved concentrations negatively correlated with the ultraviolent absorption coefficient at 254 nm and positively correlated with the spectral slope of chromophoric DOM, suggesting that the bioavailability of these emerging organic contaminants depends on the characteristics of the DOM present. The DOM-water partition coefficients (log KOC ) for the emerging organic contaminants positively correlated with the aromaticity of the DOM, measured as humic acid-like fluorescent components C1 (excitation/emission=250[313]/412 nm) and C2 (excitation/emission=268[379]/456 nm). The authors conclude that the bioavailability of emerging organic contaminants in eutrophic lakes can be affected by changes in the DOM.

  14. Effluent dissolved organic nitrogen and dissolved phosphorus removal by enhanced coagulation and microfiltration.

    PubMed

    Arnaldos, Marina; Pagilla, Krishna

    2010-10-01

    Plants aiming to achieve very low effluent nutrient levels (<3 mg N/L for N, and <0.1 mg P/L for P) need to consider removal of effluent fractions hitherto not taken into account. Two of these fractions are dissolved organic nitrogen (DON) and dissolved non-reactive phosphorus (DNRP) (mainly composed of organic phosphorus). In this research, enhanced coagulation using alum (at doses commonly employed in tertiary phosphorus removal) followed by microfiltration (using 0.22 μm pore size filters) was investigated for simultaneous effluent DON and dissolved phosphorus (DP) fractions removal. At an approximate dose of 3.2 mg Al(III)/L, corresponding to 1.5 Al(III)/initial DON-N and 3.8 Al(III)/initial DP-P molar ratios, maximum simultaneous removal of DON and DP was achieved (69% for DON and 72% for DP). At this dose, residual DON and DP concentrations were found to be 0.3 mg N/L and 0.25 mg P/L, respectively. Analysis of the trends of removal revealed that the DNRP removal pattern was similar to that commonly reported for dissolved reactive phosphorus. Since this study involved intensive analytical work, a secondary objective was to develop a simple and accurate measurement protocol for determining dissolved N and P species at very low levels in wastewater effluents. The protocol developed in this study, involving simultaneous digestion for DON and DNRP species, was found to be very reliable and accurate based on the results.

  15. DISSOLVED ORGANIC MATTER AND METALS: EFFECTS OF PH ON PARTITIONING

    EPA Science Inventory

    Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb, and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was fractionated into three operationally defined fractions: hydrophilic acids (Hyd), fulvic acids (FA), an...

  16. Yucca Mountain Area Saturated Zone Dissolved Organic Carbon Isotopic Data

    SciTech Connect

    Thomas, James; Decker, David; Patterson, Gary; Peterman, Zell; Mihevc, Todd; Larsen, Jessica; Hershey, Ronald

    2007-06-25

    Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, flow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated

  17. [Effects of dissolved organic matter on phenanthrene adsorption by soil].

    PubMed

    Xiong, Wei; Ling, Wan-ting; Gao, Yan-zheng; Li, Qiu-ling; Dai, Jing-yu

    2007-02-01

    This paper studied the effects of exotic and native dissolved organic matter (DOM) on the phenanthrene adsorption by three soils differed in soil organic carbon content (foc). The exotic DOM came from decayed rice straw, while the native DOM was extracted from the test soils. In all cases, the adsorption of phenanthrene by treated soils could be well described with linear-type model, and there was a positive correlation between adsorption coefficient (Kd) and foc Compared with the control, the Kd value of test soils after native DOM removed was increased by 7. 08% -21. 4% , and the increment (deltaKd) was positively correlated with fo,, indicating that the presence of soil native DOM impeded the phenanthrene adsorption by soil. The effects of exotic DOM on phenanthrene adsorption had a close relation with its added concentration in soil-water system. Within the range of 0-106 mg DOC x L(-1) , the K, value increased first, and then decreased with the increase of added exotic DOM concentration. Lower concentrations of added exotic DOM promoted the phenanthrene adsorption by soil, while higher concentrations ( I> or =52 mg DOC x L(-1)) of it obviously impeded this adsorption. These effects of exotic and native DOM on soil phenanthrene adsorption were considered to be related to the association of phenanthrene with DOM in solution, and the ' cumulative adsorption effect' between soil solid and aqueous phases.

  18. Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

    USGS Publications Warehouse

    Spencer, R.G.M.; Aiken, G.R.; Butler, K.D.; Dornblaser, M.M.; Striegl, R.G.; Hernes, P.J.

    2009-01-01

    The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean. Citation: Spencer, R. G. M., G. R. Aiken, K. D. Butler, M. M. Dornblaser, R. G. Striegl, and P. J. Hernes (2009), Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska, Geophys. Res. Lett., 36, L06401, doi:10.1029/ 2008GL036831. Copyright 2009 by the American Geophysical Union.

  19. Characterization Of Dissolved Organic Mattter In The Florida Keys Ecosystem

    NASA Astrophysics Data System (ADS)

    Adams, D. G.; Shank, G. C.

    2009-12-01

    Over the past few decades, Scleractinian coral populations in the Florida Keys have increasingly experienced mortality due to bleaching events as well as microbial mediated illnesses such as black band and white band disease. Such pathologies seem to be most correlated with elevated sea surface temperatures, increased UV exposures, and shifts in the microbial community living on the coral itself. Recent studies indicate that corals’ exposure to UV in the Florida Keys is primarily controlled by the concentration of CDOM (Chromophoric Dissolved Organic Matter) in the water column. Further, microbial community alterations may be linked to changes in concentration and chemical composition of the larger DOM (Dissolved Organic Matter) pool. Our research characterized the spatial and temporal properties of DOM in Florida Bay and along the Keys ecosystems using DOC analyses, in-situ water column optical measurements, and spectral analyses including absorbance and fluorescence measurements. We analyzed DOM characteristics along transects running from the mouth of the Shark River at the southwest base of the Everglades, through Florida Bay, and along near-shore Keys coastal waters. Two 12 hour time-series samplings were also performed at the Seven-Mile Bridge, the primary Florida Bay discharge channel to the lower Keys region. Photo-bleaching experiments showed that the chemical characteristics of the DOM pool are altered by exposure to solar radiation. Results also show that DOC (~0.8-5.8 mg C/L) and CDOM (~0.5-16.5 absorbance coefficient at 305nm) concentrations exhibit seasonal fluctuations in our study region. EEM analyses suggest seasonal transitions between primarily marine (summer) and terrestrial (winter) sources along the Keys. We are currently combining EEM-PARAFAC analysis with in-situ optical measurements to model changes in the spectral properties of DOM in the water column. Additionally, we are using stable δ13C isotopic analysis to further characterize DOM

  20. Measuring the bioavailability of two hydrophobic organic compounds in the presence of dissolved organic matter.

    PubMed

    Akkanen, Jarkko; Kukkonen, Jussi V K

    2003-03-01

    Bioavailability of benzo[a]pyrene (BaP) and 3,3',4,4'-tetrachlorobiphenyl (TCB) was studied in natural lake water containing dissolved organic matter (DOM). Lake water was diluted to give a dissolved organic carbon (DOC) range of 1 to 20 mg/L. Partition coefficients for the model compounds were assessed at different DOM concentrations and over time with three different methods, namely equilibrium dialysis and reverse-phase and liquid-liquid extraction. In addition, biological partition coefficients were estimated from the difference in the bioconcentration of the model compounds in Daphnia magna in the presence and absence of DOM. Results showed that bioavailability of the model compounds was reduced by the presence of DOM. The equilibrium dialysis method gave the best estimates for bioavailability of the model compounds when compared with biologically determined values. Both the reverse-phase and the liquid-liquid extraction overestimated the bioavailable fraction. The more pronounced overestimation of bioavailable fraction of TCB suggested that the sorption of TCB was not only lower but the interaction was also weaker than that of BaP. Increasing DOM concentration produced lower partition coefficients and the effect seemed to be more pronounced when measured by the reverse-phase and the extraction methods.

  1. The Impact of Microbial Metabolism on Marine Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Kujawinski, Elizabeth B.

    2011-01-01

    Microbes mediate global biogeochemical cycles through their metabolism, and all metabolic processes begin with the interaction between the microbial cell wall or membrane and the external environment. For all heterotrophs and many autotrophs, critical growth substrates and factors are present within the dilute and heterogeneous mixture of compounds that constitutes dissolved organic matter (DOM). In short, the microbe-molecule interaction is one of the fundamental reactions within the global carbon cycle. Here, I summarize recent findings from studies that examine DOM-microbe interactions from either the DOM perspective (organic geochemistry) or the microbe perspective (microbial ecology). Gaps in our knowledge are highlighted and future integrative research directions are proposed.

  2. Meridional fluxes of dissolved organic matter in the North Atlantic Ocean

    NASA Technical Reports Server (NTRS)

    Walsh, John J.; Carder, Kendall L.; Mueller-Karger, Frank E.

    1992-01-01

    Biooptical estimates of gelbstoff and a few platinum measurements of dissolved organic carbon (DOCpt) are used to construct a budget of the meridional flux of DOC and dissolved organic nitrogen (DON) across 36 deg 25 min N in the North Atlantic from previous inverse models of water and element transport. Distinct southward subsurface fluxes of dissolved organic matter within subducted shelf water, cabelled slope water, and overturned basin water are inferred. Within two cases of a positive gradient of DOCpt between terrestrial/shelf and offshore stocks, the net equatorward exports of O2 and DOCpt from the northern North Atlantic yield molar ratios of 2.1 to 9.1, compared to the expected Redfield O2/C ratio of 1.3. It is concluded that some shelf export of DOC, with a positive gradient between coastal and oceanic stocks, as well as falling particles, are required to balance carbon, nitrogen, and oxygen budgets of the North Atlantic.

  3. Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

    SciTech Connect

    Jagadamma, Sindhu; Mayes, Melanie; Phillips, Jana Randolph

    2012-01-01

    Physico-chemical sorption of dissolved organic carbon (DOC) on soil minerals is one of the major processes of organic carbon (OC) stabilization in soils, especially in deeper layers. The attachment of C on soil solids is related to the reactivity of the soil minerals and the chemistry of the sorbate functional groups, but the sorption studies conducted without controlling microbial activity may overestimate the sorption potential of soil. This study was conducted to examine the sorptive characteristics of a diverse functional groups of simple OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols, Ultisols and Alfisols) with and without biological degradative processes. Equilibrium batch experiments were conducted using 0-100 mg C L-1 at a solid-solution ratio of 1:60 for 48 hrs and the sorption parameters were calculated by Langmuir model fitting. The amount of added compounds that remained in the solution phase was detected by high performance liquid chromatography (HPLC) and total organic C (TOC) analysis. Soil sterilization was performed by -irradiation technique and experiments were repeated to determine the contribution of microbial degradation to apparent sorption. Overall, Ultisols did not show a marked preference for apparent sorption of any of the model compounds, as indicated by a narrower range of maximum sorption capacity (Smax) of 173-527 mg kg soil-1 across compounds. Mollisols exhibited a strong preference for apparent sorption of oxalic acid (Smax of 5290 mg kg soil-1) and sinapyl alcohol (Smax of 2031 mg kg soil-1) over the other compounds. The propensity for sorption of oxalic acid is mainly attributed to the precipitation of insoluble Ca-oxalate due to the calcareous nature of most Mollisol subsoils and its preference for sinapyl alcohol could be linked to the polymerization of this lignin monomer on 2:2 mineral dominated soils. The reactivity of Alfisols to DOC was in

  4. Dissolved oxygen as an indicator of bioavailable dissolved organic carbon in groundwater

    USGS Publications Warehouse

    Chapelle, Francis H.; Bradley, Paul M.; McMahon, Peter B.; Kaiser, Karl; Benner, Ron

    2012-01-01

    Concentrations of dissolved oxygen (DO) plotted vs. dissolved organic carbon (DOC) in groundwater samples taken from a coastal plain aquifer of South Carolina (SC) showed a statistically significant hyperbolic relationship. In contrast, DO-DOC plots of groundwater samples taken from the eastern San Joaquin Valley of California (CA) showed a random scatter. It was hypothesized that differences in the bioavailability of naturally occurring DOC might contribute to these observations. This hypothesis was examined by comparing nine different biochemical indicators of DOC bioavailability in groundwater sampled from these two systems. Concentrations of DOC, total hydrolysable neutral sugars (THNS), total hydrolysable amino acids (THAA), mole% glycine of THAA, initial bacterial cell counts, bacterial growth rates, and carbon dioxide production/consumption were greater in SC samples relative to CA samples. In contrast, the mole% glucose of THNS and the aromaticity (SUVA254) of DOC was greater in CA samples. Each of these indicator parameters were observed to change with depth in the SC system in a manner consistent with active biodegradation. These results are uniformly consistent with the hypothesis that the bioavailability of DOC is greater in SC relative to CA groundwater samples. This, in turn, suggests that the presence/absence of a hyperbolic DO-DOC relationship may be a qualitative indicator of relative DOC bioavailability in groundwater systems.

  5. Dissolved oxygen as an indicator of bioavailable dissolved organic carbon in groundwater.

    PubMed

    Chapelle, Francis H; Bradley, Paul M; McMahon, Peter B; Kaiser, Karl; Benner, Ron

    2012-01-01

    Concentrations of dissolved oxygen (DO) plotted vs. dissolved organic carbon (DOC) in groundwater samples taken from a coastal plain aquifer of South Carolina (SC) showed a statistically significant hyperbolic relationship. In contrast, DO-DOC plots of groundwater samples taken from the eastern San Joaquin Valley of California (CA) showed a random scatter. It was hypothesized that differences in the bioavailability of naturally occurring DOC might contribute to these observations. This hypothesis was examined by comparing nine different biochemical indicators of DOC bioavailability in groundwater sampled from these two systems. Concentrations of DOC, total hydrolysable neutral sugars (THNS), total hydrolysable amino acids (THAA), mole% glycine of THAA, initial bacterial cell counts, bacterial growth rates, and carbon dioxide production/consumption were greater in SC samples relative to CA samples. In contrast, the mole% glucose of THNS and the aromaticity (SUVA(254)) of DOC was greater in CA samples. Each of these indicator parameters were observed to change with depth in the SC system in a manner consistent with active biodegradation. These results are uniformly consistent with the hypothesis that the bioavailability of DOC is greater in SC relative to CA groundwater samples. This, in turn, suggests that the presence/absence of a hyperbolic DO-DOC relationship may be a qualitative indicator of relative DOC bioavailability in groundwater systems.

  6. Spatial and temporal variation of dissolved organic matter in the Changjiang: Fluvial transport and flux estimation

    NASA Astrophysics Data System (ADS)

    Bao, Hongyan; Wu, Ying; Zhang, Jing

    2015-09-01

    The Changjiang is the most important source of freshwater and dissolved organic matter (DOM) for the East China Sea. However, knowledge regarding the sources, seasonal fluxes, and fluvial transport of terrigenous DOM (tDOM) in the Changjiang is lacking. To fill this knowledge gap, we measured dissolved organic carbon (DOC) and dissolved lignin in water samples collected in the middle and lower Changjiang under different hydrological conditions. Additional samples were collected biweekly in the lower Changjiang. Through comparisons with other rivers, we found that the DOC in the Changjiang is mainly from soil organic matter and has a higher fraction of tDOM during flood. Mass balance model results indicate that approximately 33% of the dissolved lignin discharged into the middle and lower Changjiang is removed during its transport to the lower reach during both low-discharge and flood periods. Based on a comparison of the removal rates under these two contrasting hydrological conditions and considering the lower organic carbon content and fine grain size of the Changjiang's suspended particles, we speculate that the major process for the removal of dissolved lignin is sorption, and potentially flocculation by suspended particles. Changjiang discharges 1.4 ± 0.10 Tg yr-1 and 8.6 ± 0.30 Gg yr-1 DOC and dissolved lignin to the estuary during the period of July 2010 to June 2011, respectively. Seasonal distributions of DOC and dissolved lignin fluxes are controlled by water discharge, which will be affected by future climate change and the Three Gorges Dam.

  7. Dissolved organic matter enhances microbial mercury methylation under sulfidic conditions

    USGS Publications Warehouse

    Graham, Andrew M.; Aiken, George R.; Gilmour, Cynthia

    2012-01-01

    Dissolved organic matter (DOM) is generally thought to lower metal bioavailability in aquatic systems due to the formation of metal–DOM complexes that reduce free metal ion concentrations. However, this model may not be pertinent for metal nanoparticles, which are now understood to be ubiquitous, sometimes dominant, metal species in the environment. The influence of DOM on Hg bioavailability to microorganisms was examined under conditions (0.5–5.0 nM Hg and 2–10 μM sulfide) that favor the formation of β-HgS(s) (metacinnabar) nanoparticles. We used the methylation of stable-isotope enriched 201HgCl2 by Desulfovibrio desulfuricans ND132 in short-term washed cell assays as a sensitive, environmentally significant proxy for Hg uptake. Suwannee River humic acid (SRHA) and Williams Lake hydrophobic acid (WLHPoA) substantially enhanced (2- to 38-fold) the bioavailability of Hg to ND132 over a wide range of Hg/DOM ratios (9.4 pmol/mg DOM to 9.4 nmol/mg DOM), including environmentally relevant ratios. Methylmercury (MeHg) production by ND132 increased linearly with either SRHA or WLHPoA concentration, but SRHA, a terrestrially derived DOM, was far more effective at enhancing Hg-methylation than WLHPoA, an aquatic DOM dominated by autochthonous sources. No DOM-dependent enhancement in Hg methylation was observed in Hg–DOM–sulfide solutions amended with sufficient l-cysteine to prevent β-HgS(s) formation. We hypothesize that small HgS particles, stabilized against aggregation by DOM, are bioavailable to Hg-methylating bacteria. Our laboratory experiments provide a mechanism for the positive correlations between DOC and MeHg production observed in many aquatic sediments and wetland soils.

  8. Chromophoric Dissolved Organic Matter in Southwestern Greenland Lakes

    NASA Astrophysics Data System (ADS)

    Osburn, C. L.; Giles, M. E.; Underwood, G. J. C.

    2014-12-01

    Dissolved organic matter (DOM) is an important property of Arctic lake ecosystems, originating from allochthonous inputs from catchments and autochthonous production by plankton in the water column. Little is known about the quality of DOM in Arctic lakes that lack substantial inputs from catchments and such lakes are abundant in southwestern Greenland. Colored dissolved organic matter (CDOM), the fraction that absorbs ultraviolet (UV) and visible light, is the controlling factor for the optical properties of many surface waters and as well informs on the quality of DOM. We examined the quality of CDOM in 21 lakes in southwestern Greenland, from the ice sheet to the coast, as part of a larger study examining the role of DOM in regulating microbial communities in these lakes. DOM was size fractioned and absorbance and fluorescence was measured on each size fraction, as well as on bulk DOM. The specific ultraviolet absorbance (SUVA) at 254 nm (SUVA254), computed by normalizing absorption (a254) to dissolved organic carbon (DOC) concentration, provided an estimate of the aromatic carbon content of DOM. SUVA values were generally <2, indicating low aromatic content. Parallel factor analysis (PARAFAC) of CDOM fluorescence was used to determine the relative abundance of allochthonous and autochthonous DOM in all size fractions. Younger lakes near the ice sheet and lakes near the coast had lower amounts of CDOM and appeared more microbial in quality. However, lakes centrally located between the ice sheet and the coast had the highest CDOM concentrations and exhibited strong humic fluorescence. Overall distinct differences in CDOM quality were observed between lake locations and among DOM size fractions.

  9. Bacterial biomarkers thermally released from dissolved organic matter

    USGS Publications Warehouse

    Greenwood, P.F.; Leenheer, J.A.; McIntyre, C.; Berwick, L.; Franzmann, P.D.

    2006-01-01

    Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.

  10. Characterization of Biologically Produced Colored Dissolved Organic Matter in Seawater

    DTIC Science & Technology

    2005-11-29

    Seritti, A. Environ. Tech. 1993, 14, 94.1-948. (19) Lombardi, A.T.; Jardim, W.F. Water Research. 1999, 33, 512-520. (20) Parlanti, E .; Morin , B.; Vacher...REPORT DOCUMENTATION PAGE Form Approved Public reporting burden for this collection of I•mo,,ation , e dlat ed to average hour per response. ind•uding... e -mail: drepeta(atwhoi.edu Grant# N00014-98-1-0579 & N00014-03-1-0387 Chromophoric, or colored dissolved organic matter (CDOM), influences the

  11. First-order kinetics-controlled multiple species reactive transport of dissolved organic compounds in groundwater: Development and application of a numerical model

    SciTech Connect

    McNab, W.W. Jr.

    1990-05-01

    Reactive chemical transport models developed over the past decade have generally relied on the assumption that local thermodynamic equilibrium is achieved at all times between aqueous species in a given system. Consequently, homogeneous aqueous systems characterized by a number of kinetically slow reactions, particularly problems involving organic species, cannot be satisfactorily modeled. In this study, we present a prototype computer model, KINETRAN, which is designed to handle kinetically-controlled homogeneous reactions in the aqueous phase, along with the transport of the various species involved, through geologic media. 31 refs., 53 figs., 10 tabs.

  12. Effects of water hardness and dissolved organic material on bioavailability of selected organic chemicals.

    PubMed

    Akkanen, J; Kukkonen, J V

    2001-10-01

    The influence of water hardness and dissolved organic matter (DOM) on bioavailability of organic chemicals to Daphnia magna was studied by using benzo[a]pyrene (BaP), pyrene, atrazine, and 3,3',4,4'-tetrachlorobiphenyl (TCB) as model compounds. Two types of DOM were used, namely Lake Kontiolampi, Joensuu, Finland water (KL) and Nordic reference fulvic acid (NoFA) dissolved in artificial freshwater. Binding of the four contaminants by KL DOM decreased with increasing water hardness. Furthermore, increasing hardness reduced the binding of BaP and pyrene to NoFA. The binding of atrazine and TCB by NoFA was low and was not significantly affected by water hardness. In the DOM-free samples, the bioconcentration of the four contaminants in D. magna usually was not affected by water hardness. In the presence of DOM, the bioconcentration factors (BCFs) were lower (except for atrazine) than in the DOM-free controls. In the presence of both types of DOM, increasing water hardness resulted in higher BCFs for BaP. The bioconcentration of pyrene and TCB increased with increasing water hardness in the presence of KL DOM. In conclusion, the effects of DOM and water hardness on bioavailability of hydrophobic chemicals depend on the type of chemical and on the properties of DOM.

  13. Global effects of agriculture on fluvial dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Graeber, Daniel; Boëchat, Iola G.; Encina-Montoya, Francisco; Esse, Carlos; Gelbrecht, Jörg; Goyenola, Guillermo; Gücker, Björn; Heinz, Marlen; Kronvang, Brian; Meerhoff, Mariana; Nimptsch, Jorge; Pusch, Martin T.; Silva, Ricky C. S.; von Schiller, Daniel; Zwirnmann, Elke

    2015-11-01

    Agricultural land covers approximately 40% of Earth’s land surface and affects hydromorphological, biogeochemical and ecological characteristics of fluvial networks. In the northern temperate region, agriculture also strongly affects the amount and molecular composition of dissolved organic matter (DOM), which constitutes the main vector of carbon transport from soils to fluvial networks and to the sea, and is involved in a large variety of biogeochemical processes. Here, we provide first evidence about the wider occurrence of agricultural impacts on the concentration and composition of fluvial DOM across climate zones of the northern and southern hemispheres. Both extensive and intensive farming altered fluvial DOM towards a more microbial and less plant-derived composition. Moreover, intensive farming significantly increased dissolved organic nitrogen (DON) concentrations. The DOM composition change and DON concentration increase differed among climate zones and could be related to the intensity of current and historical nitrogen fertilizer use. As a result of agriculture intensification, increased DON concentrations and a more microbial-like DOM composition likely will enhance the reactivity of catchment DOM emissions, thereby fuelling the biogeochemical processing in fluvial networks, and resulting in higher ecosystem productivity and CO2 outgassing.

  14. Low photolability of yedoma permafrost dissolved organic carbon

    NASA Astrophysics Data System (ADS)

    Stubbins, Aron; Mann, Paul J.; Powers, Leanne; Bittar, Thais B.; Dittmar, Thorsten; McIntyre, Cameron P.; Eglinton, Timothy I.; Zimov, Nikita; Spencer, Robert G. M.

    2017-01-01

    Vast stores of arctic permafrost carbon that have remained frozen for millennia are thawing, releasing ancient dissolved organic carbon (DOC) to arctic inland waters. Once in arctic waters, DOC can be converted to CO2 and emitted to the atmosphere, accelerating climate change. Sunlight-driven photoreactions oxidize DOC, converting a portion to CO2 and leaving behind a photomodified pool of dissolved organic matter (DOM). Samples from the Kolyma River, its tributaries, and streams draining thawing yedoma permafrost were collected. Irradiation experiments and radiocarbon dating were employed to assess the photolability of ancient permafrost-DOC in natural and laboratory generated samples containing a mix of modern and ancient DOC. Photolabile DOC was always modern, with no measurable photochemical loss of ancient permafrost-DOC. However, optical and ultrahigh resolution mass spectrometric measurements revealed that both modern river DOM and ancient permafrost-DOM were photomodified during the irradiations, converting aromatic compounds to less conjugated compounds. These findings suggest that although sunlight-driven photoreactions do not directly mineralize permafrost-DOC, photomodification of permafrost-DOM chemistry may influence its fate and ecological functions in aquatic systems.

  15. Contaminant-mediated photobleaching of wetland chromophoric dissolved organic matter.

    PubMed

    Langlois, Maureen C; Weavers, Linda K; Chin, Yu-Ping

    2014-09-20

    Photolytic transformation of organic contaminants in wetlands can be mediated by chromophoric dissolved organic matter (CDOM), which in turn can lose its reactivity from photobleaching. We collected water from a small agricultural wetland (Ohio), Kawai Nui Marsh (Hawaii), the Everglades (Florida), and Okefenokee Swamp (Georgia) to assess the effect of photobleaching on the photofate of two herbicides, acetochlor and isoproturon. Analyte-spiked water samples were irradiated using a solar simulator and monitored for changes in CDOM light absorbance and dissolved oxygen. Photobleaching did not significantly impact the indirect photolysis rates of either herbicide over 24 hours of irradiation. Surprisingly, the opposite effect was observed with isoproturon, which accelerated DOM photobleaching. This phenomenon was more pronounced in higher-CDOM waters, and we believe that the redox pathway between triplet-state CDOM and isoproturon may be responsible for our observations. By contrast, acetochlor indirect photolysis was dependent on reaction with the hydroxyl radical and did not accelerate photobleaching of wetland water as much as isoproturon. Finally, herbicide indirect photolysis rate constants did not correlate strongly to any one chemical or optical property of the sampled waters.

  16. Global effects of agriculture on fluvial dissolved organic matter.

    PubMed

    Graeber, Daniel; Boëchat, Iola G; Encina-Montoya, Francisco; Esse, Carlos; Gelbrecht, Jörg; Goyenola, Guillermo; Gücker, Björn; Heinz, Marlen; Kronvang, Brian; Meerhoff, Mariana; Nimptsch, Jorge; Pusch, Martin T; Silva, Ricky C S; von Schiller, Daniel; Zwirnmann, Elke

    2015-11-06

    Agricultural land covers approximately 40% of Earth's land surface and affects hydromorphological, biogeochemical and ecological characteristics of fluvial networks. In the northern temperate region, agriculture also strongly affects the amount and molecular composition of dissolved organic matter (DOM), which constitutes the main vector of carbon transport from soils to fluvial networks and to the sea, and is involved in a large variety of biogeochemical processes. Here, we provide first evidence about the wider occurrence of agricultural impacts on the concentration and composition of fluvial DOM across climate zones of the northern and southern hemispheres. Both extensive and intensive farming altered fluvial DOM towards a more microbial and less plant-derived composition. Moreover, intensive farming significantly increased dissolved organic nitrogen (DON) concentrations. The DOM composition change and DON concentration increase differed among climate zones and could be related to the intensity of current and historical nitrogen fertilizer use. As a result of agriculture intensification, increased DON concentrations and a more microbial-like DOM composition likely will enhance the reactivity of catchment DOM emissions, thereby fuelling the biogeochemical processing in fluvial networks, and resulting in higher ecosystem productivity and CO2 outgassing.

  17. Global effects of agriculture on fluvial dissolved organic matter

    PubMed Central

    Graeber, Daniel; Boëchat, Iola G.; Encina-Montoya, Francisco; Esse, Carlos; Gelbrecht, Jörg; Goyenola, Guillermo; Gücker, Björn; Heinz, Marlen; Kronvang, Brian; Meerhoff, Mariana; Nimptsch, Jorge; Pusch, Martin T.; Silva, Ricky C. S.; von Schiller, Daniel; Zwirnmann, Elke

    2015-01-01

    Agricultural land covers approximately 40% of Earth’s land surface and affects hydromorphological, biogeochemical and ecological characteristics of fluvial networks. In the northern temperate region, agriculture also strongly affects the amount and molecular composition of dissolved organic matter (DOM), which constitutes the main vector of carbon transport from soils to fluvial networks and to the sea, and is involved in a large variety of biogeochemical processes. Here, we provide first evidence about the wider occurrence of agricultural impacts on the concentration and composition of fluvial DOM across climate zones of the northern and southern hemispheres. Both extensive and intensive farming altered fluvial DOM towards a more microbial and less plant-derived composition. Moreover, intensive farming significantly increased dissolved organic nitrogen (DON) concentrations. The DOM composition change and DON concentration increase differed among climate zones and could be related to the intensity of current and historical nitrogen fertilizer use. As a result of agriculture intensification, increased DON concentrations and a more microbial-like DOM composition likely will enhance the reactivity of catchment DOM emissions, thereby fuelling the biogeochemical processing in fluvial networks, and resulting in higher ecosystem productivity and CO2 outgassing. PMID:26541809

  18. Chromophoric dissolved organic matter export from U.S. rivers

    USGS Publications Warehouse

    Spencer, Robert G. M.; Aiken, George R.; Dornblaser, Mark M.; Butler, Kenna D.; Holmes, R. Max; Fiske, Greg; Mann, Paul J.; Stubbins, Aron

    2013-01-01

    Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. A robust relationship between CDOM and dissolved organic carbon (DOC) loads is established (e.g., a350 versus DOC; r2 = 0.96, p < 0.001). Calculated CDOM yields are also correlated to watershed percent wetland (e.g. a350; r2 = 0.81, p < 0.001) providing a method for the estimation of CDOM export from ungauged watersheds. A large variation in CDOM yields was found across the rivers. The two rivers in the north-eastern U.S. (Androscoggin and Penobscot), the Edisto draining into the South Atlantic Bight, and some rivers draining into the Gulf of Mexico (Atchafalaya and Mobile) exhibit the highest CDOM yields, linked to extensive wetlands in these watersheds. If the Edisto CDOM yield is representative of other rivers draining into the South Atlantic Bight, this would result in a CDOM load equivalent to that of the Mississippi from a region of approximately 10% of the Mississippi watershed, indicating the importance of certain regions with respect to the role of terrigenous CDOM in ocean color budgets.

  19. Photochemical and Nonphotochemical Transformations of Cysteine with Dissolved Organic Matter.

    PubMed

    Chu, Chiheng; Erickson, Paul R; Lundeen, Rachel A; Stamatelatos, Dimitrios; Alaimo, Peter J; Latch, Douglas E; McNeill, Kristopher

    2016-06-21

    Cysteine (Cys) plays numerous key roles in the biogeochemistry of natural waters. Despite its importance, a full assessment of Cys abiotic transformation kinetics, products and pathways under environmental conditions has not been conducted. This study is a mechanistic evaluation of the photochemical and nonphotochemical (dark) transformations of Cys in solutions containing chromophoric dissolved organic matter (CDOM). The results show that Cys underwent abiotic transformations under both dark and irradiated conditions. Under dark conditions, the transformation rates of Cys were moderate and were highly pH- and temperature-dependent. Under UVA or natural sunlight irradiations, Cys transformation rates were enhanced by up to two orders of magnitude compared to rates under dark conditions. Product analysis indicated cystine and cysteine sulfinic acid were the major photooxidation products. In addition, this study provides an assessment of the contributions of singlet oxygen, hydroxyl radical, hydrogen peroxide, and triplet dissolved organic matter to the CDOM-sensitized photochemical oxidation of Cys. The results suggest that another unknown pathway was dominant in the CDOM-sensitized photodegradation of Cys, which will require further study to identify.

  20. Carbon isotopic exchange between dissolved inorganic and organic carbon

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Freeman, K. H.; House, C. H.; Arthur, M. A.

    2009-12-01

    The pools of inorganic and organic carbon are often considered to be separate and distinct. Isotopic exchange between the inorganic and organic carbon pools in natural waters is rarely considered plausible at low temperatures owing to kinetic barriers to exchange. In certain circumstances, however carboxyl carbon of dissolved organic matter (DOM) may be subject to exchange with the dissolved inorganic carbon (DIC) pool. We report results from an isotopic labeling experiment that resulted in rapid methanogen-catalyzed isotopic exchange between DIC and the carboxyl carbon of acetate. This exchange rapidly mixes the isotopic composition of the DIC pool into the dissolved organic carbon (DOC) acetate pool. This exchange is likely associated with the reversible nature of the carbon monoxide dehydrogenase enzyme. In nature, many decarboxylase enzymes are also reversible and some can be shown to facilitate similar exchange reactions. Those decarboxylase enzymes that are important in lignin decomposition and other organic carbon (OC) transformations may help to mask the isotopic composition of the precursor DOC with as much as 15% contribution from DIC. Though this dilution is unlikely to matter in soils where DOC and DIC are similar in composition, this exchange may be extremely important in systems where the stable or radioisotope composition of DOC and DIC differ significantly. As an example of the importance of this effect, we demonstrate that the stable and radiocarbon isotopic composition of fluvial DOC could be altered by mixing with marine DIC to produce a DOC composition similar to those observed in the deep marine DOC pool. We hypothesize that this exchange resolves the conundrum of apparently old (>5 kyr) marine-derived DOC. If most of the carboxyl carbon of pre-aged, terrestrial-derived DOC (15% of total carbon) is subject to exchange with marine DIC, the resulting carbon isotopic composition of deep DOC will be similar to that observed in deep marine studies

  1. Nature and transformation of dissolved organic matter in treatment wetlands.

    PubMed

    Barber, L B; Leenheer, J A; Noyes, T I; Stiles, E A

    2001-12-15

    This investigation into the occurrence, character, and transformation of dissolved organic matter (DOM) in treatment wetlands in the western United States shows that (i) the nature of DOM in the source water has a major influence on transformations that occur during treatment, (ii) the climate factors have a secondary effect on transformations, (iii) the wetlands receiving treated wastewater can produce a net increase in DOM, and (iv) the hierarchical analytical approach used in this study can measure the subtle DOM transformations that occur. As wastewater treatment plant effluent passes through treatment wetlands, the DOM undergoes transformation to become more aromatic and oxygenated. Autochthonous sources are contributed to the DOM, the nature of which is governed by the developmental stage of the wetland system as well as vegetation patterns. Concentrations of specific wastewater-derived organic contaminants such as linear alkylbenzene sulfonate, caffeine, and ethylenediaminetetraacetic acid were significantly attenuated by wetland treatment and were not contributed by internal loading.

  2. Nature and transformation of dissolved organic matter in treatment wetlands

    USGS Publications Warehouse

    Barber, L.B.; Leenheer, J.A.; Noyes, T.I.; Stiles, E.A.

    2001-01-01

    This investigation into the occurrence, character, and transformation of dissolved organic matter (DOM) in treatment wetlands in the western United States shows that (i) the nature of DOM in the source water has a major influence on transformations that occur during treatment, (ii) the climate factors have a secondary effect on transformations, (iii) the wetlands receiving treated wastewater can produce a net increase in DOM, and (iv) the hierarchical analytical approach used in this study can measure the subtle DOM transformations that occur. As wastewater treatment plant effluent passes through treatment wetlands, the DOM undergoes transformation to become more aromatic and oxygenated. Autochthonous sources are contributed to the DOM, the nature of which is governed by the developmental stage of the wetland system as well as vegetation patterns. Concentrations of specific wastewaterderived organic contaminants such as linear alkylbenzene sulfonate, caffeine, and ethylenediaminetetraacetic acid were significantly attenuated by wetland treatment and were not contributed by internal loading.

  3. Dissolved organic matter photolysis in Canadian arctic thaw ponds

    NASA Astrophysics Data System (ADS)

    Laurion, Isabelle; Mladenov, Natalie

    2013-09-01

    The abundant thaw lakes and ponds in the circumarctic receive a new pool of organic carbon as permafrost peat soils degrade, which can be exposed to significant irradiance that potentially increases as climate warms and ice cover shortens. Exposure to sunlight is known to accelerate the transformation of dissolved organic matter (DOM) into molecules that can be more readily used by microbes. We sampled the water from two common classes of ponds found in the ice-wedge system of continuous permafrost regions of Canada, polygonal and runnel ponds, and followed the transformation of DOM over 12 days by looking at dissolved organic carbon (DOC) concentration and DOM absorption and fluorescence properties. The results indicate a relatively fast decay of color (3.4 and 1.6% loss d-1 of absorption at 320 nm for the polygonal and runnel pond, respectively) and fluorescence (6.1 and 8.3% loss d-1 of total fluorescent components, respectively) at the pond surface, faster in the case of humic-like components, but insignificant losses of DOC over the observed period. This result indicates that direct DOM mineralization (photochemical production of CO2) is apparently minor in thaw ponds compared to the photochemical transformation of DOM into less chromophoric and likely more labile molecules with a greater potential for microbial mineralization. Therefore, DOM photolysis in arctic thaw ponds can be considered as a catalytic mechanism, accelerating the microbial turnover of mobilized organic matter from thawing permafrost and the production of greenhouse gases, especially in the most shallow ponds. Under a warming climate, this mechanism will intensify as summers lengthen.

  4. Use of Passive Samplers to Measure Dissolved Organic Contaminants in a Temperate Estuary

    EPA Science Inventory

    Measuring dissolved concentrations of organic contaminants can be challenging given their low solubilities and high particle association. However, to perform accurate risk assessments of these chemicals, knowing the dissolved concentration is critical since it is considered to b...

  5. THE ROLE OF NITROGEN IN CHROMOPHORIC AND FLUORESCENT DISSOLVED ORGANIC MATTER FORMATION

    EPA Science Inventory

    Microbial and photochemical processes affect chromophoric dissolved organic matter (CDOM) dynamics in the ocean. Some evidence suggests that dissolved nitrogen plays a role in CDOM formation, although this has received little systematic attention in marine ecosystems. Coastal sea...

  6. Dynamics of dissolved organic matter in fjord ecosystems: Contributions of terrestrial dissolved organic matter in the deep layer

    NASA Astrophysics Data System (ADS)

    Yamashita, Youhei; McCallister, S. Leigh; Koch, Boris P.; Gonsior, Michael; Jaffé, Rudolf

    2015-06-01

    Annually, rivers and inland water systems deliver a significant amount of terrestrial organic matter (OM) to the adjacent coastal ocean in both particulate and dissolved forms; however, the metabolic and biogeochemical transformations of OM during its seaward transport remains one of the least understood components of the global carbon cycle. This transfer of terrestrial carbon to marine ecosystems is crucial in maintaining trophic dynamics in coastal areas and critical in global carbon cycling. Although coastal regions have been proposed as important sinks for exported terrestrial materials, most of the global carbon cycling data, have not included fjords in their budgets. Here we present distributional patterns on the quantity and quality of dissolved OM in Fiordland National Park, New Zealand. Specifically, we describe carbon dynamics under diverse environmental settings based on dissolved organic carbon (DOC) depth profiles, oxygen concentrations, optical properties (fluorescence) and stable carbon isotopes. We illustrate a distinct change in the character of DOC in deep waters compared to surface and mid-depth waters. Our results suggest that, both, microbial reworking of terrestrially derived plant detritus and subsequent desorption of DOC from its particulate counterpart (as verified in a desorption experiment) are the main sources of the humic-like enriched DOC in the deep basins of the studied fjords. While it has been suggested that short transit times and protection of OM by mineral sorption may ultimately result in significant terrestrial carbon burial and preservation in fjords, our data suggests the existence of an additional source of terrestrial OM in the form of DOC generated in deep, fjord water.

  7. Optical Characterization of Dissolved Organic Matter in Maine Rivers

    NASA Astrophysics Data System (ADS)

    White, D. P.; Roesler, C. S.; Bourakovsky, A.; Drapeau, S.; Huntington, T. G.; Billmire, M.; Camill, P.

    2014-12-01

    The coastal waters of the Gulf of Maine are significantly impacted by the input of fresh water from a distributed river system. In this study, we focus on the four largest watersheds (Androscoggin, Kennebec, Penobscot and St. John) that contribute to the freshwater inputs. In particular, we investigated the input of dissolved organic carbon via PARAFAC analysis of excitation/emission matrix fluorescence spectroscopy. Monthly sampling of over 65 stations for three years has yielded a wealth of information about tributary characteristics. Specifically, we investigated the role of water quality properties and landscape coverage in the mobilization and flux of different components of DOC and how those properties vary spatially across the landscape and temporally over seasons and between years. Across all rivers, humic-like materials were the most prevalent components at the river mouths; accumulating along the rivers due to sequential tributary inputs. The concentration of humic-like materials increased latitudinally from the Androscoggin to St John, a geographic progression in source material also correlated to climate variations, land coverage or bedrock acidity. Dissolved proteins displayed positive relationships with climatological Chlorophyll a and total Nitrogen values. In all rivers, peak fluorescence of dissolved proteins was observed during summer months, with the maximum intensity observed in the Androscoggin River. The magnitude and pattern of seasonal flux of fluorescent materials into the Gulf of Maine was very similar between the Penobscot and the Kennebec rivers. The flux of all DOM components was highest during the spring freshet, with a secondary peak during fall precipitation maxima and lowest during August, likely due to both low mobilization and photo degradation of river borne materials.

  8. Improved automation of dissolved organic carbon sampling for organic-rich surface waters.

    PubMed

    Grayson, Richard P; Holden, Joseph

    2016-02-01

    In-situ UV-Vis spectrophotometers offer the potential for improved estimates of dissolved organic carbon (DOC) fluxes for organic-rich systems such as peatlands because they are able to sample and log DOC proxies automatically through time at low cost. In turn, this could enable improved total carbon budget estimates for peatlands. The ability of such instruments to accurately measure DOC depends on a number of factors, not least of which is how absorbance measurements relate to DOC and the environmental conditions. Here we test the ability of a S::can Spectro::lyser™ for measuring DOC in peatland streams with routinely high DOC concentrations. Through analysis of the spectral response data collected by the instrument we have been able to accurately measure DOC up to 66 mg L(-1), which is more than double the original upper calibration limit for this particular instrument. A linear regression modelling approach resulted in an accuracy >95%. The greatest accuracy was achieved when absorbance values for several different wavelengths were used at the same time in the model. However, an accuracy >90% was achieved using absorbance values for a single wavelength to predict DOC concentration. Our calculations indicated that, for organic-rich systems, in-situ measurement with a scanning spectrophotometer can improve fluvial DOC flux estimates by 6 to 8% compared with traditional sampling methods. Thus, our techniques pave the way for improved long-term carbon budget calculations from organic-rich systems such as peatlands.

  9. Effect of Dissolved Organic Matter on Basalt Weathering Rates under Flow Conditions

    NASA Astrophysics Data System (ADS)

    Dontsova, K.; Steefel, C. I.; Chorover, J. D.

    2009-12-01

    Rock weathering is an important aspect of soil formation that is tightly coupled to the progressive colonization of grain surfaces by microorganisms and plant tissue, both of which are associated with the exudation of complexing ligands and reducing equivalents that are incorporated into dissolved organic matter. As part of a larger hillslope experimental study being designed for Biosphere 2 (Oracle, AZ), we seek to determine how the presence and concentration of dissolved organic matter affects the incongruent dissolution rates of basaltic tuff. Saturated flow column experiments are being conducted using plant-derived soluble organic matter solutions of variable concentrations, and comparisons are being made to experiments conducted with malic acid, a low-molecular weight organic acid commonly exuded into the rhizosphere. Dissolved organic matter was extracted from Ponderosa Pine forest floor and was characterized for aqueous geochemical parameters (pH, EC, ion balance, DOC/TN) and also for DOC composition (UV-Vis, FTIR spectroscopy). Column effluents are being analyzed for major and trace cations, anions, silica and organic solutes. Dissolution rates of primary minerals and precipitation rates of secondary phases will be estimated by fitting the data to a numerical reactive transport model, CrunchFlow2007. At the end of the fluid flow experiment, column materials will be analyzed for biogeochemical composition to detect preferential dissolution of specific phases, the precipitation of new ones, and to monitor the associated formation of biofilms. The influence of organic solutions on weathering patterns of basalt will be discussed.

  10. Structuring of bacterioplankton communities by specific dissolved organic carbon compounds.

    PubMed

    Gómez-Consarnau, Laura; Lindh, Markus V; Gasol, Josep M; Pinhassi, Jarone

    2012-09-01

    The main role of microorganisms in the cycling of the bulk dissolved organic carbon pool in the ocean is well established. Nevertheless, it remains unclear if particular bacteria preferentially utilize specific carbon compounds and whether such compounds have the potential to shape bacterial community composition. Enrichment experiments in the Mediterranean Sea, Baltic Sea and the North Sea (Skagerrak) showed that different low-molecular-weight organic compounds, with a proven importance for the growth of marine bacteria (e.g. amino acids, glucose, dimethylsulphoniopropionate, acetate or pyruvate), in most cases differentially stimulated bacterial growth. Denaturing gradient gel electrophoresis 'fingerprints' and 16S rRNA gene sequencing revealed that some bacterial phylotypes that became abundant were highly specific to enrichment with specific carbon compounds (e.g. Acinetobacter sp. B1-A3 with acetate or Psychromonas sp. B3-U1 with glucose). In contrast, other phylotypes increased in relative abundance in response to enrichment with several, or all, of the investigated carbon compounds (e.g. Neptuniibacter sp. M2-A4 with acetate, pyruvate and dimethylsulphoniopropionate, and Thalassobacter sp. M3-A3 with pyruvate and amino acids). Furthermore, different carbon compounds triggered the development of unique combinations of dominant phylotypes in several of the experiments. These results suggest that bacteria differ substantially in their abilities to utilize specific carbon compounds, with some bacteria being specialists and others having a more generalist strategy. Thus, changes in the supply or composition of the dissolved organic carbon pool can act as selective forces structuring bacterioplankton communities.

  11. GROUNDWATER TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN THE PRESENCE OF DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    The effects of dissolved organic matter (DOM) on the transport of hydrophobic organic compounds in soil columns were investigated. Three compounds (naphthalene, phenanthrene and DDT) that spanned three orders of magnitude in water solubility were used. Instead of humic matter, mo...

  12. Catchment scale molecular composition of hydrologically mobilized dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Raeke, Julia; Lechtenfeld, Oliver J.; Oosterwoud, Marieke R.; Bornmann, Katrin; Tittel, Jörg; Reemtsma, Thorsten

    2016-04-01

    Increasing concentrations of dissolved organic matter (DOM) in rivers of temperate catchments in Europe and North Amerika impose new technical challenges for drinking water production. The driving factors for this decadal increase in DOM concentration are not conclusive and changes in annual temperatures, precipitation and atmospheric deposition are intensely discussed. It is known that the majority of DOM is released by few but large hydrologic events, mobilizing DOM from riparian wetlands for export by rivers and streams. The mechanisms of this mobilization and the resulting molecular composition of the released DOM may be used to infer long-term changes in the biogeochemistry of the respective catchment. Event-based samples collected over two years from streams in three temperate catchments in the German mid-range mountains were analyzed after solid-phase extraction of DOM for their molecular composition by ultra-high resolution mass spectrometry (FT-ICR MS). Hydrologic conditions, land use and water chemistry parameters were used to complement the molecular analysis. The molecular composition of the riverine DOM was strongly dependent on the magnitude of the hydrologic events, with unsaturated, oxygen-enriched compounds being preferentially mobilized by large events. This pattern is consistent with an increase in dissolved iron and aluminum concentrations. In contrast, the relative proportions of nitrogen and sulfur bearing compounds increased with an increased agricultural land use but were less affected by the mobilization events. Co-precipitation experiments with colloidal aluminum showed that unsaturated and oxygen-rich compounds are preferentially removed from the dissolved phase. The precipitated compounds thus had similar chemical characteristics as compared to the mobilized DOM from heavy rain events. Radiocarbon analyses also indicated that this precipitated fraction of DOM was of comparably young radiocarbon age. DOM radiocarbon from field samples

  13. Adsorption of Compounds that Mimic Urban Stormwater Dissolved Organic Nitrogen.

    PubMed

    Mohtadi, Mehrdad; James, Bruce R; Davis, Allen P

    2017-02-01

      Stormwater runoff carrying nitrogen can accelerate eutrophication. Bioretention facilities are among low impact development systems which are commonly used to manage urban stormwater quality and quantity. They are, however, not designed to remove dissolved organic nitrogen (DON) and may become a net DON exporter. Adsorption of seven organic nitrogenous compounds onto several adsorbents was examined. Batch adsorption study revealed that coal activated carbon (AC) exhibited the best performance in adsorption of the selected organic nitrogenous compounds. The highest adsorption capacity of coal AC was 0.4 mg N/g for pyrrole at an equilibrium concentration of 0.02 mg N/L, while adsorption was not detectable for urea at the same equilibrium concentration. The fastest compound to reach equilibrium adsorption capacity onto the coal AC was pyrrole (1 hour). The adsorption capacity of the coal AC for pyrrole and N-acetyl-d-glucosamine and 1-hour contact time is recommended for designing bioretention systems targeting organic nitrogenous compounds.

  14. Dissolved organic matter uptake by Trichodesmium in the Southwest Pacific

    NASA Astrophysics Data System (ADS)

    Benavides, Mar; Berthelot, Hugo; Duhamel, Solange; Raimbault, Patrick; Bonnet, Sophie

    2017-01-01

    The globally distributed diazotroph Trichodesmium contributes importantly to nitrogen inputs in the oligotrophic oceans. Sites of dissolved organic matter (DOM) accumulation could promote the mixotrophic nutrition of Trichodesmium when inorganic nutrients are scarce. Nano-scale secondary ion mass spectrometry (nanoSIMS) analyses of individual trichomes sampled in the South Pacific Ocean, showed significant 13C-enrichments after incubation with either 13C-labeled carbohydrates or amino acids. These results suggest that DOM could be directly taken up by Trichodesmium or primarily consumed by heterotrophic epibiont bacteria that ultimately transfer reduced DOM compounds to their host trichomes. Although the addition of carbohydrates or amino acids did not significantly affect bulk N2 fixation rates, N2 fixation was enhanced by amino acids in individual colonies of Trichodesmium. We discuss the ecological advantages of DOM use by Trichodesmium as an alternative to autotrophic nutrition in oligotrophic open ocean waters.

  15. Refractory dissolved organic nitrogen accumulation in high-elevation lakes.

    PubMed

    Goldberg, S J; Ball, G I; Allen, B C; Schladow, S G; Simpson, A J; Masoom, H; Soong, R; Graven, H D; Aluwihare, L I

    2015-02-23

    The role of dissolved organic matter (DOM) as either a sink for inorganic nutrients or an additional nutrient source is an often-neglected component of nutrient budgets in aquatic environments. Here, we examined the role of DOM in reactive nitrogen (N) storage in Sierra Nevada (California, USA) lakes where atmospheric deposition of N has shifted the lakes toward seasonal phosphorus (P)-limitation. Nuclear magnetic resonance (NMR) spectroscopy and isotope analyses performed on DOM isolated from Lake Tahoe reveal the accumulation of refractory proteinaceous material with a 100-200-year residence time. In contrast, smaller lakes in the same watershed contain DOM with typical terrestrial characteristics, indicating that proteins in Lake Tahoe are autochthonously produced. These data support the role of DOM as a possible sink for reactive N in these lake ecosystems and identify a potential role for DOM in affecting the inorganic nutrient stoichiometry of these environments.

  16. Dissolved organic matter uptake by Trichodesmium in the Southwest Pacific

    PubMed Central

    Benavides, Mar; Berthelot, Hugo; Duhamel, Solange; Raimbault, Patrick; Bonnet, Sophie

    2017-01-01

    The globally distributed diazotroph Trichodesmium contributes importantly to nitrogen inputs in the oligotrophic oceans. Sites of dissolved organic matter (DOM) accumulation could promote the mixotrophic nutrition of Trichodesmium when inorganic nutrients are scarce. Nano-scale secondary ion mass spectrometry (nanoSIMS) analyses of individual trichomes sampled in the South Pacific Ocean, showed significant 13C-enrichments after incubation with either 13C-labeled carbohydrates or amino acids. These results suggest that DOM could be directly taken up by Trichodesmium or primarily consumed by heterotrophic epibiont bacteria that ultimately transfer reduced DOM compounds to their host trichomes. Although the addition of carbohydrates or amino acids did not significantly affect bulk N2 fixation rates, N2 fixation was enhanced by amino acids in individual colonies of Trichodesmium. We discuss the ecological advantages of DOM use by Trichodesmium as an alternative to autotrophic nutrition in oligotrophic open ocean waters. PMID:28117432

  17. Dissolved Organic Carbon in the North Atlantic Meridional Overturning Circulation

    PubMed Central

    Fontela, Marcos; García-Ibáñez, Maribel I.; Hansell, Dennis A.; Mercier, Herlé; Pérez, Fiz F.

    2016-01-01

    The quantitative role of the Atlantic Meridional Overturning Circulation (AMOC) in dissolved organic carbon (DOC) export is evaluated by combining DOC measurements with observed water mass transports. In the eastern subpolar North Atlantic, both upper and lower limbs of the AMOC transport high-DOC waters. Deep water formation that connects the two limbs of the AMOC results in a high downward export of non-refractory DOC (197 Tg-C·yr−1). Subsequent remineralization in the lower limb of the AMOC, between subpolar and subtropical latitudes, consumes 72% of the DOC exported by the whole Atlantic Ocean. The contribution of DOC to the carbon sequestration in the North Atlantic Ocean (62 Tg-C·yr−1) is considerable and represents almost a third of the atmospheric CO2 uptake in the region. PMID:27240625

  18. Response of Dissolved Organic Matter to Warming and Nitrogen Addition

    NASA Astrophysics Data System (ADS)

    Choi, J. H.; Nguyen, H.

    2014-12-01

    Dissolved Organic Matter (DOM) is a ubiquitous mixture of soluble organic components. Since DOM is produced from the terrestrial leachate of various soil types, soil may influence the chemistry and biology of freshwater through the input of leachate and run-off. The increased temperature by climate change could dramatically change the DOM characteristics of soils through enhanced decomposition rate and losses of carbon from soil organic matter. In addition, the increase in the N-deposition affects DOM leaching from soils by changing the carbon cycling and decomposition rate of soil decay. In this study, we conducted growth chamber experiments using two types of soil (wetland and forest) under the conditions of temperature increase and N-deposition in order to investigate how warming and nitrogen addition influence the characteristics of the DOM leaching from different soil types. This leachate controls the quantity and quality of DOM in surface water systems. After 10 months of incubation, the dissolved organic carbon (DOC) concentrations decreased for almost samples in the range of 7.6 to 87.3% (ANOVA, p<0.05). The specific UV absorption (SUVA) values also decreased for almost samples after the first 3 months and then increased gradually afterward in range of 3.3 to 108.4%. Both time and the interaction between time and the temperature had the statistically significant effects on the SUVA values (MANOVA, p<0.05). Humification index (HIX) showed the significant increase trends during the duration of incubation and temperature for almost the samples (ANOVA, p<0.05). Higher decreases in the DOC values and increases in HIX were observed at higher temperatures, whereas the opposite trend was observed for samples with N-addition. The PARAFAC results showed that three fluorescence components: terrestrial humic (C1), microbial humic-like (C2), and protein-like (C3), constituted the fluorescence matrices of soil samples. During the experiment, labile DOM from the soils was

  19. Association of Dissolved Mercury with Dissolved Organic Carbon in Rivers and Streams: The Role of Watershed Soil Organic Carbon

    NASA Astrophysics Data System (ADS)

    Stoken, O.; Riscassi, A.; Scanlon, T. M.

    2014-12-01

    Surface waters are an important pathway for the transport of atmospherically deposited mercury (Hg) from terrestrial watersheds. Dissolved Hg (HgD) is thought to be more bioavailable than particulate Hg and has been found to be strongly correlated with dissolved organic carbon (DOC) in numerous watersheds. The ratio of HgD to DOC is highly variable from site to site, which we hypothesize is strongly dependent on local environmental factors such as atmospheric deposition and soil organic carbon (SOC). Sixteen watersheds throughout the United States were used in this study to determine the relationship between the ratio of HgD:DOC, Hg wet deposition, and SOC. The Soil Survey Geographic database (SSURGO) and Northern Circumpolar Soil Carbon Database (NCSCD) were used to determine SOC values while HgD:DOC values were obtained from previous studies. Hg wet deposition was reported by the Mercury Deposition Network. There was no correlation found between atmospheric mercury wet deposition and HgD:DOC (r2 = 0.04; p = 0.44) but SOC was able to explain about 71% of the variation in the HgD:DOC ratio (r2 = 0.71; p < 0.01). A mathematical framework was developed to explain the power-law relationship between SOC and HgD:DOC based on soil carbon pools. The framework infers that the amount of Hg adsorbed to SOC does not increase in proportion to SOC at high SOC levels and points towards a Hg supply limitation for adsorption to soils with relatively deep carbon pools. Overall, this study identifies SOC as a first-order control on the association of HgD and DOC and indicates that globally available SOC datasets can be utilized to predict Hg transport in stream systems.

  20. Role of dissolved organic matter in ice photochemistry.

    PubMed

    Grannas, Amanda M; Pagano, Lisa P; Pierce, Brittany C; Bobby, Rachel; Fede, Alexis

    2014-09-16

    In this study, we provide evidence that dissolved organic matter (DOM) plays an important role in indirect photolysis processes in ice, producing reactive oxygen species (ROS) and leading to the efficient photodegradation of a probe hydrophobic organic pollutant, aldrin. Rates of DOM-mediated aldrin loss are between 2 and 56 times faster in ice than in liquid water (depending on DOM source and concentration), likely due to a freeze-concentration effect that occurs when the water freezes, providing a mechanism to concentrate reactive components into smaller, liquid-like regions within or on the ice. Rates of DOM-mediated aldrin loss are also temperature dependent, with higher rates of loss as temperature decreases. This also illustrates the importance of the freeze-concentration effect in altering reaction kinetics for processes occurring in environmental ices. All DOM source types studied were able to mediate aldrin loss, including commercially available fulvic and humic acids and an authentic Arctic snow DOM sample isolated by solid phase extraction, indicating the ubiquity of DOM in indirect photochemistry in environmental ices.

  1. CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) DERIVED FROM DECOMPOSITION OF VARIOUS VASCULAR PLANT AND ALGAL SOURCES

    EPA Science Inventory

    Chromophoric dissolved organic (CDOM) in aquatic environments is derived from the microbial decomposition of terrestrial and microbial organic matter. Here we present results of studies of the spectral properties and photoreactivity of the CDOM derived from several organic matter...

  2. Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

    PubMed

    Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

    2007-04-01

    The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

  3. Data-based mechanistic modeling of dissolved organic carbon load through storms using continuous 15-minute resolution observations within UK upland watersheds

    NASA Astrophysics Data System (ADS)

    Jones, T.; Chappell, N. A.

    2013-12-01

    Few watershed modeling studies have addressed DOC dynamics through storm hydrographs (notable exceptions include Boyer et al., 1997 Hydrol Process; Jutras et al., 2011 Ecol Model; Xu et al., 2012 Water Resour Res). In part this has been a consequence of an incomplete understanding of the biogeochemical processes leading to DOC export to streams (Neff & Asner, 2001, Ecosystems) & an insufficient frequency of DOC monitoring to capture sometimes complex time-varying relationships between DOC & storm hydrographs (Kirchner et al., 2004, Hydrol Process). We present the results of a new & ongoing UK study that integrates two components - 1/ New observations of DOC concentrations (& derived load) continuously monitored at 15 minute intervals through multiple seasons for replicated watersheds; & 2/ A dynamic modeling technique that is able to quantify storage-decay effects, plus hysteretic, nonlinear, lagged & non-stationary relationships between DOC & controlling variables (including rainfall, streamflow, temperature & specific biogeochemical variables e.g., pH, nitrate). DOC concentration is being monitored continuously using the latest generation of UV spectrophotometers (i.e. S::CAN spectro::lysers) with in situ calibrations to laboratory analyzed DOC. The controlling variables are recorded simultaneously at the same stream stations. The watersheds selected for study are among the most intensively studied basins in the UK uplands, namely the Plynlimon & Llyn Brianne experimental basins. All contain areas of organic soils, with three having improved grasslands & three conifer afforested. The dynamic response characteristics (DRCs) that describe detailed DOC behaviour through sequences of storms are simulated using the latest identification routines for continuous time transfer function (CT-TF) models within the Matlab-based CAPTAIN toolbox (some incorporating nonlinear components). To our knowledge this is the first application of CT-TFs to modelling DOC processes

  4. Relationships between Nitrate and Dissolved Organic Nitrogen and Watershed Characteristics in a Rural Temperate Basin

    NASA Astrophysics Data System (ADS)

    Daley, M. L.; McDowell, W. H.

    2002-05-01

    Global models have been developed to predict nitrate export, a main component of dissolved inorganic nitrogen (DIN) export, based on human population density and human activity. Controls on dissolved organic nitrogen (DON) export are largely unknown. We tested several global nitrate models and examined potential sources of riverine DON in the Lamprey River basin (479 km2) located in rural southeastern New Hampshire, and 11 of its sub-catchments. Dissolved organic nitrogen dominated total N export. Export of nitrate and DON from the Lamprey was 0.53 and 1.28 kg/ha/yr respectively. Mean annual nitrate and DON concentration in the Lamprey was 0.11 and 0.30 mg/L respectively. The global nitrate models over predicted (>200% difference) nitrate export for the Lamprey and all its sub-catchments except for the smallest most populated catchment. Population density (R2>0.89, p<0.00001) and riparian percentage agriculture (R2>0.90, p<0.00001) showed strong positive relationships with nitrate concentration and export. Dissolved organic nitrogen was not related to factors that control inorganic nitrogen (human population density or percentage agriculture). Non-purgeable organic carbon (NPOC) concentration and export (R2>0.84, p<0.0001), percentage wetland (R2=0.79, p<0.001) and riparian carbon storage (R2=0.84, p<0.0001) all showed strong positive relationships with DON. We conclude from the results of this study that human population density and activity are the main factors controlling DIN export and that wetlands and riparian soils are main sources of DON.

  5. Photolytic processing of secondary organic aerosols dissolved in cloud droplets.

    PubMed

    Bateman, Adam P; Nizkorodov, Sergey A; Laskin, Julia; Laskin, Alexander

    2011-07-14

    The effect of UV irradiation on the molecular composition of aqueous extracts of secondary organic aerosol (SOA) was investigated. SOA was prepared by the dark reaction of ozone and d-limonene at 0.05-1 ppm precursor concentrations and collected with a particle-into-liquid sampler (PILS). The PILS extracts were photolyzed by 300-400 nm radiation for up to 24 h. Water-soluble SOA constituents were analyzed using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) at different stages of photolysis for all SOA precursor concentrations. Exposure to UV radiation increased the average O/C ratio and decreased the average double bond equivalent (DBE) of the dissolved SOA compounds. Oligomeric compounds were significantly decreased by photolysis relative to the monomeric compounds. Direct pH measurements showed that acidic compounds increased in abundance upon photolysis. Methanol reactivity analysis revealed significant photodissociation of molecules containing carbonyl groups and the formation of carboxylic acids. Aldehydes, such as limononaldehyde, were almost completely removed. The removal of carbonyls was further confirmed by the UV/Vis absorption spectroscopy of the SOA extracts where the absorbance in the carbonyl n→π* band decreased significantly upon photolysis. The effective quantum yield (the number of carbonyls destroyed per photon absorbed) was estimated as ∼0.03. The total concentration of peroxides did not change significantly during photolysis as quantified with an iodometric test. Although organic peroxides were photolyzed, the likely end products of photolysis were smaller peroxides, including hydrogen peroxide, resulting in a no net change in the peroxide content. Photolysis of dry limonene SOA deposited on substrates was investigated in a separate set of experiments. The observed effects on the average O/C and DBE were similar to the aqueous photolysis, but the extent of chemical change was smaller in dry SOA. Our results suggest

  6. Colored dissolved organic matter in Tampa Bay, Florida

    USGS Publications Warehouse

    Chen, Z.; Hu, C.; Conmy, R.N.; Muller-Karger, F.; Swarzenski, P.

    2007-01-01

    Absorption and fluorescence of colored dissolved organic matter (CDOM) and concentrations of dissolved organic carbon (DOC), chlorophyll and total suspended solids in Tampa Bay and its adjacent rivers were examined in June and October of 2004. Except in Old Tampa Bay (OTB), the spatial distribution of CDOM showed a conservative relationship with salinity in June, 2004 (aCDOM(400) = − 0.19 × salinity + 6.78, R2 = 0.98, n = 17, salinity range = 1.1–32.5) with little variations in absorption spectral slope and fluorescence efficiency. This indicates that CDOM distribution was dominated by mixing. In October, 2004, CDOM distribution was nonconservative with an average absorption coefficient (aCDOM(400), ∼ 7.76 m-1) about seven times higher than that in June (∼ 1.11 m-1). The nonconservative behavior was caused largely by CDOM removal at intermediate salinities (e.g., aCDOM(400) removal > 15% at salinity ∼ 13.0), which likely resulted from photobleaching due to stronger stratification. The spatial and seasonal distributions of CDOM in Tampa Bay showed that the two largest rivers, the Alafia River (AR) and Hillsborough River (HR) were dominant CDOM sources to most of the bay. In OTB, however, CDOM showed distinctive differences: lower absorption coefficient, higher absorption spectral slopes, and lower ratios of CDOM absorption to DOC and higher fluorescence efficiency. These differences may have stemmed from (1) changes in CDOM composition by more intensive photobleaching due to the longer residence time of water mass in OTB; (2) other sources of CDOM than the HR/AR inputs, such as local creeks, streams, groundwater, and/or bottom re-suspension. Average CDOM absorption in Tampa Bay at 443 nm, aCDOM(443), was about five times higher in June and about ten times higher in October than phytoplankton pigment absorption, aph(443), indicating that blue light attenuation in the water column was dominated by CDOM rather than by phytoplankton absorption throughout the

  7. The soil organic carbon content of anthropogenically altered organic soils effects the dissolved organic matter quality, but not the dissolved organic carbon concentrations

    NASA Astrophysics Data System (ADS)

    Frank, Stefan; Tiemeyer, Bärbel; Bechtold, Michel; Lücke, Andreas; Bol, Roland

    2016-04-01

    Dissolved organic carbon (DOC) is an important link between terrestrial and aquatic ecosystems. This is especially true for peatlands which usually show high concentrations of DOC due to the high stocks of soil organic carbon (SOC). Most previous studies found that DOC concentrations in the soil solution depend on the SOC content. Thus, one would expect low DOC concentrations in peatlands which have anthropogenically been altered by mixing with sand. Here, we want to show the effect of SOC and groundwater level on the quantity and quality of the dissolved organic matter (DOM). Three sampling sites were installed in a strongly disturbed bog. Two sites differ in SOC (Site A: 48%, Site B: 9%) but show the same mean annual groundwater level of 15 and 18 cm below ground, respectively. The SOC content of site C (11%) is similar to Site B, but the groundwater level is much lower (-31 cm) than at the other two sites. All sites have a similar depth of the organic horizon (30 cm) and the same land-use (low-intensity sheep grazing). Over two years, the soil solution was sampled bi-weekly in three depths (15, 30 and 60 cm) and three replicates. All samples were analyzed for DOC and selected samples for dissolved organic nitrogen (DON) and delta-13C and delta-15N. Despite differences in SOC and groundwater level, DOC concentrations did not differ significantly (A: 192 ± 62 mg/L, B: 163 ± 55 mg/L and C: 191 ± 97 mg/L). At all sites, DOC concentrations exceed typical values for peatlands by far and emphasize the relevance even of strongly disturbed organic soils for DOC losses. Individual DOC concentrations were controlled by the temperature and the groundwater level over the preceding weeks. Differences in DOM quality were clearer. At site B with a low SOC content, the DOC:DON ratio of the soil solution equals the soil's C:N ratio, but the DOC:DON ratio is much higher than the C:N ratio at site A. In all cases, the DOC:DON ratio strongly correlates with delta-13C. There is no

  8. Study of fouling and scaling in capacitive deionisation by using dissolved organic and inorganic salts.

    PubMed

    Mossad, Mohamed; Zou, Linda

    2013-01-15

    In this work, fouling, scaling and cleaning of the capacitive deionisation (CDI) with activated carbon electrodes were systematically investigated for the first time. Electrode fouling caused by dissolved organic matter using sodium salt of humic acid as a model foulant (measured by total organic carbon concentration, TOC) and inorganic salt (NaCl, MgCl(2), CaCl(2) and FeCl(3)) in the CDI feed solutions was investigated in a series of controlled fouling experiments. After each CDI experiment, a series of cleaning steps was performed to understand the reversibility of fouling accumulated on the electrode surface by analysing the cleaning solutions. The higher the TOC concentration in the CDI feed solution, the more the reduction of salt removal efficiency, declination in the production rate and energy consumption. Dissolved organic matter is the main cause of electrode fouling, as it blocks the activated carbon pores and reduces their electrosorption capacitance. Ca and Mg have no noticeable effect on the CDI treatment performance. However, Fe seemed to have a greater effect on CDI electrode fouling. Alkaline and acid cleaning solutions were able to restore the recovery of the CDI performance from fouling. Pre-treatment to reduce the dissolved organic matter levels is recommended to achieve sustainable treatment performance.

  9. Towards an understanding of feedbacks between plant productivity, acidity and dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Rowe, Ed; Tipping, Ed; Davies, Jessica; Monteith, Don; Evans, Chris

    2014-05-01

    The recent origin of much dissolved organic carbon (DOC) (Tipping et al., 2010) implies that plant productivity is a major control on DOC fluxes. However, the flocculation, sorption and release of potentially-dissolved organic matter are governed by pH, and widespread increases in DOC concentrations observed in northern temperate freshwater systems seem to be primarily related to recovery from acidification (Monteith et al., 2007). We explore the relative importance of changes in productivity and pH using a model, MADOC, that incorporates both these effects (Rowe et al., 2014). The feedback whereby DOC affects pH is included. The model uses an annual timestep and relatively simple flow-routing, yet reproduces observed changes in DOC flux and pH in experimental (Evans et al., 2012) and survey data. However, the first version of the model probably over-estimated responses of plant productivity to nitrogen (N) deposition in upland semi-natural ecosystems. There is a strong case that plant productivity is an important regulator of DOC fluxes, and theoretical reasons for suspecting widespread productivity increases in recent years due not only to N deposition but to temperature and increased atmospheric CO2 concentrations. However, evidence that productivity has increased in upland semi-natural ecosystems is sparse, and few studies have assessed the major limitations to productivity in these habitats. In systems where phosphorus (P) limitation prevails, or which are co-limited, productivity responses to anthropogenic drivers will be limited. We present a revised version of the model that incorporates P cycling and appears to represent productivity responses to atmospheric N pollution more realistically. Over the long term, relatively small fluxes of nutrient elements into and out of ecosystems can profoundly affect productivity and the accumulation of organic matter. Dissolved organic N (DON) is less easily intercepted by plants and microbes than mineral N, and DON

  10. Chemical composition of dissolved organic matter draining permafrost soils

    NASA Astrophysics Data System (ADS)

    Ward, Collin P.; Cory, Rose M.

    2015-10-01

    Northern circumpolar permafrost soils contain roughly twice the amount of carbon stored in the atmosphere today, but the majority of this soil organic carbon is perennially frozen. Climate warming in the arctic is thawing permafrost soils and mobilizing previously frozen dissolved organic matter (DOM) from deeper soil layers to nearby surface waters. Previous studies have reported that ancient DOM draining deeper layers of permafrost soils was more susceptible to degradation by aquatic bacteria compared to modern DOM draining the shallow active layer of permafrost soils, and have suggested that DOM chemical composition may be an important control for the lability of DOM to bacterial degradation. However, the compositional features that distinguish DOM drained from different depths in permafrost soils are poorly characterized. Thus, the objective of this study was to characterize the chemical composition of DOM drained from different depths in permafrost soils, and relate these compositional differences to its susceptibility to biological degradation. DOM was leached from the shallow organic mat and the deeper permafrost layer of soils within the Imnavait Creek watershed on the North Slope of Alaska. DOM draining both soil layers was characterized in triplicate by coupling ultra-high resolution mass spectrometry, 13C solid-state NMR, and optical spectroscopy methods with multi-variate statistical analyses. Reproducibility of replicate mass spectra was high, and compositional differences resulting from interfering species or isolation effects were significantly smaller than differences between DOM drained from each soil layer. All analyses indicated that DOM leached from the shallower organic mat contained higher molecular weight, more oxidized, and more unsaturated aromatic species compared to DOM leached from the deeper permafrost layer. Bacterial production rates and bacterial efficiencies were significantly higher for permafrost compared to organic mat DOM

  11. Dissolved organic matter reduces algal accumulation of methylmercury

    USGS Publications Warehouse

    Luengen, Allison C.; Fisher, Nicholas S.; Bergamaschi, Brian A.

    2012-01-01

    Dissolved organic matter (DOM) significantly decreased accumulation of methylmercury (MeHg) by the diatom Cyclotella meneghiniana in laboratory experiments. Live diatom cells accumulated two to four times more MeHg than dead cells, indicating that accumulation may be partially an energy-requiring process. Methylmercury enrichment in diatoms relative to ambient water was measured by a volume concentration factor (VCF). Without added DOM, the maximum VCF was 32 x 104, and the average VCF (from 10 to 72 h) over all experiments was 12.6 x 104. At very low (1.5 mg/L) added DOM, VCFs dropped by approximately half. At very high (20 mg/L) added DOM, VCFs dropped 10-fold. Presumably, MeHg was bound to a variety of reduced sulfur sites on the DOM, making it unavailable for uptake. Diatoms accumulated significantly more MeHg when exposed to transphilic DOM extracts than hydrophobic ones. However, algal lysate, a labile type of DOM created by resuspending a marine diatom in freshwater, behaved similarly to a refractory DOM isolate from San Francisco Bay. Addition of 67 μM L-cysteine resulted in the largest drop in VCFs, to 0.28 x 104. Although the DOM composition influenced the availability of MeHg to some extent, total DOM concentration was the most important factor in determining algal bioaccumulation of MeHg.

  12. Hidden cycle of dissolved organic carbon in the deep ocean.

    PubMed

    Follett, Christopher L; Repeta, Daniel J; Rothman, Daniel H; Xu, Li; Santinelli, Chiara

    2014-11-25

    Marine dissolved organic carbon (DOC) is a large (660 Pg C) reactive carbon reservoir that mediates the oceanic microbial food web and interacts with climate on both short and long timescales. Carbon isotopic content provides information on the DOC source via δ(13)C and age via Δ(14)C. Bulk isotope measurements suggest a microbially sourced DOC reservoir with two distinct components of differing radiocarbon age. However, such measurements cannot determine internal dynamics and fluxes. Here we analyze serial oxidation experiments to quantify the isotopic diversity of DOC at an oligotrophic site in the central Pacific Ocean. Our results show diversity in both stable and radio isotopes at all depths, confirming DOC cycling hidden within bulk analyses. We confirm the presence of isotopically enriched, modern DOC cocycling with an isotopically depleted older fraction in the upper ocean. However, our results show that up to 30% of the deep DOC reservoir is modern and supported by a 1 Pg/y carbon flux, which is 10 times higher than inferred from bulk isotope measurements. Isotopically depleted material turns over at an apparent time scale of 30,000 y, which is far slower than indicated by bulk isotope measurements. These results are consistent with global DOC measurements and explain both the fluctuations in deep DOC concentration and the anomalous radiocarbon values of DOC in the Southern Ocean. Collectively these results provide an unprecedented view of the ways in which DOC moves through the marine carbon cycle.

  13. Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

    NASA Technical Reports Server (NTRS)

    Mannino, Antonio; Harvey, H. Rodger

    2003-01-01

    Black carbon (BC) in ultrafiltered high-molecular-weight DOM (UDOM) was measured in surface waters of Delaware Bay, Chesapeake Bay and the adjacent Atlantic Ocean (USA) to ascertain the importance of riverine and estuarine DOM as a source of BC to the ocean. BC comprised 5-72% of UDOM-C (27+/-l7%) and on average 8.9+/-6.5% of dissolved organic carbon (DOC) with higher values in the turbid region of the Delaware Estuary and lower yields in the river and coastal ocean. The spatial and seasonal distributions of BC along the salinity gradient of Delaware Bay suggest that the higher levels of BC in surface water UDOM originated from localized sources, possibly from atmospheric deposition or released from resuspended sediments. Black carbon comprised 4 to 7% of the DOC in the coastal Atlantic Ocean, revealing that river-estuary systems are important exporters of colloidal BC to the ocean. The annual flux of BC from Delaware Bay UDOM to the Atlantic Ocean was estimated at 2.4x10(exp 10) g BC yr(exp -1). The global river flux of BC through DOM to the ocean could be on the order of 5.5x1O(exp 12)g BC yr (exp -1). These results support the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition.

  14. Light-mediated release of dissolved organic carbon by phytoplankton

    NASA Astrophysics Data System (ADS)

    Cherrier, Jennifer; Valentine, SarahKeith; Hamill, Barbara; Jeffrey, Wade H.; Marra, John F.

    2015-07-01

    Laboratory and field studies were carried out to examine the effects of irradiance variability on dissolved organic carbon (DOC) extracellular release by phytoplankton (ER) and the response of natural bacteria assemblages. In axenic laboratory cultures, ER was 3× greater in cultures shifted to 330 μmol photons m-2 s-1 compared to cultures kept at their cultured irradiance, 110 μmol photons m-2 s-1. Natural bacterial assemblages incubated in the dark for 24 h in algal-free culture filtrate generated from both light treatments consumed the DOC from the high-light treatment at a faster rate than that for the low-light treatment. Field measurements in the coastal waters of the northeastern Gulf of Mexico (GOM) and the Eastern North Pacific (ENP) mirrored the laboratory findings, with short-term increases in DOC concentrations occurring concurrently with short-term increases in irradiance, followed by rapid consumption by bacteria. Where no diurnal irradiance increase was observed (overcast skies), no increase in DOC concentration was observed. An experiment using 14C as a tracer for plankton interactions (GOM) was consistent with data on bulk DOC concentrations. For all the field measurements, the rate of irradiance change was correlated with the quantity of DOC released. Collectively these results indicated that release of DOC by phytoplankton populations as a function of incident irradiance can be significant and may have important implications for estimates of ocean carbon flux.

  15. Photochemical Degradation of Persistent Organic Pollutants: A Study of Ice Photochemistry Mediated by Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Bobby, R.; Pagano, L.; Grannas, A. M.

    2012-12-01

    It is well established that ice is a reactive medium in the environment and that active photochemistry occurs in frozen systems. Snow and ice contain a number of absorbing species including nitrate, peroxide and organic matter. Upon irradiation, they can generate a variety of reactive intermediates such as hydroxyl radical and singlet oxygen. It has been shown that dissolved organic matter is a ubiquitous component of snow and ice and plays an important role in overall light absorption properties of the sample. Additionally, the reactive intermediates produced can further react with contaminants present and alter their fate in the environment. Unfortunately, the role of dissolved organic matter in ice photochemistry has received little attention. Here we present results from laboratory-based studies aimed at elucidating the role of dissolved organic matter photochemistry on contaminant degradation in ice. Aqueous samples of our target pollutant, aldrin (20 μg/L), in liquid and frozen phases, were irradiated under Q-Panel 340 lamps to simulate the UV radiation profile of natural sunlight. Results indicated that frozen samples degraded more quickly than liquid samples and that the addition of dissolved organic matter increases the aldrin degradation rate significantly. Both terrestrial (Suwannee River, U.S.) and microbial sources (Pony Lake, Antarctica) of DOM were able to sensitize aldrin loss in ice. Scavengers of singlet oxygen, such as furfuryl alcohol and β-carotene, were also added to DOM solutions. Based on the type of organic matter present, the scavengers had different effects on the photochemical degradation of aldrin. Our results indicate that natural organic matter present in ice is an important component of ice photochemical processes.

  16. Dissolved Organic Carbon In Precipitation At A Coastal Rural Site

    NASA Astrophysics Data System (ADS)

    Liptzin, D.; Daley, M.; Sive, B. C.; Talbot, R. W.; McDowell, W. H.

    2013-12-01

    Dissolved organic carbon (DOC) is a ubiquitous component of precipitation. This DOC is a complex mixture of compounds from biogenic and anthropogenic sources. The amount and chemistry of the DOC in precipitation has been studied for a variety of reasons: as a source of acidity, as a source of C to marine and terrestrial ecosystems, or to track the fate of individual compounds or pollutants. In most cases, past studies have focused on particular compounds or a limited number of precipitation events. Very little is known about the temporal trends in DOC or the relationship between DOC and other constituents of precipitation. We collected precipitation events for more than five years at a rural coastal site in New Hampshire. We evaluated the seasonal patterns and compared the DOC concentrations to other typical measures of the wet atmospheric deposition (ammonium, nitrate, sulfate, and chloride). In addition, we compared the DOC in precipitation to the concentrations of various organic constituents of the atmosphere. The volume weighted mean C concentration was 0.75 mg C/L with concentrations in the summer significantly higher than in the other three seasons. The DOC concentration was most strongly associated with ammonium concentrations (r=0.81), but was also significantly related to nitrate (r=0.50) and sulfate (r=0.63) concentrations. There was no significant association between DOC and chloride concentrations. Preliminary regression tree analysis suggests that the DOC concentration in precipitation was best predicted by the atmospheric concentration of methyl vinyl ketone, an oxidation product of isoprene. These results suggest that both terrestrial biogenic and anthropogenic sources may be important precursors to the C removed from the atmosphere during precipitation events.

  17. Ocean warming-acidification synergism undermines dissolved organic matter assembly.

    PubMed

    Chen, Chi-Shuo; Anaya, Jesse M; Chen, Eric Y-T; Farr, Erik; Chin, Wei-Chun

    2015-01-01

    Understanding the influence of synergisms on natural processes is a critical step toward determining the full-extent of anthropogenic stressors. As carbon emissions continue unabated, two major stressors--warming and acidification--threaten marine systems on several scales. Here, we report that a moderate temperature increase (from 30°C to 32°C) is sufficient to slow--even hinder--the ability of dissolved organic matter, a major carbon pool, to self-assemble to form marine microgels, which contribute to the particulate organic matter pool. Moreover, acidification lowers the temperature threshold at which we observe our results. These findings carry implications for the marine carbon cycle, as self-assembled marine microgels generate an estimated global seawater budget of ~1016 g C. We used laser scattering spectroscopy to test the influence of temperature and pH on spontaneous marine gel assembly. The results of independent experiments revealed that at a particular point, both pH and temperature block microgel formation (32°C, pH 8.2), and disperse existing gels (35°C). We then tested the hypothesis that temperature and pH have a synergistic influence on marine gel dispersion. We found that the dispersion temperature decreases concurrently with pH: from 32°C at pH 8.2, to 28°C at pH 7.5. If our laboratory observations can be extrapolated to complex marine environments, our results suggest that a warming-acidification synergism can decrease carbon and nutrient fluxes, disturbing marine trophic and trace element cycles, at rates faster than projected.

  18. Photolytic processing of secondary organic aerosols dissolved in cloud droplets

    SciTech Connect

    Bateman, Adam P; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2011-05-26

    The effect of UV irradiation on the molecular composition of aqueous extracts of secondary organic aerosol (SOA) was investigated. SOA was prepared by the dark reaction of ozone and d-limonene at 0.05 - 1 ppm precursor concentrations and collected with a particle-into-liquid sampler (PILS). The PILS extracts were photolyzed by 300 - 400 nm radiation for up to 24 hours. Water-soluble SOA constituents were analyzed using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) at different stages of photolysis for all SOA precursor concentrations. Exposure to UV radiation increased the average O/C ratio and decreased the average double bond equivalent (DBE) of the dissolved SOA compounds. Oligomeric compounds were significantly reduced by photolysis relative to the monomeric compounds. Direct pH measurements showed that compounds containing carboxylic acids increased upon photolysis. Methanol reactivity analysis revealed significant photodissociation of molecules containing carbonyl groups and formation of carboxylic acids. Aldehydes, such as limononaldehyde, were almost completely removed. The removal of carbonylswas confirmed by the UV-Vis absorption spectroscopy of the SOA extracts where the absorbance in the carbonyl n→π* band decreased significantly upon photolysis. The effective quantum yield (the number of carbonyls destroyed per photon absorbed) was estimated as ~ 0.03. The concentration of peroxides did not change significantly during photolysis as quantified with an iodometric test. Although organic peroxides were photolyzed, the likely end products of photolysis were smaller peroxides, including hydrogen peroxide, resulting in a no net change in the peroxide content.

  19. Ocean Warming–Acidification Synergism Undermines Dissolved Organic Matter Assembly

    PubMed Central

    Chen, Chi-Shuo; Anaya, Jesse M.; Chen, Eric Y-T; Farr, Erik; Chin, Wei-Chun

    2015-01-01

    Understanding the influence of synergisms on natural processes is a critical step toward determining the full-extent of anthropogenic stressors. As carbon emissions continue unabated, two major stressors—warming and acidification—threaten marine systems on several scales. Here, we report that a moderate temperature increase (from 30°C to 32°C) is sufficient to slow— even hinder—the ability of dissolved organic matter, a major carbon pool, to self-assemble to form marine microgels, which contribute to the particulate organic matter pool. Moreover, acidification lowers the temperature threshold at which we observe our results. These findings carry implications for the marine carbon cycle, as self-assembled marine microgels generate an estimated global seawater budget of ~1016 g C. We used laser scattering spectroscopy to test the influence of temperature and pH on spontaneous marine gel assembly. The results of independent experiments revealed that at a particular point, both pH and temperature block microgel formation (32°C, pH 8.2), and disperse existing gels (35°C). We then tested the hypothesis that temperature and pH have a synergistic influence on marine gel dispersion. We found that the dispersion temperature decreases concurrently with pH: from 32°C at pH 8.2, to 28°C at pH 7.5. If our laboratory observations can be extrapolated to complex marine environments, our results suggest that a warming–acidification synergism can decrease carbon and nutrient fluxes, disturbing marine trophic and trace element cycles, at rates faster than projected. PMID:25714090

  20. Chemodiversity of dissolved organic matter in the Amazon Basin

    NASA Astrophysics Data System (ADS)

    Gonsior, Michael; Valle, Juliana; Schmitt-Kopplin, Philippe; Hertkorn, Norbert; Bastviken, David; Luek, Jenna; Harir, Mourad; Bastos, Wanderley; Enrich-Prast, Alex

    2016-07-01

    Regions in the Amazon Basin have been associated with specific biogeochemical processes, but a detailed chemical classification of the abundant and ubiquitous dissolved organic matter (DOM), beyond specific indicator compounds and bulk measurements, has not yet been established. We sampled water from different locations in the Negro, Madeira/Jamari and Tapajós River areas to characterize the molecular DOM composition and distribution. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC) revealed a large proportion of ubiquitous DOM but also unique area-specific molecular signatures. Unique to the DOM of the Rio Negro area was the large abundance of high molecular weight, diverse hydrogen-deficient and highly oxidized molecular ions deviating from known lignin or tannin compositions, indicating substantial oxidative processing of these ultimately plant-derived polyphenols indicative of these black waters. In contrast, unique signatures in the Madeira/Jamari area were defined by presumably labile sulfur- and nitrogen-containing molecules in this white water river system. Waters from the Tapajós main stem did not show any substantial unique molecular signatures relative to those present in the Rio Madeira and Rio Negro, which implied a lower organic molecular complexity in this clear water tributary, even after mixing with the main stem of the Amazon River. Beside ubiquitous DOM at average H / C and O / C elemental ratios, a distinct and significant unique DOM pool prevailed in the black, white and clear water areas that were also highly correlated with EEM-PARAFAC components and define the frameworks for primary production and other aspects of aquatic life.

  1. The characteristics of dissolved organic matter (DOM) and chromophoric dissolved organic matter (CDOM) in Antarctic sea ice

    NASA Astrophysics Data System (ADS)

    Norman, Louiza; Thomas, David N.; Stedmon, Colin A.; Granskog, Mats A.; Papadimitriou, Stathys; Krapp, Rupert H.; Meiners, Klaus M.; Lannuzel, Delphine; van der Merwe, Pier; Dieckmann, Gerhard S.

    2011-05-01

    An investigation of coloured dissolved organic matter (CDOM) and its relationships to physical and biogeochemical parameters in Antarctic sea ice and oceanic water have indicated that ice melt may both alter the spectral characteristics of CDOM in Antarctic surface waters and serve as a likely source of fresh autochthonous CDOM and labile DOC. Samples were collected from melted bulk sea ice, sea ice brines, surface gap layer waters, and seawater during three expeditions: one during the spring to summer and two during the winter to spring transition period. Variability in both physical (temperature and salinity) and biogeochemical parameters (dissolved and particulate organic carbon and nitrogen, as well as chlorophyll a) was observed during and between studies, but CDOM absorption coefficients measured at 375 nm (a 375) did not differ significantly. Distinct peaked absorption spectra were consistently observed for bulk ice, brine, and gap water, but were absent in the seawater samples. Correlation with the measured physical and biogeochemical parameters could not resolve the source of these peaks, but the shoulders and peaks observed between 260 and 280 nm and between 320 to 330 nm respectively, particularly in the samples taken from high light-exposed gap layer environment, suggest a possible link to aromatic and mycosporine-like amino acids. Sea ice CDOM susceptibility to photo-bleaching was demonstrated in an in situ 120 hour exposure, during which we observed a loss in CDOM absorption of 53% at 280 nm, 58% at 330 nm, and 30% at 375 nm. No overall coincidental loss of DOC or DON was measured during the experimental period. A relationship between the spectral slope (S) and carbon-specific absorption (a *375) indicated that the characteristics of CDOM can be described by the mixing of two broad end-members; and aged material, present in brine and seawater samples characterised by high S values and low a *375; and a fresh material, due to elevated in situ

  2. Effect of organic fertilizers derived dissolved organic matter on pesticide sorption and leaching.

    PubMed

    Li, Kun; Xing, Baoshan; Torello, William A

    2005-03-01

    Incorporation of organic fertilizers/amendments has been, and continues to be, a popular strategy for golf course turfgrass management. Dissolved organic matter (DOM) derived from these organic materials may, however, facilitate organic chemical movement through soils. A batch equilibrium technique was used to evaluate the effects of organic fertilizer-derived DOM on sorption of three organic chemicals (2,4-D, naphthalene and chlorpyrifos) in USGA (United States Golf Association) sand, a mixed soil (70% USGA sand and 30% native soil) and a silt loam soil (Typic Fragiochrept). DOM was extracted from two commercial organic fertilizers. Column leaching experiments were also performed using USGA sand. Sorption experiments showed that sorption capacity was significantly reduced with increasing DOM concentration in solution for all three chemicals. Column experimental results were consistent with batch equilibrium data. These results suggest that organic fertilizer-derived DOM might lead to enhanced transport of applied chemicals in turf soils.

  3. FACTORS INFLUENCING PHOTOREACTIONS OF DISSOLVED ORGANIC MATTER IN A COASTAL RIVER OF THE SOUTHEASTERN UNITED STATES

    EPA Science Inventory

    Photoreactions of dissolved organic matter can affect the oxidizing capacity, nutrient dynamics, trace gas exchange, and color of surface waters. This study focuses on factors that affect the photoreactions of the colored dissolved organic matter (CDOM) in the Satilla River, a co...

  4. Bioavailable and biodegradable dissolved organic nitrogen in activated sludge and trickling filter wastewater treatment plants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A study was carried out to understand the fate of biodegradable dissolved organic nitrogen (BDON) and bioavailable dissolved organic nitrogen (ABDON) along the treatment trains of a wastewater treatment facility (WWTF) equipped with an activated sludge (AS) system and a WWTF equipped with a two-stag...

  5. DISSOLVED ORGANIC CARBON (DOC) CONCENTRATIONS IN SMALL STREAMS OF THE GEORGIA PIEDMONT

    EPA Science Inventory

    Dissolved organic matter (DOM) supports microbial activity and contributes to transport of N and P in streams. We have studied the impact of land uses on dissolved organic carbon (DOC) concentrations in 17 Georgia Piedmont headwater streams since January 2001. We classified the w...

  6. Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil.

    PubMed

    Weng, Liping; Temminghoff, Erwin J M; Lofts, Stephen; Tipping, Edward; Van Riemsdijk, Willem H

    2002-11-15

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.

  7. Long-term dynamics of dissolved organic carbon: implications for drinking water supply.

    PubMed

    Ledesma, José L J; Köhler, Stephan J; Futter, Martyn N

    2012-08-15

    Surface waters are the main source of drinking water in many regions. Increasing organic carbon concentrations are a cause for concern in Nordic countries since both dissolved and particulate organic carbon can transport contaminants and adversely affect drinking water treatment processes. We present a long-term study of dynamics of total (particulate and dissolved) organic carbon (TOC) concentrations in the River Fyris. This river supplies drinking water to approximately 200000 people in Uppsala, Sweden. The River Fyris is a main tributary to Lake Mälaren, which supplies drinking water to approximately 2 million people in the greater Stockholm area. Utilities responsible for drinking water supply in both Uppsala and Stockholm have expressed concerns about possible increases in TOC. We evaluate organic carbon dynamics within the Fyris catchment by calculating areal mass exports using observed TOC concentrations and modeled flows and by modeling dissolved organic carbon (as a proxy for TOC) using the dynamic, process based INCA-C model. Exports of TOC from the catchment ranged from 0.8 to 5.8 g m(-2) year(-1) in the period 1995-2010. The variation in annual exports was related to climatic variability which influenced seasonality and amount of runoff. Exports and discharge uncoupled at the end of 2008. A dramatic increase in TOC concentrations was observed in 2009, which gradually declined in 2010-2011. INCA-C successfully reproduced the intra- and inter-annual variation in concentrations during 1996-2008 and 2010-2011 but failed to capture the anomalous increase in 2009. We evaluated a number of hypotheses to explain the anomaly in 2009 TOC values, ultimately none proved satisfactory. We draw two main conclusions: there is at least one unknown or unmeasured process controlling or influencing surface water TOC and INCA-C can be used as part of the decision-making process for current and future use of rivers for drinking water supply.

  8. Determining Passive Sampler Partition Coefficients for Dissolved-phase Organic Contaminants

    EPA Science Inventory

    Passive samplers are used for environmental and analytical purposes to measure dissolved nonionic organic contaminants (NOCs) by absorption from a contaminated medium into a clean phase, usually in the form of a synthetic organic film. Recently developed passive sampler techniqu...

  9. Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter

    USGS Publications Warehouse

    Fleck, Jacob A.; Gill, Gary W.; Bergamaschi, Brian A.; Kraus, Tamara E.C.; Downing, Bryan D.; Alpers, Charles N.

    2014-01-01

    Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5 × 10-3 m2 mol-1 (s.d. 3.5 × 10-3) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg–DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

  10. [Spectral Characteristic of Dissolved Organic Matter in Xiaohe River, Hebei].

    PubMed

    Yu, Min-da; Zhang, Hui; He, Xiao-song; Tan, Wen-bing; Zhang, Yuan; Ma, Li-na; Xi, Bei-dou; Dang, Qiu-ling; Gao, Ru-tai

    2015-09-01

    The spectral characteristic of dissolved organic matter (DOM) in Xiaohe River, Hebei, was investigated by fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, and basic chemical water quality indicators. The data was then statistical analyzed using principal component analysis and correlation analysis method. The result based on 3D excitation-emission matrix fluorescence spectroscopy showed that DOM in Xiaohe River contained both protein-like and humus-like components. DOM and N-containing compounds were obviously correlated with COD, especially between NH4+ -N and humic-like component, indicating that COD of water in Xiaohe River can be reduced by removing NH4+ -N and DOM, which could be good indicators for monitoring water quality in the future. The relative content of protein-like component reduces gradually along the downstream, while that of humic-like component showed an increasing trend. DOM in samples S1 and S2 was mainly consisted of humic-like components with larger molecular weight and higher aromaticity, while that in samples S3 and S6 was mainly consisted of protein-like components with smaller molecular weight, lower aromaticity, which are easier to be degraded. Therefore, in order to enhance the remove of refractory humic-like substances, sewage treatment plants of S1 and S2 or improved membrane treatment equipment with better removal effect of macromolecules should be provide. On the other hand, the anaerobic and aerobic biological treatment processes should be optimized in S3 and S6, so as to better remove these degradable protein-like substances.

  11. Biogeochemical Processes That Produce Dissolved Organic Matter From Wheat Straw

    USGS Publications Warehouse

    Wershaw, Robert L.; Rutherford, David W.; Leenheer, Jerry A.; Kennedy, Kay R.; Cox, Larry G.; Koci, Donald R.

    2003-01-01

    The chemical reactions that lead to the formation of dissolved organic matter (DOM) in natural waters are poorly understood. Studies on the formation of DOM generally are complicated because almost all DOM isolates have been derived from mixtures of plant species composed of a wide variety of different types of precursor compounds for DOM formation. This report describes a study of DOM derived mainly from bales of wheat straw that had been left in a field for several years. During this period of time, black water from the decomposing wheat straw accumulated in pools in the field. The nuclear magnetic resonance and infrared spectra of the black water DOM indicate that it is composed almost entirely of lignin and carbohydrate polymeric units. Analysis by high-performance size-exclusion chromatography with multi-angle laser-light scattering detection indicates that the number average molecular weight of the DOM is 124,000 daltons. The results presented in this report indicate that the black water DOM is composed of hemicellulose chains cross-linked to lignin oligomers. These types of structures have been shown to exist in the hemicellulose matrix of plant cell walls. The cross-linked lignin-hemicellulose complexes apparently were released from partially degraded wheat-straw cell walls with little alteration. In solution in the black water, these lignin-hemicellulose polymers fold into compact globular particles in which the nonpolar parts of the polymer form the interiors of the particles and the polar groups are on the exterior surfaces of the particles. The tightly folded, compact conformation of these particles probably renders them relatively resistant to microbial degradation. This should be especially the case for the aromatic lignin structures that will be buried in the interiors of the particles.

  12. Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

    PubMed

    Fleck, Jacob A; Gill, Gary; Bergamaschi, Brian A; Kraus, Tamara E C; Downing, Bryan D; Alpers, Charles N

    2014-06-15

    Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

  13. Seqestration of dissolved organic carbon in the deep sea

    SciTech Connect

    Daniel J. Repeta

    2006-03-01

    There are 600 GT of dissolved organic carbon (DOC) sequestered in seawater. The marine inventory of DOC is set by its concentration in the deep sea, which is nearly constant at 35+2µM C, irrespective of sample location or depth. Isotopic measurements show deep sea DOC to be depleted in radiocarbon, with an apparent radiocarbon age of between 4000ybp (Atlantic) and 6000ybp (Pacific). From the radiocarbon data, we can infer that deep sea DOC is inert and does not cycle on less than millennial time scales. However, high precision DOC measurements show deep sea concentrations are variable at the + 1-2µM DOC level, suggesting a fraction of deep sea DOC, equivalent to 15-30Gt C, is cycling on short time scales, acting as a sink for new, atmospheric carbon. This project is designed to identify and quantify the biological and physical processes that sequester DOM in the deep sea by making compound specific radiocarbon measurements on sugars and proteins extracted from deep sea DOC. Our Hawaii surface seawater sample has a DIC Δ14C value of 72 + 7 ‰ and shows the influence of bomb radiocarbon on surface water DIC values. HMWDOC Δ14C is 10 ‰, significantly depleted in radiocarbon relative to DIC. Purification of HMWDOC by reverse phase HPLC yields seven neutral sugars with radiocarbon values of 47 – 67‰. Assuming the radiocarbon determinations of individual sugars in HMWDOC serve as replicates, then the average Δ14C for neutral sugars in HMWDOC is 57 + 6 ‰(1 SD, n=11), only slightly depleted in 14C relative to DIC. There has been a sharp decrease in radiocarbon values for DIC in the North Pacific Ocean over the past few decades. If neutral sugars cycle more slowly than DIC, we would expect them to have correspondingly higher radiocarbon values. Previous studies have modeled upper ocean DOC as a two component mixture of newly synthesized DOC with a radiocarbon value equal to DIC, and an old component with a radiocarbon value equal to deep sea DO14C. In order to

  14. Impact of dataset diversity on accuracy and sensitivity of parallel factor analysis model of dissolved organic matter fluorescence excitation-emission matrix

    PubMed Central

    Yu, Huarong; Liang, Heng; Qu, Fangshu; Han, Zheng-shuang; Shao, Senlin; Chang, Haiqing; Li, Guibai

    2015-01-01

    Parallel factor (PARAFAC) analysis enables a quantitative analysis of excitation-emission matrix (EEM). The impact of a spectral variability stemmed from a diverse dataset on the representativeness of the PARAFAC model needs to be examined. In this study, samples from a river, effluent of a wastewater treatment plant, and algae secretion were collected and subjected to PARAFAC analysis. PARAFAC models of global dataset and individual datasets were compared. It was found that the peak shift derived from source diversity undermined the accuracy of the global model. The results imply that building a universal PARAFAC model that can be widely available for fitting new EEMs would be quite difficult, but fitting EEMs to existing PARAFAC model that belong to a similar environment would be more realistic. The accuracy of online monitoring strategy that monitors the fluorescence intensities at the peaks of PARAFAC components was examined by correlating the EEM data with the maximum fluorescence (Fmax) modeled by PARAFAC. For the individual datasets, remarkable correlations were obtained around the peak positions. However, an analysis of cocktail datasets implies that the involvement of foreign components that are spectrally similar to local components would undermine the online monitoring strategy. PMID:25958786

  15. Hydropedological hotspots for dissolved organic carbon loading to streams along the perhumid temperate rainforest coastal margin of Alaska.

    NASA Astrophysics Data System (ADS)

    D'Amore, D. V.; Edwards, R.; Herendeen, P. A.; Fellman, J.; Hood, E. W.

    2015-12-01

    Integrating terrestrial and aquatic biogeochemical research is essential for understanding the amount of material exported from terrestrial systems to streams and coastal margins. Integrated models are needed to elucidate how shifts in vegetation communities driven by soil moisture can predict plant community composition and biomass changes that alter the balance of carbon cycling and export to aquatic systems. Soil saturation has long been recognized as an important control on many ecological and biogeochemical relationships in coastal rainforests. However, the lack of working models for soil drainage with enough precision to provide accurate site assessments has limited interpretations of biogeochemical fluxes from terrestrial ecosystems to coastal zones. We have established a hydropedological model that can be used to identify the spatial distribution and seasonal fluctuations of soil saturation and associated anaerobic conditions in soils. Periods of critical DOC loading and peak export associated with these conditions highlight the ability of rainforest soils to produce copious quantities of dissolved organic carbon export to streams. The loading of dissolved organic carbon to streams is closely coupled to seasonal temperature cycles, but constrained by the flow of water through the soil matrix. Episodic storm surges produce varying amounts of dissolved organic carbon flow depending on antecedent conditions. The largest amount of dissolved organic carbon loading to streams occurs after peak temperature and coincident with higher storm surges. Dissolved organic carbon flows more frequently and in higher quantities from wetland soils, but is also produced in large quantities from upland soils. These advances in modeling hydropedologic functions and dissolved organic carbon export establish a framework for climate change vulnerability assessments in rainforest soils.

  16. Applications of Fluorescence Spectroscopy for dissolved organic matter characterization in wastewater treatment plants

    NASA Astrophysics Data System (ADS)

    Goffin, Angélique; Guérin, Sabrina; Rocher, Vincent; Varrault, Gilles

    2016-04-01

    Dissolved organic matter (DOM) influences wastewater treatment plants efficiency (WTTP): variations in its quality and quantity can induce a foaming phenomenon and a fouling event inside biofiltration processes. Moreover, in order to manage denitrification step (control and optimization of the nitrate recirculation), it is important to be able to estimate biodegradable organic matter quantity before biological treatment. But the current methods used to characterize organic matter quality, like biological oxygen demand are laborious, time consuming and sometimes not applicable to directly monitor organic matter in situ. In the context of MOCOPEE research program (www.mocopee.com), this study aims to assess the use of optical techniques, such as UV-Visible absorbance and more specifically fluorescence spectroscopy in order to monitor and to optimize process efficiency in WWTP. Fluorescence excitation-emission matrix (EEM) spectroscopy was employed to prospect the possibility of using this technology online and in real time to characterize dissolved organic matter in different effluents of the WWTP Seine Centre (240,000 m3/day) in Paris, France. 35 sewage water influent samples were collected on 10 days at different hours. Data treatment were performed by two methods: peak picking and parallel factor analysis (PARAFAC). An evolution of DOM quality (position of excitation - emission peaks) and quantity (intensity of fluorescence) was observed between the different treatment steps (influent, primary treatment, biological treatment, effluent). Correlations were found between fluorescence indicators and different water quality key parameters in the sewage influents. We developed different multivariate linear regression models in order to predict a variety of water quality parameters by fluorescence intensity at specific excitation-emission wavelengths. For example dissolved biological oxygen demand (r2=0,900; p<0,0001) and ammonium concentration (r2=0,898; p<0

  17. Analytical Determinations of the Phenolic Content of Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Pagano, T.; Kenny, J. E.

    2010-12-01

    Indicators suggest that the amount of dissolved organic matter (DOM) in natural waters is increasing. Climate Change has been proposed as a potential contributor to the trend, and under this mechanism, the phenolic content of DOM may also be increasing. We have explored the possibility of assessing the phenolic character of DOM using fluorescence spectroscopy as a more convenient alternative to wet chemistry methods. In this work, parallel factor analysis (PARAFAC) was applied to fluorescence excitation emission matrices (EEMs) of humic samples in an attempt to analyze their phenolic content. The PARAFAC results were correlated with phenol concentrations derived from the Folin-Ciocalteau reagent-based method. The reagent-based method showed that the phenolic content of five International Humic Substance Society (IHSS) DOM samples vary from approximately 5 to 22 ppm Tannic Acid Equivalents (TAE) in phenol concentration. A five-component PARAFAC fit was applied to the EEMs of the IHSS sample dataset and it was determined by PARAFAC score correlations with phenol concentrations from the reagent-based method that components C1 (R2=0.78), C4 (R2=0.82), and C5 (R2=0.88) have the highest probability of containing phenolic groups. Furthermore, when the scores of components C4 and C5 were summed, the correlation improved (R2=0.99). Likewise, when the scores of C1, C4, and C5 were summed, their correlations were stronger than their individual parts (R2=0.89). Since the reagent-based method is providing an indicator of “total phenol” amount, regardless of the exact molecular structure of C1, C4, and C5, it seems reasonable that each of these components individually contributes a portion to the summed “total phenol” profile, and that the sum of their phenol-related spectral parts represents a larger portion of the “total phenol” index. However, when the sum of all five components were plotted against the reagent-based phenol concentrations, due to the considerable

  18. Insight into dissolved organic matter fractions in Lake Wivenhoe during and after a major flood.

    PubMed

    Aryal, Rupak; Grinham, Alistair; Beecham, Simon

    2016-03-01

    Dissolved organic matter is an important component of biogeochemical processes in aquatic environments. Dissolved organic matter may consist of a myriad of different fractions and resultant processing pathways. In early January 2011, heavy rainfall occurred across South East Queensland, Australia causing significant catchment inflow into Lake Wivenhoe, which is the largest water supply reservoir for the city of Brisbane, Australia. The horizontal and vertical distributions of dissolved organic matter fractions in the lake during the flood period were investigated and then compared with stratified conditions with no catchment inflows. The results clearly demonstrate a large variation in dissolved organic matter fractions associated with inflow conditions compared with stratified conditions. During inflows, dissolved organic matter concentrations in the reservoir were fivefold lower than during stratified conditions. Within the dissolved organic matter fractions during inflow, the hydrophobic and humic acid fractions were almost half those recorded during the stratified period whilst low molecular weight neutrals were higher during the flood period compared to during the stratified period. Information on dissolved organic matter and the spatial and vertical variations in its constituents' concentrations across the lake can be very useful for catchment and lake management and for selecting appropriate water treatment processes.

  19. Influence of dissolved organic substances in groundwater on sorption behavior of americium and neptunium

    SciTech Connect

    Boggs, S. Jr.; Seitz, M.G.

    1984-01-01

    Groundwaters typically contain dissolved organic carbon consisting largely of high molecular weight compounds of humic and fulvic acids. To evaluate whether these dissolved organic substances can enhance the tranport of radionuclides through the groundwater system, experiments were conducted to examine the sorption of americium and neptunium onto crushed basalt in the presence of dissolved humic- and fulvic-acid organic carbon introduced into synthetic groundwater. The partitioning experiments with synthetic groundwater show that increasing the concentration of either humic or fulvic acid in the water has a significant inhibiting effect on sorption of both americium and neptunium. At 22/sup 0/C, adsorption of these radionuclides, as measured by distribution ratios (the ratio of nuclide sorbed onto the solid to nuclide in solution at the end of the experiment), decreased by 25% to 50% by addition of as little as 1 mg/L dissolved organic carbon and by one to two orders of magnitude by addition of 100 to 200 mg/L dissolved organic carbon. Distribution ratios measured in solutions reacted at 90/sup 0/C similarly decreased with the addition of dissolved organic carbon but generally ranged from one to two orders of magnitude higher than those determined in the 22/sup 0/C experiment. These results suggest that organic carbon dissolved in deep groundwaters may significantly enhance the mobility of radionuclides of americium and neptunium. 23 references, 5 figures, 11 tables.

  20. Determination of the Fate of Dissolved Organic Nitrogen in the Three Wastewater Treatment Plants, Jordan

    ERIC Educational Resources Information Center

    Wedyan, Mohammed; Al Harahsheh, Ahmed; Qnaisb, Esam

    2016-01-01

    This research aimed to assess the composition of total dissolved nitrogen (TDN) species, particularly dissolved organic nitrogen (DON), over the traditional wastewater treatment operations in three biological nutrient removal (BNR) wastewater treatment plants (WWTPs) in Jordan. It had been found that the DON percentage was up to 30% of TDN within…

  1. Pulsed, cross-shelf export of terrigenous dissolved organic carbon to the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Fichot, Cédric G.; Lohrenz, Steven E.; Benner, Ronald

    2014-02-01

    The export of terrigenous dissolved organic carbon (tDOC) and other river-borne material across the continental shelf boundary has important ramifications for biological productivity and the cycling of continentally derived bioelements in the ocean. Recent studies revealed the 275-295 nm spectral slope coefficient of chromophoric dissolved organic matter (CDOM), S275-295, is a reliable tracer for terrigenous dissolved organic carbon (tDOC) in river-influenced ocean margins. Here an empirical algorithm for the accurate retrieval of S275-295 from ocean color was developed and validated using in situ optical properties collected seasonally in the northern Gulf of Mexico. This study also demonstrated S275-295 is a robust proxy for tDOC concentration in this environment, thereby providing a means to derive surface tDOC concentrations on synoptic scales and in quasi-real time using remote sensing. The resulting tDOC-algorithm was implemented using Aqua-MODIS in a retrospective analysis of surface tDOC concentrations over the northern Gulf of Mexico between July 2002 and June 2013. Large pulses of tDOC were observed in continental-slope surface waters off the Mississippi River delta, indicating cross-shelf export of tDOC was sporadic and exhibited considerable interannual variability. Favorable winds following an anomalously high discharge from the Mississippi-Atchafalaya river system always coincided with a major export event, and in general, cross-shelf export was enhanced during years of anomalously high discharge. The tDOC-algorithm will find applicability in the assessment of future climate- and human-induced changes in tDOC export, in biogeochemical models of the continental shelf, and in the validation of high-resolution coastal models of buoyancy-driven shelf circulation.

  2. Kinetics and equilibrium of adsorption of dissolved organic matter fractions from secondary effluent by fly ash.

    PubMed

    Wei, Liangliang; Wang, Kun; Zhao, Qingliang; Xie, Chunmei; Qiu, Wei; Jia, Ting

    2011-01-01

    Fly ash was used as a low-cost adsorbent for removing dissolved organic matter (DOM) in secondary effluent. Batch experiments were conducted under various adsorbent dosages, pH, contact time, temperatures and DOM fractional characteristics. Under the optimum conditions of fly ash dosage of 15 g/L, temperature of 303 K and contact time of 180 min, a removal of 22.5% of the dissolved organic carbon (DOC), 23.7% of UV-254, 25.9% of the trihalomethanes precursors in secondary effluent was obtained. The adsorption of DOM fractions onto fly ash all followed the pseudo second-order kinetic model, and the hydrophilic fraction adsorption by fly ash also fitted the intraparticle diffusion model quite well. Freundlich and Langmuir models were applicable to the fly ash adsorption and their constants were evaluated. The maximum adsorption capacities of the adsorptions revealed that fly ash was more effective in adsorbing hydrophilic fraction than the acidic fractions. Structure changes of the DOM fractions after fly ash adsorption were also characterized via spectrum analyzing. Those mechanisms presented critical step toward improved efficiencies of fly ash adsorption via further surface-modification.

  3. Influence of dissolved organic matter on dissolved vanadium speciation in the Churchill River estuary (Manitoba, Canada).

    PubMed

    Shi, Yong Xiang; Mangal, Vaughn; Guéguen, Céline

    2016-07-01

    Diffusive gradients in thin films (DGT) devices were used to investigate the temporal and spatial changes in vanadium (V) speciation in the Churchill estuary system (Manitoba). Thirty-six DGT sets and 95 discrete water samples were collected at 8 river and 3 estuary sites during spring freshet and summer base flow. Dissolved V concentration in the Churchill River at summer base flow was approximately 5 times higher than those during the spring high flow (27.3 ± 18.9 nM vs 4.8 ± 3.5 nM). DGT-labile V showed an opposite trend with greater values found during the spring high flow (2.6 ± 1.8 nM vs 1.4 ± 0.3 nM). Parallel factor analysis (PARAFAC) conducted on 95 excitation-emission matrix spectra validated four humic-like (C1C4) and one protein-like (C5) fluorescent components. Significant positive relationship was found between protein-like DOM and DGT-labile V (r = 0.53, p < 0.05), indicating that protein-like DOM possibly affected the DGT-labile V concentration in Churchill River. Sediment leachates were enriched in DGT-labile V and protein-like DOM, which can be readily released when river sediment began to thaw during spring freshet.

  4. EFFECTS OF REVERSE OSMOSIS ISOLATION ON REACTIVITY OF NATURALLY OCCURRING DISSOLVED ORGANIC MATTER IN PHYSICOCHEMICAL PROCESSES. (R828045)

    EPA Science Inventory

    A field reverse osmosis system was used to isolate dissolved organic matter (DOM) from two lacustrine and two riverine surface water sources. The rejection of DOM was on the order of 99% and did not vary significantly with pressure. A simple mass balance model using a single m...

  5. Dissolved organic carbon source integration in an agricultural watershed

    NASA Astrophysics Data System (ADS)

    Hernes, P. J.; Spencer, R. G.; Dyda, R. Y.; Pellerin, B. A.; Bachand, P. A.; Bergamaschi, B. A.

    2012-12-01

    The dissolved organic carbon (DOC) chemistry and concentration at the mouth of a watershed represents an integrated signal of all sources and process that occur upstream of the mouth, however, the relative contributions of all those sources and processes to the chemistry and concentration is not equal. We sampled an agricultural watershed in the Sacramento River valley in California synoptically on multiple occasions in order to better identify the most important contributors to DOC chemistry. Our samples included headwater samples from native grasslands in three sub-catchments, samples within the agricultural portions of those sub-watersheds, samples near the conjunctions, and irrigation field inputs and outputs. DOC concentrations increase considerably in the agricultural portion of the watershed, demonstrating the impacts of anthropogenic disturbance of landscapes as well as the potential for local landscapes to contribute significantly to the overall DOC concentration and chemistry. The central sub-catchment in particular had significantly greater DOC concentrations, which appears to correspond to the much greater proportion of flood irrigation land management in this portion, as our field runoff measurements indicate much higher added DOC during flood irrigation than during furrow irrigation. Flow-weighted averaging of the three sub-catchment DOC concentrations does not replicate concentrations at the mouth (1-6 km downstream of the confluences), indicating the importance of in-stream processing and/or source inputs from riparian zones even along the mainstem. Optical characterization of DOC demonstrates changing chemistry from season to season, and differences in chemistry from different areas of the catchment. The storm-influenced spring sampling yielded higher carbon-specific UV absorbance at 254 nm (SUVA254), indicating a higher proportion of aromaticity, while the southern sub-catchment consistently yielded the highest spectral slope values, which

  6. Characteristics and transformations of dissolved organic nitrogen in municipal biological nitrogen removal wastewater treatment plants

    NASA Astrophysics Data System (ADS)

    Huo, Shouliang; Xi, Beidou; Yu, Honglei; Qin, Yanwen; Zan, Fengyu; Zhang, Jingtian

    2013-12-01

    Dissolved organic nitrogen (DON) represents most of the dissolved nitrogen in the effluent of biological nitrogen removal (BNR) wastewater treatment plants (WWTPs). The characteristics of wastewater-derived DON in two different WWTPs were investigated by several different methods. The major removals of DON and biodegradable dissolved organic nitrogen (BDON) along the treatment train were observed in the anaerobic process. Dissolved combined amino acids (DCAA) and dissolved free amino acids (DFAA) in the effluent accounted approximately for less than 4% and 1% of the effluent DON, respectively. Approximately half of wastewater-derived DON was capable of passing through a 1 kDa ultrafilter, and low MW DON cannot effectively be removed by BNR processes. More than 80% of effluent DON was composed of hydrophilic compounds, which stimulate algal growth. The study provided important information for future upgrading of WWTPs or the selection of DON removal systems to meet more demanding nitrogen discharge limits.

  7. Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

    USGS Publications Warehouse

    Pohlman, J.W.; Bauer, J.E.; Waite, W.F.; Osburn, C.L.; Chapman, N.R.

    2011-01-01

    Marine sediments contain about 500-10,000 Gt of methane carbon, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined, but it releases relatively little methane to the ocean and atmosphere. Sedimentary microbes convert most of the dissolved methane to carbon dioxide. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use ??14 C and ??13 C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13 C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000-6,000 year age of dissolved organic carbon in the deep ocean, and provide reduced organic matter and energy to deep-ocean microbial communities. ?? 2011 Macmillan Publishers Limited. All rights reserved.

  8. Impact of solids retention time on dissolved organic nitrogen and its biodegradability in treated wastewater

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic nitrogen (DON) and its biodegradability in treated wastewater have recently gained attention because DON potentially causes oxygen depletion and/or eutrophication in receiving waters. Laboratory scale chemostat experiments were conducted at 9 different solids retention times (SRTs)...

  9. Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic carbon (DOC) components of soil amendments such as biochar will influence the fundamental soil chemistry including the metal speciation, nutrient availability, and microbial activity. Quantitative correlation is necessary between (i) pyrogenic DOC components of varying aromaticity...

  10. CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) SOURCE CHARACTERIZATION IN THE LOUISIANA BIGHT

    EPA Science Inventory

    Chromophoric dissolved organic matter (CDOM) in the Mississippi plume region may have several distinct sources: riverine (terrestrial soils), wetland (terrestrial plants), biological production (phytoplankton, zooplankton, microbial), and sediments. Complex mixing, photodegradati...

  11. Northern Gulf of Mexico estuarine coloured dissolved organic matter derived from MODIS data

    EPA Science Inventory

    Coloured dissolved organic matter (CDOM) is relevant for water quality management and may become an important measure to complement future water quality assessment programmes. An approach to derive CDOM using the Moderate Resolution Imaging Spectroradiometer (MODIS) was developed...

  12. DISSOLVED ORGANIC CARBON TRENDS RESULTING FROM CHANGES IN ATMOSPHERIC DEPOSITION CHEMISTRY

    EPA Science Inventory

    Several hypotheses have been proposed to explain recent, widespread increases in concentrations of dissolved organic carbon (DOC) in the surface waters of glaciated landscapes across eastern North America and northern and central Europe. Some invoke anthropogenic forcing through ...

  13. Sources and Fates of Dissolved Organic Matter in the Mid-Atlantic Bight

    SciTech Connect

    Hopkinson, C. S.

    2000-08-16

    The objectives of the research program were to identify and determine the relative importance of various sources of dissolved organic matter to the continental shelf, and to estimate the net carbon balance for the Middle Atlantic Bight.

  14. Photobleaching Kinetics of Chromophoric Dissolved Organic Matter Derived from Mangrove Leaf Litter and Floating Sargassum Colonies

    EPA Science Inventory

    We examined the photoreactivity of chromophoric dissolved organic matter (CDOM) derived from Rhizophora mangle (red mangrove) leaf litter and floating Sargassum colonies as these marine plants can be important contributors to coastal and open ocean CDOM pools, respectively. Mangr...

  15. [Sources of dissolved organic carbon and the bioavailability of dissolved carbohydrates in the tributaries of Lake Taihu].

    PubMed

    Ye, Lin-Lin; Wu, Xiao-Dong; Kong, Fan-Xiang; Liu, Bo; Yan, De-Zhi

    2015-03-01

    Surface water samples of Yincungang and Chendonggang Rivers were collected from September 2012 to August 2013 in Lake Taihu. Water temperature, Chlorophyll a and bacterial abundance were analyzed, as well as dissolved organic carbon (DOC) concentrations, stable carbon isotope of DOC (Δ13C(DOC)), specific UV absorbance (SUVA254 ) and dissolved carbohydrates concentrations. Δ13C(DOC) ranged from -27.03% per thousand ± 0.30% per thousand to -23.38%per thousand ± 0.20% per thousand, indicating a terrestrial source. Both the autochthonous and allochthonous sources contributed to the carbohydrates pool in the tributaries. Significant differences in PCHO (polysaccharides) and MCHO (monosaccharides) concentrations were observed between spring-summer and autumn-winter (P < 0.01, n = 12; P < 0.01, n = 12), which might be caused by the variation in the sources and bioavailability of carbohydrates. PCHO contributed a major fraction to TCHO (total dissolved carbohydrates) in autumn and winter, which could be explained by the accumulation of undegradable PCHO limited by the low water temperature; MCHO contributed a major fraction to TCHO in spring and summer, which might be caused by the transformation from PCHO by microbes at high water temperature.

  16. Mechanisms of dissolved organic carbon cycling in an ocean margin. Final technical report

    SciTech Connect

    Benner, R.

    1997-11-24

    Dissolved organic carbon (DOC) is the largest reservoir of organic carbon in the ocean, and the objectives of this project were to investigate the mechanisms and pathways of DOC formation and consumption in seawater. Carbohydrates are the most abundant form of DOC, and this project included measurements of dissolved carbohydrates as well as DOC to help delineate the cycling of DOC. Many of the methods and approaches for investigating DOC production were developed as part of this project.

  17. PHOTOCHEMICAL ALTERATION OF DISSOLVED ORGANIC MATTER: EFFECTS ON THE CONCENTRATION AND ACIDITIES OF IONIZABLE SITES IN DISSOLVED ORGANIC MATTER IN THE SATILLA RIVER OF GEORGIA, USA

    EPA Science Inventory

    The acid-base properties of humic substances, the major component of dissolved organic matter (DOM), area major control on the alkalinity, or acid neutralizing capacity of freshwater systems. Alkalinity is one of the fundamental parameters measured in aquatic sciences, and is an ...

  18. Effect of dissolved organic matter from treated effluents on sorption of atrazine and prometryn by soils

    SciTech Connect

    Seol, Y.; Lee, L.S.

    2000-01-02

    The apparent enhanced transport of soil-applied atrazine following irrigation of treated effluents has been hypothesized to be from complexation of atrazine with effluent-borne dissolved organic matter (DOM). Under long-term effluent irrigation, even small DOM-induced decreases in pesticide sorption can result in significant enhanced pesticide movement due to cumulative effects. The effect of atrazine and prometryn association with DOM extracted from municipal wastewater (MW), swine-derived lagoon wastewater (SW), and dissolved Aldrich humic acid (HA) on sorption by two soils was measured in batch equilibration studies. Individual association of pesticides to DOM, sorption of DOM to soil, and pesticide sorption by soil were also quantified. Pesticide association to DOM normalized to organic carbon (OC) ranged from 30 to 1000 L/kg OC. DOM sorption by soil ranged from 1.5 to 10 L/kg with a silt loam having a higher affinity for the DOM than the sandy loam. DOM up to 150 mg OC/L did not significantly suppress sorption by soils of either atrazine or prometryne in agreement with predictions using the independently measured binary distribution coefficients in a model that assumed linear equilibrium behavior among pesticide, soil, and DOM. A sensitivity analysis was performed using the same model to identify what combination of soil, pesticide, and DOC variables may suppress sorption, resulting in facilitated transport. Results from the sensitivity analysis are presented and the potential for effluent properties other than DOM to facilitate pesticide transport is discussed.

  19. The removal kinetics of dissolved organic matter and the optical clarity of groundwater

    NASA Astrophysics Data System (ADS)

    Chapelle, Francis H.; Shen, Yuan; Strom, Eric W.; Benner, Ronald

    2016-09-01

    Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d-1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d-1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20-75 μM; 0.26-1 mg L-1) and ultraviolet absorption coefficient values ( a 254 < 5 m-1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.

  20. Dissolved organic matter in anoxic pore waters from Mangrove Lake, Bermuda

    USGS Publications Warehouse

    Orem, W.H.; Hatcher, P.G.; Spiker, E. C.; Szeverenyi, N.M.; Maciel, G.E.

    1986-01-01

    Dissolved organic matter and dissolved inorganic chemical species in anoxic pore water from Mangrove Lake, Bermuda sediments were studied to evaluate the role of pore water in the early diagenesis of organic matter. Dissolved sulphate, titration alkalinity, phosphate, and ammonia concentration versus depth profiles were typical of many nearshore clastic sediments and indicated sulphate reduction in the upper 100 cm of sediment. The dissolved organic matter in the pore water was made up predominantly of large molecules, was concentrated from large quantities of pore water by using ultrafiltration and was extensively tudied by using elemental and stable carbon isotope analysis and high-resolution, solid state 13C nuclear magnetic resonance and infrared spectroscopy. The results indicate that this material has a predominantly polysaccharide-like structure and in addition contains a large amount of oxygen-containing functional groups (e.g., carboxyl groups). The 13C nulcear magnetic resonance spectra of the high-molecular-weight dissolved organic matter resemble those of the organic matter in the surface sediments of Mangrove Lake. We propose that this high-molecular-weight organic matter in pore waters represents the partially degraded, labile organic components of the sedimentary organic matter and that pore waters serve as a conduit for removal of these labile organic components from the sediments. The more refractory components are, thus, selectively preserved in the sediments as humic substances (primarily humin). ?? 1986.

  1. Chemical characterization of dissolved organic compounds from coastal sea surface microlayers (Baltic Sea, Germany).

    PubMed

    van Pinxteren, Manuela; Müller, Conny; Iinuma, Yoshiteru; Stolle, Christian; Herrmann, Hartmut

    2012-10-02

    The physicochemical properties of the sea surface microlayer (SML), i.e. the boundary layer between the air and the sea, and its impact on air-sea exchange processes have been investigated for decades. However, a detailed description about these processes remains incomplete. In order to obtain a better chemical characterization of the SML, in a case study three pairs of SML and corresponding bulk water samples were taken in the southern Baltic Sea. The samples were analyzed for dissolved organic carbon and dissolved total nitrogen, as well as for several organic nitrogen containing compounds and carbohydrates, namely aliphatic amines, dissolved free amino acids, dissolved free monosaccharides, sugar alcohols, and monosaccharide anhydrates. Therefore, reasonable analytical procedures with respect to desalting and enrichment were established. All aliphatic amines and the majority of the investigated amino acids (11 out of 18) were found in the samples with average concentrations between 53 ng L(-1) and 1574 ng L(-1). The concentrations of carbohydrates were slightly higher, averaging 2900 ng L(-1). Calculation of the enrichment factor (EF) between the sea surface microlayer and the bulk water showed that dissolved total nitrogen was more enriched (EF: 1.1 and 1.2) in the SML than dissolved organic carbon (EF: 1.0 and 1.1). The nitrogen containing organic compounds were generally found to be enriched in the SML (EF: 1.9-9.2), whereas dissolved carbohydrates were not enriched or even depleted (EF: 0.7-1.2). Although the investigated compounds contributed on average only 0.3% to the dissolved organic carbon and 0.4% to the total dissolved nitrogen fraction, these results underline the importance of single compound analysis to determine SML structure, function, and its potential for a transfer of compounds into the atmosphere.

  2. Photoproduction of dissolved organic carbon and inorganic nutrients from resuspended lake sediments.

    PubMed

    Hu, Bin; Wang, Peifang; Zhang, Nannan; Wang, Chao; Ao, Yanhui

    2016-11-01

    Sediments exposed to simulated solar radiation can serve as an important source of dissolved organic carbon (DOC) to surrounding waters. However, it is still unclear if dissolved nutrients can be photoproduced from lake sedimentary organic matter. In this study, a series of laboratory-based experiments was conducted to address the photoproduction of dissolved inorganic nutrients and DOC from resuspended Taihu Lake sediments. Dissolved inorganic nutrients and DOC were photoproduced after 8-h irradiation. The released NH4(+), NOx(-), and DOC levels ranged from 3.57 to 12.14, 1.43 to 6.43, and 24.17 to 69.17 μmol L(-1), respectively. The variation in the amount released indicated that sediment source had an effect on DOC and nutrient photorelease. More DOC and nutrients were released from higher concentration suspensions. However, due to the light absorption by suspended sediment, less DOC and nutrients were released from per gram of suspended sediment in high concentration suspensions. The decrease in DOC and increase in dissolved inorganic nitrogen during the last 2-h irradiation indicated that the photoproduction of inorganic nutrients proceeded via direct photodissolution of suspended sediments and subsequent photodegradation of the produced dissolved organic matter. Our results demonstrated that the photoproduction flux of NH4(+) and NOx(-) accounts for 12.3 and 6.5 % of wet deposition, respectively, which suggest that the photodissolution of suspended sediment could be a potential source of DOC and dissolved nutrients in shallow water ecosystems.

  3. Landscape controls on dissolved nutrients, organic matter and major ions in a suburbanizing watershed

    NASA Astrophysics Data System (ADS)

    Daley, M. L.; McDowell, W. H.

    2010-12-01

    differently to hydrologic events. Concentrations of DON were negatively correlated with discharge (r2= 0.06, p < 0.01), but DOC concentrations did not respond to discharge, suggesting there is much to learn about the decoupling of C and N rich dissolved organic matter (DOM). Our landscape models do not account for spatial variability in dissolved inorganic carbon (DIC), dissolved organic P (DOP) or particulate C, N and P; however, at our site with the longest record, the Lamprey River, DIC and particulate C account for only 25% and 5% respectively of the total C flux. Among three sites ranging from 3-16% development, particulate N only accounted for 12-18% of total N, but particulate P accounted for 30-50% and DOP accounted for an additional 40-50% of total P. Landscape characteristics may in fact be better predictors of spatial variability in particulate-P and DOP than PO4-P. Nonetheless, the landscape models that we have developed for DIN and DOM flux can be used by local watershed managers to predict changes in water quality in response to changes in land use.

  4. Direct estimation of dissolved organic carbon using synchronous fluorescence and independent component analysis (ICA): advantages of a multivariate calibration.

    PubMed

    De Almeida Brehm, Franciane; de Azevedo, Julio Cesar R; da Costa Pereira, Jorge; Burrows, Hugh D

    2015-11-01

    Dissolved organic carbon (DOC) is frequently used as a diagnostic parameter for the identification of environmental contamination in aqueous systems. Since this organic matter is evolving and decaying over time. If samples are collected under environmental conditions, some sample stabilization process is needed until the corresponding analysis can be made. This may affect the analysis results. This problem can be avoided using the direct determination of DOC. We report a study using in situ synchronous fluorescence spectra, with independent component analysis to retrieve relevant major spectral contributions and their respective component contributions, for the direct determination of DOC. Fluorescence spectroscopy is a very powerful and sensitive technique to evaluate vestigial organic matter dissolved in water and is thus suited for the analytical task of direct monitoring of dissolved organic matter in water, thus avoiding the need for the stabilization step. We also report the development of an accurate calibration model for dissolved organic carbon determinations using environmental samples of humic and fulvic acids. The method described opens the opportunity for a fast, in locus, DOC estimation in environmental or other field studies using a portable fluorescence spectrometer. This combines the benefits of the use of fresh samples, without the need of stabilizers, and also allows the interpretation of various additional spectral contributions based on their respective estimated properties. We show how independent component analysis may be used to describe tyrosine, tryptophan, humic acid and fulvic acid spectra and, thus, to retrieve the respective individual component contribution to the DOC.

  5. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

    SciTech Connect

    Lindsey, M.E.; Tarr, M.A.

    2000-02-01

    Remediation of hydrophobic pollutants is complicated by sorption of these compounds to hydrophobic sites of dissolved natural organic matter (NOM), suspended particulates, soil, and sediment. This sorption causes the pollutants to be less easily degraded by remediation techniques. Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H{sub 2}O{sub 2} + Fe{sup 2+} {yields} Fe{sup 3+} + HO{sup {minus}} + HO{sm_bullet}). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

  6. High molecular weight dissolved organic matter enrichment selects for methylotrophs in dilution to extinction cultures.

    PubMed

    Sosa, Oscar A; Gifford, Scott M; Repeta, Daniel J; DeLong, Edward F

    2015-12-01

    The role of bacterioplankton in the cycling of marine dissolved organic matter (DOM) is central to the carbon and energy balance in the ocean, yet there are few model organisms available to investigate the genes, metabolic pathways, and biochemical mechanisms involved in the degradation of this globally important carbon pool. To obtain microbial isolates capable of degrading semi-labile DOM for growth, we conducted dilution to extinction cultivation experiments using seawater enriched with high molecular weight (HMW) DOM. In total, 93 isolates were obtained. Amendments using HMW DOM to increase the dissolved organic carbon concentration 4x (280 μM) or 10x (700 μM) the ocean surface water concentrations yielded positive growth in 4-6% of replicate dilutions, whereas <1% scored positive for growth in non-DOM-amended controls. The majority (71%) of isolates displayed a distinct increase in cell yields when grown in increasing concentrations of HMW DOM. Whole-genome sequencing was used to screen the culture collection for purity and to determine the phylogenetic identity of the isolates. Eleven percent of the isolates belonged to the gammaproteobacteria including Alteromonadales (the SAR92 clade) and Vibrio. Surprisingly, 85% of isolates belonged to the methylotrophic OM43 clade of betaproteobacteria, bacteria thought to metabolically specialize in degrading C1 compounds. Growth of these isolates on methanol confirmed their methylotrophic phenotype. Our results indicate that dilution to extinction cultivation enriched with natural sources of organic substrates has a potential to reveal the previously unsuspected relationships between naturally occurring organic nutrients and the microorganisms that consume them.

  7. High molecular weight dissolved organic matter enrichment selects for methylotrophs in dilution to extinction cultures

    PubMed Central

    Sosa, Oscar A; Gifford, Scott M; Repeta, Daniel J; DeLong, Edward F

    2015-01-01

    The role of bacterioplankton in the cycling of marine dissolved organic matter (DOM) is central to the carbon and energy balance in the ocean, yet there are few model organisms available to investigate the genes, metabolic pathways, and biochemical mechanisms involved in the degradation of this globally important carbon pool. To obtain microbial isolates capable of degrading semi-labile DOM for growth, we conducted dilution to extinction cultivation experiments using seawater enriched with high molecular weight (HMW) DOM. In total, 93 isolates were obtained. Amendments using HMW DOM to increase the dissolved organic carbon concentration 4x (280 μM) or 10x (700 μM) the ocean surface water concentrations yielded positive growth in 4–6% of replicate dilutions, whereas <1% scored positive for growth in non-DOM-amended controls. The majority (71%) of isolates displayed a distinct increase in cell yields when grown in increasing concentrations of HMW DOM. Whole-genome sequencing was used to screen the culture collection for purity and to determine the phylogenetic identity of the isolates. Eleven percent of the isolates belonged to the gammaproteobacteria including Alteromonadales (the SAR92 clade) and Vibrio. Surprisingly, 85% of isolates belonged to the methylotrophic OM43 clade of betaproteobacteria, bacteria thought to metabolically specialize in degrading C1 compounds. Growth of these isolates on methanol confirmed their methylotrophic phenotype. Our results indicate that dilution to extinction cultivation enriched with natural sources of organic substrates has a potential to reveal the previously unsuspected relationships between naturally occurring organic nutrients and the microorganisms that consume them. PMID:25978545

  8. Distinct Optical Chemistry of Dissolved Organic Matter in Urban Pond Ecosystems

    PubMed Central

    McEnroe, Nicola A.; Williams, Clayton J.; Xenopoulos, Marguerite A.; Porcal, Petr; Frost, Paul C.

    2013-01-01

    Urbanization has the potential to dramatically alter the biogeochemistry of receiving freshwater ecosystems. We examined the optical chemistry of dissolved organic matter (DOM) in forty-five urban ponds across southern Ontario, Canada to examine whether optical characteristics in these relatively new ecosystems are distinct from other freshwater systems. Dissolved organic carbon (DOC) concentrations ranged from 2 to 16 mg C L-1 across the ponds with an average value of 5.3 mg C L-1. Excitation-emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) modelling showed urban pond DOM to be characterized by microbial-like and, less importantly, by terrestrial derived humic-like components. The relatively transparent, non-humic DOM in urban ponds was more similar to that found in open water, lake ecosystems than to rivers or wetlands. After irradiation equivalent to 1.7 days of natural solar radiation, DOC concentrations, on average, decreased by 38% and UV absorbance decreased by 25%. Irradiation decreased the relative abundances of terrestrial humic-like components and increased protein-like aspects of the DOM pool. These findings suggest that high internal production and/or prolonged exposure to sunlight exerts a distinct and significant influence on the chemistry of urban pond DOM, which likely reduces its chemical similarity with upstream sources. These properties of urban pond DOM may alter its biogeochemical role in these relatively novel aquatic ecosystems. PMID:24348908

  9. Effects of pore size and dissolved organic matters on diffusion of arsenate in aqueous solution.

    PubMed

    Wang, Yulong; Wang, Shaofeng; Wang, Xin; Jia, Yongfeng

    2017-02-01

    Presented here is the influence of membrane pore size and dissolved organic matters on the diffusion coefficient (D) of aqueous arsenate, investigated by the diffusion cell method for the first time. The pH-dependent diffusion coefficient of arsenate was determined and compared with values from previous studies; the coefficient was found to decrease with increasing pH, showing the validity of our novel diffusion cell method. The D value increased dramatically as a function of membrane pore size at small pore sizes, and then increased slowly at pore sizes larger than 2.0μm. Using the ExpAssoc model, the maximum D value was determined to be 11.2565×10(-6)cm(2)/sec. The presence of dissolved organic matters led to a dramatic increase of the D of arsenate, which could be attributed to electrostatic effects and ionic effects of salts. These results improve the understanding of the diffusion behavior of arsenate, especially the important role of various environmental parameters in the study and prediction of the migration of arsenate in aquatic water systems.

  10. Radioacarbon in dissolved organic carbon, a possible groundwater dating method: Case studies from western Canada

    SciTech Connect

    Wassenaar, L.; Aravena, R. ); Hendry, J. ); Fritz, P. )

    1991-08-01

    This paper explores the feasibility of using {sup 14}C in dissolved organic carbon (DOC) as an alternative isotopic groundwater dating method. Two hydrogeologically contrasting groundwater systems were tested; the Cretaceous age Milk River aquifer, and low-permeability, organic rich, Wisconsinan age Prairie tills in southern Alberta, Canada. Comparisons of radiocarbon data were made between DOC fractions, dissolved inorganic carbon (DIC), and several DIC geochemical age correction models along well defined flow paths. The data presented demonstrate that {sup 14}C dating of DOC fractions can indeed provide an alternative method for determining isotopic groundwater ages, under suitable conditions. However, detailed information may be required regarding (1) the geologic nature of the aquifer and its flow system, (2) the isotopically conservative behavior of DOC, (3) the initial {sup 14}C activity of DOC in recharge, and (4) the effect of bacterial redox processes on the {sup 14}C activity of DOC. In the Milk River aquifer, DOC {sup 14}C ages were successfully used to estimate groundwater residence times, as well as to further refine input parameter assumptions for the DIC method. In the Prairie tills, DOC {sup 14}C ages were used to establish a maximum age for the pore waters in an environment where the DIC method is especially problematic.

  11. Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

    PubMed

    McNeill, Kristopher; Canonica, Silvio

    2016-11-09

    Excited triplet states of chromophoric dissolved organic matter ((3)CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of (3)CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize (3)CDOM*. Information on (3)CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing (3)CDOM* using transient spectroscopic methods. Singlet molecular oxygen ((1)O2), which is a product of the reaction between (3)CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of (3)CDOM*. There are two major modes of reaction of (3)CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of (3)CDOM* can be achieved.

  12. Distinct optical chemistry of dissolved organic matter in urban pond ecosystems.

    PubMed

    McEnroe, Nicola A; Williams, Clayton J; Xenopoulos, Marguerite A; Porcal, Petr; Frost, Paul C

    2013-01-01

    Urbanization has the potential to dramatically alter the biogeochemistry of receiving freshwater ecosystems. We examined the optical chemistry of dissolved organic matter (DOM) in forty-five urban ponds across southern Ontario, Canada to examine whether optical characteristics in these relatively new ecosystems are distinct from other freshwater systems. Dissolved organic carbon (DOC) concentrations ranged from 2 to 16 mg C L(-1) across the ponds with an average value of 5.3 mg C L(-1). Excitation-emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) modelling showed urban pond DOM to be characterized by microbial-like and, less importantly, by terrestrial derived humic-like components. The relatively transparent, non-humic DOM in urban ponds was more similar to that found in open water, lake ecosystems than to rivers or wetlands. After irradiation equivalent to 1.7 days of natural solar radiation, DOC concentrations, on average, decreased by 38% and UV absorbance decreased by 25%. Irradiation decreased the relative abundances of terrestrial humic-like components and increased protein-like aspects of the DOM pool. These findings suggest that high internal production and/or prolonged exposure to sunlight exerts a distinct and significant influence on the chemistry of urban pond DOM, which likely reduces its chemical similarity with upstream sources. These properties of urban pond DOM may alter its biogeochemical role in these relatively novel aquatic ecosystems.

  13. Characterization and origin of polar dissolved organic matter from the Great Salt Lake

    USGS Publications Warehouse

    Leenheer, J.A.; Noyes, T.I.; Rostad, C.E.; Davisson, M.L.

    2004-01-01

    Polar dissolved organic matter (DOM) was isolated from a surface-water sample from the Great Salt Lake by separating it from colloidal organic matter by membrane dialysis, from less-polar DOM fractions by resin sorbents, and from inorganic salts by a combination of sodium cation exchange followed by precipitation of sodium salts by acetic acid during evaporative concentration. Polar DOM was the most abundant DOM fraction, accounting for 56% of the isolated DOM. Colloidal organic matter was 14C-age dated to be about 100% modern carbon and all of the DOM fractions were 14C-age dated to be between 94 and 95% modern carbon. Average structural models of each DOM fraction were derived that incorporated quantitative elemental and infrared, 13C-NMR, and electrospray/mass spectrometric data. The polar DOM model consisted of open-chain N-acetyl hydroxy carboxylic acids likely derived from N-acetyl heteropolysaccharides that constituted the colloidal organic matter. The less polar DOM fraction models consisted of aliphatic alicyclic ring structures substituted with carboxyl, hydroxyl, ether, ester, and methyl groups. These ring structures had characteristics similar to terpenoid precursors. All DOM fractions in the Great Salt Lake are derived from algae and bacteria that dominate DOM inputs in this lake.

  14. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

    USGS Publications Warehouse

    Lindsey, M.E.; Tarr, M.A.

    2000-01-01

    Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical

  15. Spatial and temporal variation in dissolved organic carbon composition in a peaty catchment draining a windfarm

    NASA Astrophysics Data System (ADS)

    Zheng, Ying; Waldron, Susan; Flowers, Hugh

    2015-04-01

    Peatlands are an important terrestrial carbon reserve and a principal source of dissolved organic carbon (DOC) to the fluvial environment (Wallage et al. 2006). Recently it has been observed that DOC concentrations [DOC] in surface waters have increased in Europe and North America (Monteith et al. 2007). This has been attributed primarily to reduced acid deposition. However, land use change can also release C from peat soils. A significant land use change in Scotland is hosting windfarms. Whether windfarm construction causes such impacts has been a research focus, particularly considering fluvial losses, but usually assessing if there are changes in DOC concentration rather than composition. Our study area is a peaty catchment that hosts wind turbines, has peat restoration activities and forest felling and is drained by two streams. We are using UV-visible and fluorescence spectrophotometry to assess if there are differences between the two steams or temporal changes in DOC composition. We will present data from samples collected since February 2014. The parameters we are focusing on are SUVA254, E4/E6 and E2/E4 ratios as these are indicators of DOC aromaticity, humic acid (HA): fulvic acid (FA) ratio and the proportion of humic substances in DOC (Weishaar, 2003; Spencer et al. 2007; Graham et al. 2012). To assess these we have measured UV-visible absorbance spectra from 200 nm to 800 nm. Meanwhile sample fluorescence emission and excitation matrix (EEM) will be applied with the PARAFAC model to obtain more information about the variations in humic substances in this catchment. Our current analysis indicates spatial differences not only in DOC concentration but also in composition. For example, the mainstem draining the windfarm area had a smaller [DOC] but higher E4/E6 and lower E2/E4 ratio values than the tributary draining an area of felled forestry. This may be indicative of more HAs in the mainstem DOC. Seasonal variations have also been observed. Both streams

  16. Colored dissolved organic matter in shallow estuaries: relationships between carbon sources and light attenuation

    NASA Astrophysics Data System (ADS)

    Oestreich, W. K.; Ganju, N. K.; Pohlman, J. W.; Suttles, S. E.

    2016-02-01

    Light availability is of primary importance to the ecological function of shallow estuaries. For example, benthic primary production by submerged aquatic vegetation is contingent upon light penetration to the seabed. A major component that attenuates light in estuaries is colored dissolved organic matter (CDOM). CDOM is often measured via a proxy, fluorescing dissolved organic matter (fDOM), due to the ease of in situ fDOM sensor measurements. Fluorescence must be converted to CDOM absorbance for use in light attenuation calculations. However, this CDOM-fDOM relationship varies among and within estuaries. We quantified the variability in this relationship within three estuaries along the mid-Atlantic margin of the eastern United States: West Falmouth Harbor (MA), Barnegat Bay (NJ), and Chincoteague Bay (MD/VA). Land use surrounding these estuaries ranges from urban to developed, with varying sources of nutrients and organic matter. Measurements of fDOM (excitation and emission wavelengths of 365 nm (±5 nm) and 460 nm (±40 nm), respectively) and CDOM absorbance were taken along a terrestrial-to-marine gradient in all three estuaries. The ratio of the absorption coefficient at 340 nm (m-1) to fDOM (QSU) was higher in West Falmouth Harbor (1.22) than in Barnegat Bay (0.22) and Chincoteague Bay (0.17). The CDOM : fDOM absorption ratio was variable between sites within West Falmouth Harbor and Barnegat Bay, but consistent between sites within Chincoteague Bay. Stable carbon isotope analysis for constraining the source of dissolved organic matter (DOM) in West Falmouth Harbor and Barnegat Bay yielded δ13C values ranging from -19.7 to -26.1 ‰ and -20.8 to -26.7 ‰, respectively. Concentration and stable carbon isotope mixing models of DOC (dissolved organic carbon) indicate a contribution of 13C-enriched DOC in the estuaries. The most likely source of 13C-enriched DOC for the systems we investigated is Spartina cordgrass. Comparison of DOC source to CDOM : f

  17. Colored dissolved organic matter in shallow estuaries: relationships between carbon sources and light attenuation

    USGS Publications Warehouse

    Oestreich, W.K.; Ganju, Neil Kamal; Pohlman, John; Suttles, Steven

    2016-01-01

    Light availability is of primary importance to the ecological function of shallow estuaries. For example, benthic primary production by submerged aquatic vegetation is contingent upon light penetration to the seabed. A major component that attenuates light in estuaries is colored dissolved organic matter (CDOM). CDOM is often measured via a proxy, fluorescing dissolved organic matter (fDOM), due to the ease of in situ fDOM sensor measurements. Fluorescence must be converted to CDOM absorbance for use in light attenuation calculations. However, this CDOM–fDOM relationship varies among and within estuaries. We quantified the variability in this relationship within three estuaries along the mid-Atlantic margin of the eastern United States: West Falmouth Harbor (MA), Barnegat Bay (NJ), and Chincoteague Bay (MD/VA). Land use surrounding these estuaries ranges from urban to developed, with varying sources of nutrients and organic matter. Measurements of fDOM (excitation and emission wavelengths of 365 nm (±5 nm) and 460 nm (±40 nm), respectively) and CDOM absorbance were taken along a terrestrial-to-marine gradient in all three estuaries. The ratio of the absorption coefficient at 340 nm (m−1) to fDOM (QSU) was higher in West Falmouth Harbor (1.22) than in Barnegat Bay (0.22) and Chincoteague Bay (0.17). The CDOM : fDOM absorption ratio was variable between sites within West Falmouth Harbor and Barnegat Bay, but consistent between sites within Chincoteague Bay. Stable carbon isotope analysis for constraining the source of dissolved organic matter (DOM) in West Falmouth Harbor and Barnegat Bay yielded δ13C values ranging from −19.7 to −26.1 ‰ and −20.8 to −26.7 ‰, respectively. Concentration and stable carbon isotope mixing models of DOC (dissolved organic carbon) indicate a contribution of 13C-enriched DOC in the estuaries. The most likely source of 13C-enriched DOC for the systems we investigated is Spartina cordgrass. Comparison of

  18. Effects of sulfate deposition on pore water dissolved organic carbon, nutrients, and microbial enzyme activities in a northern peatland

    EPA Science Inventory

    Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolve...

  19. DISTRIBUTION AND COMPOSITION OF DISSOLVED AND PARTICULATE ORGANIC CARBON IN NORTHERN SAN FRANCISCO BAY DURING LOW FRESHWATER FLOW CONDITIONS

    EPA Science Inventory

    The distribution of organic matter was studied in northern San Francisco Bay monthly through spring and summer 1996 along the salinity gradient from the Sacramento River to Central Bay. Dissolved constituents included monosaccharides (MONO), total carbohydrates (TCHO), dissolved ...

  20. Leaching of Particulate and Dissolved Organic Carbon from Compost Applied to Bioretention Systems

    NASA Astrophysics Data System (ADS)

    Iqbal, Hamid; Flury, Markus; Mullane, Jessica; Baig, Muhammad

    2015-04-01

    Compost is used in bioretention systems to improve soil quality, to promote plant growth, and to remove metal contaminants from stormwater. However, compost itself, particularly when applied freshly, can be a source of contamination of the stormwater. To test the potential contamination caused by compost when applied to bioretention systems, we continuously leached a compost column with water under unsaturated conditions and characterized dissolved and particulate organic matter in the leachate. Freshly applied, mature compost leached up to 400 mg/L of dissolved organic carbon and 2,000 mg/L of suspended particulate organic carbon. It required a cumulative water flux of 4,000 mm until concentrations of dissolved and particulate organic carbon declined to levels typical for surface waters. Although, dissolved and particulate organic carbon are not contaminants per se, they can facilitate the movement of metals, thereby enhancing the mobility of toxic metals present in stormwater. Therefore, we recommended that compost is washed before it is applied to bioretention systems. Keywords compost; leachate; alkali extract; dissolved organic carbon; flux

  1. Dissolved organic matter composition of Arctic rivers: Linking permafrost and parent material to riverine carbon

    USGS Publications Warehouse

    O’Donnell, Jonathan A.; Aiken, George R.; Swanson, David K.; Santosh, Panda; Butler, Kenna; Baltensperger, Andrew P.

    2016-01-01

    Recent climate change in the Arctic is driving permafrost thaw, which has important implications for regional hydrology and global carbon dynamics. Permafrost is an important control on groundwater dynamics and the amount and chemical composition of dissolved organic matter (DOM) transported by high-latitude rivers. The consequences of permafrost thaw for riverine DOM dynamics will likely vary across space and time, due in part to spatial variation in ecosystem properties in Arctic watersheds. Here we examined watershed controls on DOM composition in 69 streams and rivers draining heterogeneous landscapes across a broad region of Arctic Alaska. We characterized DOM using bulk dissolved organic carbon (DOC) concentration, optical properties, and chemical fractionation and classified watersheds based on permafrost characteristics (mapping of parent material and ground ice content, modeling of thermal state) and ecotypes. Parent material and ground ice content significantly affected the amount and composition of DOM. DOC concentrations were higher in watersheds underlain by fine-grained loess compared to watersheds underlain by coarse-grained sand or shallow bedrock. DOC concentration was also higher in rivers draining ice-rich landscapes compared to rivers draining ice-poor landscapes. Similarly, specific ultraviolet absorbance (SUVA254, an index of DOM aromaticity) values were highest in watersheds underlain by fine-grained deposits or ice-rich permafrost. We also observed differences in hydrophobic organic acids, hydrophilic compounds, and DOM fluorescence across watersheds. Both DOC concentration and SUVA254 were negatively correlated with watershed active layer thickness, as determined by high-resolution permafrost modeling. Together, these findings highlight how spatial variations in permafrost physical and thermal properties can influence riverine DOM.

  2. Dissolved organic matter composition of Arctic rivers: Linking permafrost and parent material to riverine carbon

    NASA Astrophysics Data System (ADS)

    O'Donnell, Jonathan A.; Aiken, George R.; Swanson, David K.; Panda, Santosh; Butler, Kenna D.; Baltensperger, Andrew P.

    2016-12-01

    Recent climate change in the Arctic is driving permafrost thaw, which has important implications for regional hydrology and global carbon dynamics. Permafrost is an important control on groundwater dynamics and the amount and chemical composition of dissolved organic matter (DOM) transported by high-latitude rivers. The consequences of permafrost thaw for riverine DOM dynamics will likely vary across space and time, due in part to spatial variation in ecosystem properties in Arctic watersheds. Here we examined watershed controls on DOM composition in 69 streams and rivers draining heterogeneous landscapes across a broad region of Arctic Alaska. We characterized DOM using bulk dissolved organic carbon (DOC) concentration, optical properties, and chemical fractionation and classified watersheds based on permafrost characteristics (mapping of parent material and ground ice content, modeling of thermal state) and ecotypes. Parent material and ground ice content significantly affected the amount and composition of DOM. DOC concentrations were higher in watersheds underlain by fine-grained loess compared to watersheds underlain by coarse-grained sand or shallow bedrock. DOC concentration was also higher in rivers draining ice-rich landscapes compared to rivers draining ice-poor landscapes. Similarly, specific ultraviolet absorbance (SUVA254, an index of DOM aromaticity) values were highest in watersheds underlain by fine-grained deposits or ice-rich permafrost. We also observed differences in hydrophobic organic acids, hydrophilic compounds, and DOM fluorescence across watersheds. Both DOC concentration and SUVA254 were negatively correlated with watershed active layer thickness, as determined by high-resolution permafrost modeling. Together, these findings highlight how spatial variations in permafrost physical and thermal properties can influence riverine DOM.

  3. Dissolved organic matter transport reflects hillslope to stream connectivity during snowmelt in a montane catchment

    NASA Astrophysics Data System (ADS)

    Burns, Margaret A.; Barnard, Holly R.; Gabor, Rachel S.; McKnight, Diane M.; Brooks, Paul D.

    2016-06-01

    Dissolved organic matter (DOM) transport is a key biogeochemical linkage across the terrestrial-aquatic interface in headwater catchments, and quantifying the biological and hydrological controls on DOM composition provides insight into DOM cycling at the catchment scale. We evaluated the mobility of DOM components during snowmelt in a montane, semiarid catchment. DOM composition was evaluated on a near-daily basis within the soil and the stream during snowmelt, and was compared to groundwater samples using a site-specific parallel factor analysis (PARAFAC) model derived from soil extracts. The fluorescent component loadings in the interstitial soil water and in the groundwater were significantly different and did not temporally change during snowmelt. In the stream, a transition occurred during snowmelt from fluorescent DOM with higher contributions of amino acid-like components indicative of groundwater to higher humic-like contributions indicative of soil water. Furthermore, we identified a humic-like fluorescent component in the soil water and the stream that is typically only observed in extracted water soluble organic matter from soil which may suggest hillslope to stream connectivity over very short time scales. Qualitative interpretations of changes in stream fluorescent DOM were supported by two end-member mixing analyses of conservative tracers. After normalizing fluorescent DOM loadings for dissolved organic carbon (DOC) concentration, we found that the peak in DOC concentration in the stream was driven by the nonfluorescent fraction of DOM. This study demonstrated how PARAFAC analysis can be used to refine our conceptual models of runoff generation sources, as well as provide a more detailed understanding of stream chemistry dynamics.

  4. Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory

    NASA Astrophysics Data System (ADS)

    Ksionzek, Kerstin B.; Lechtenfeld, Oliver J.; McCallister, S. Leigh; Schmitt-Kopplin, Philippe; Geuer, Jana K.; Geibert, Walter; Koch, Boris P.

    2016-10-01

    Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. Although molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (sulfur/nitrogen ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 petagrams of sulfur, exceeding all other marine organic sulfur reservoirs by an order of magnitude.

  5. On the borderline of dissolved and particulate organic matter: partitioning and bioavailability of polycyclic aromatic hydrocarbons.

    PubMed

    Akkanen, Jarkko; Tuikka, Anita; Kukkonen, Jussi V K

    2012-04-01

    The functionality of dissolved organic matter (DOM) was studied by assessing the availability of polycyclic aromatic hydrocarbons (PAHs) spiked in pore water samples separated from sediments by water extraction and centrifugation with or without subsequent filtration. The purpose was to compare the effects of traditionally defined DOM (0.45-μm cut off) and larger colloidal material present in the separated pore water samples on the partitioning and bioavailability of PAHs. The tested PAHs included phenanthrene (Phe), fluoranthene (Flu), pyrene (Pyr) and benzo[a]pyrene (BaP). Bioavailability of the selected PAHs was tested with two ecologically different organisms: pelagic filter feeder Daphnia magna and sediment-dwelling deposit feeder Lumbriculus variegatus. Sorption to DOM (i.e. in filtered samples) was clearly higher for BaP than for the other PAH. This was also reflected in significantly reduced bioavailability for both model organisms in the filtered samples compared to DOM-free conditions. For the other PAHs the sorption was significant only in the unfiltered samples indicating the importance of larger colloidal material. Thus, the bioavailability of PAHs was also more effectively reduced by the colloidal material. This holds true for both the model organisms, indicating that the ecological differences i.e. filter feeder vs. deposit feeder do not affect in this respect. It appears that considering only traditionally defined DOM, material that may be present in environmental samples and is important for the speciation and bioavailability of contaminants is ignored.

  6. Amount, composition and seasonality of dissolved organic carbon and nitrogen export from agriculture in contrasting climates

    NASA Astrophysics Data System (ADS)

    Graeber, Daniel; Meerhof, Mariana; Zwirnmann, Elke; Ovesen, Niels; Gelbrecht, Jörg; Teixeira de Mello, Franco; González-Bergonzoni, Ivan; Jeppesen, Erik; Kronvang, Brian

    2014-05-01

    Agricultural catchments are potentially important but often neglected sources of dissolved organic matter (DOM), of which a large part is dissolved organic carbon (DOC) and nitrogen (DON). DOC is an important source of aquatic microbial respiration and DON may be an important source of nitrogen to aquatic ecosystems. However, there is still a lack of comprehensive studies on the amount, composition and seasonality of DOM export from agricultural catchments in different climates. The aim of our study was to assess the amount, composition and seasonality of DOM in a total of four streams in the wet-temperate and subtropical climate of Denmark and Uruguay, respectively. In each climate, we investigated one stream with extensive agriculture (mostly pasture) and one stream with intensive agriculture (mostly intensively used arable land) in the catchment. We sampled each stream taking grab samples fortnightly for two years and measured DOC and DON concentration, as well as molecular composition by size-exclusion chromatography. We used absorbance, fluorescence and parallel factor analysis to gather additional information on the sources and composition of the DOM. The results were coupled to measurements of precipitation, water temperature, discharge, water residence time and physicochemical data measured at each study site to investigate the effects these environmental variables have on the amount and composition of DOM in the streams. Average annual DOM concentration and seasonality were highest in the stream with intensive agriculture in Uruguay and lowest in the stream with extensive agriculture in Denmark. In all streams, the molecular-size composition of DOC and DON were similar and most DOC and DON were exported as humic substances with low C:N ratio, which indicates high bioavailability. Moreover, DON was of higher relative importance in the Uruguayan streams than in the Danish streams, as can be seen from the lower dissolved inorganic to total dissolved nitrogen

  7. Dissolved Organic Matter Dynamics in a Suburbanizing Watershed: The Importance of Wetlands, People, and Flowpaths

    NASA Astrophysics Data System (ADS)

    Koenig, L.; Daley, M. L.; Potter, J.; McDowell, W. H.

    2013-12-01

    Human development of a watershed often yields fundamental and quantifiable changes in water quality and inorganic nutrient cycling. The effects of suburban development on the cycling of dissolved organic matter (DOM), however, have received relatively less attention, and the understanding of local dissolved organic matter dynamics is rarely a stated goal of watershed management. In this study, we examine the effects of suburbanization on concentrations of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) as well as the optical properties of DOM using 17 study sites in the Lamprey River watershed, NH that integrate varying levels of human development and population density. We show that concentration of DOC and DON is related to wetland cover but is not correlated with population density. Further, we observed no response in DOC concentration with increased flow at the mainstem site, while DON concentration is diluted. The optical properties of dissolved organic matter, however, showed different trends. Fluorescence Index (FI) decreases with increasing wetland cover and lower population density. We show that in a coastal watershed, while DOM quantity is driven by the presence of wetlands, DOM quality changes with both wetland cover and human development. The decoupling of DOM quantity and quality in this suburbanizing watershed indicate that DOM quality may be an important yet overlooked control on watershed-scale biogeochemical cycling and nutrient export.

  8. Characterization of Plant-derived Dissolved Organic Matter by Multiple Spectroscopic Techniques

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic matter (DOM) derived from fresh or early-stage decomposing soil amendment materials may play an important role in the process of organic matter accumulation. In this study, eight DOM samples from alfalfa, corn, crimson clover, hairy vetch, lupin, soybean, wheat and dairy manure wer...

  9. FACTORS AFFECTING COLORED DISSOLVED ORGANIC MATTER IN AQUATIC ENVIRONMENTS OF THE SOUTHEASTERN UNITED STATES

    EPA Science Inventory

    The sunlight-absorbing (colored) component of dissolved organic matter (CDOM) in aquatic environments is widely distributed in freshwaters and coastal regions where it influences the fate and transport of toxic organic substances and biologically-important metals such as mercury,...

  10. Effects of Low Dissolved Oxygen on Organisms Used in Freshwater Sediment Toxicity Tests

    EPA Science Inventory

    This manuscript describes the results of tests to determine the tolerance of three benthic organisms to reduced dissolved oxygen (DO). These three organisms are those recommended by EPA for use in toxicity testing of contaminated sediments. The results of the exposures indicate ...

  11. Spatial connectivity in a large river system: resolving the sources and fate of dissolved organic matter.

    PubMed

    Massicotte, Philippe; Frenette, Jean-Jacques

    2011-10-01

    Large rivers are generally heterogeneous and productive systems that receive important inputs of dissolved organic matter (DOM) from terrestrial and in situ sources. Thus, they are likely to play a significant role in the biogeochemical cycling of the DOM flowing to the oceans. The asymmetric spatial gradient driven by directional flow and environmental heterogeneity contributes to the fate of DOM flowing downstream. Yet, the relative effects of spatial connectivity and environmental heterogeneity on DOM dynamics are poorly understood. For example, since environmental variables show spatial heterogeneity, the variation explained by environmental and spatial variables may be redundant. We used the St. Lawrence River (SLR) as a representative large river to resolve the unique influences of environmental heterogeneity and spatial connectivity on DOM dynamics. We used three-dimensional fluorescence matrices combined with parallel factor analysis (PARAFAC) to characterize the DOM pool in the SLR. Seven fluorophores were modeled, of which two were identified to be of terrestrial origin and three from algal exudates. We measured a set of environmental variables that are known to drive the fate of DOM in aquatic systems. Additionally, we used asymmetric eigenvector map (AEM) modeling to take spatial connectivity into account. The combination of spatial and environmental models explained 85% of the DOM variation. We show that spatial connectivity is an important driver of DOM dynamics, as a large fraction of environmental heterogeneity was attributable to the asymmetric spatial gradient. Along the longitudinal axis, we noted a rapid increase in dissolved organic carbon (DOC), mostly controlled by terrestrial input of DOM originating from the tributaries. Variance partitioning demonstrated that freshly produced protein-like DOM was found to be the preferential substrate for heterotrophic bacteria undergoing rapid proliferation, while humic-like DOM was more correlated to the

  12. Transport of organic contaminants in subsoil horizons and effects of dissolved organic matter related to organic waste recycling practices.

    PubMed

    Chabauty, Florian; Pot, Valérie; Bourdat-Deschamps, Marjolaine; Bernet, Nathalie; Labat, Christophe; Benoit, Pierre

    2016-04-01

    Compost amendment on agricultural soil is a current practice to compensate the loss of organic matter. As a consequence, dissolved organic carbon concentration in soil leachates can be increased and potentially modify the transport of other solutes. This study aims to characterize the processes controlling the mobility of dissolved organic matter (DOM) in deep soil layers and their potential impacts on the leaching of organic contaminants (pesticides and pharmaceutical compounds) potentially present in cultivated soils receiving organic waste composts. We sampled undisturbed soil cores in the illuviated horizon (60-90 cm depth) of an Albeluvisol. Percolation experiments were made in presence and absence of DOM with two different pesticides, isoproturon and epoxiconazole, and two pharmaceutical compounds, ibuprofen and sulfamethoxazole. Two types of DOM were extracted from two different soil surface horizons: one sampled in a plot receiving a co-compost of green wastes and sewage sludge applied once every 2 years since 1998 and one sampled in an unamended plot. Results show that DOM behaved as a highly reactive solute, which was continuously generated within the soil columns during flow and increased after flow interruption. DOM significantly increased the mobility of bromide and all pollutants, but the effects differed according the hydrophobic and the ionic character of the molecules. However, no clear effects of the origin of DOM on the mobility of the different contaminants were observed.

  13. Removal of dissolved organic matter in water-hyacinth waste-water treatment lagoons

    SciTech Connect

    Victoria-Rueda, C.H.

    1991-01-01

    Secondary treatment of domestic wastewater in water hyacinth lagoons was evaluated under experimental conditions to assess the role of the roots' bacterial biofilm in the removal of dissolved organic matter (DOM). Research was conducted to (1) quantify removal rates by the biofilm as a function of bulk DOM concentration, (2) formulate an analytical model of DOM removal incorporating biofilm activity, and (3) test the model response to variable organic loads in a pilot-scale plant. Removal of DOM by the biofilm was quantified in continuous-flow water hyacinth tanks at ten concentrations ranging from 45 to 330 g COD m {sup {minus}3} . Total DOM removal in the denitrifying, acetate-based experimental system was measured and partitioned into two fractions associated with the activity of biofilm and suspended bacteria. Calculated DOM removal by the biofilm was adjusted for the release of organic compounds by debris decomposition. Values of DOM removal were used to calculate oxygen transfer rates from the water hyacinth roots. A model of DOM removal in water hyacinth lagoons was formulated. The model, composed of four differential equations, was solved at steady-state conditions and the validity of its simulation results was tested in pilot-scale tanks. Hydraulic detection times ranging from 2 to 28 days were evaluated using biofilm density and concentrations of DOM and particulate organics as monitoring parameters of the model response. The observed decrease of suspended bacterial biomass along the tank was correctly simulated by the model, but predictions of effluent concentrations were not always consistent. Predicted values of biofilm bacterial mass were similar to those measured in the tanks, except when large algal populations were present in the film.

  14. Dissolved Organic Matter Composition of Arctic Rivers: Linking Permafrost, Parent Material, and Groundwater to Riverine Carbon

    NASA Astrophysics Data System (ADS)

    O'Donnell, J. A.; Aiken, G.; Butler, K. D.; Swanson, D. K.

    2015-12-01

    Recent warming in the Arctic is modifying the chemical composition of riverine dissolved organic matter (DOM) through changes in growing season length, wildfire, and permafrost thaw. In arctic rivers, DOM composition is an important control on nutrient availability, trace metal mobilization, and greenhouse gas emissions. As a result, shifts in DOM associated with a changing arctic landscape may alter how aquatic ecosystems function in this region. Here, we examined spatial variation in DOM composition in 72 rivers in the Brooks Range and Seward Peninsula of northern Alaska. We characterized DOM using a suite of techniques, including dissolved organic carbon (DOC) concentration, absorbance spectra, fluorescence, and chemical fractionation. Watersheds were classified based on traits that influence subsurface hydrology, including parent material (volcanic deposits, loess, sand, glacial moraine, bedrock) and permafrost extent (continuous vs. discontinuous zone) and state (ice-rich vs. ice-poor). We observed considerable variability in DOM composition across rivers. DOC concentrations were lowest in rivers influenced by glacial deposits (<2 mgC L-1) and highest in rivers draining lowland tundra or extensive wetlands (>10 mgC L-1). Specific ultraviolet absorbance (SUVA254), which serves as an index of DOM aromaticity, was also variable across rivers; spring-fed mountain streams had the lowest SUVA254 values (<1.5 L mgC-1 m-1), whereas tundra and wetland-dominated streams had the highest values (>4 L mgC-1 m-1). While hydrophobic organic acids were the dominant DOM fraction in all rivers, we observed a significant increase in the proportion of hydrophilic compounds during winter flow and in groundwater-fed systems. We also observed variation in DOM composition with permafrost extent and ground ice distribution across the region. Model projections over the next century suggest a heterogeneous response of DOM to thaw, likely mediated by spatial variations in ground ice and

  15. Terrestrial C sequestration at elevated CO2 and temperature: the role of dissolved organic N loss

    USGS Publications Warehouse

    Rastetter, Edward B.; Perakis, Steven S.; Shaver, Gaius R.; Agren, Goran I.

    2005-01-01

    We used a simple model of carbona??nitrogen (Ca??N) interactions in terrestrial ecosystems to examine the responses to elevated CO2 and to elevated CO2 plus warming in ecosystems that had the same total nitrogen loss but that differed in the ratio of dissolved organic nitrogen (DON) to dissolved inorganic nitrogen (DIN) loss. We postulate that DIN losses can be curtailed by higher N demand in response to elevated CO2, but that DON losses cannot. We also examined simulations in which DON losses were held constant, were proportional to the amount of soil organic matter, were proportional to the soil C:N ratio, or were proportional to the rate of decomposition. We found that the mode of N loss made little difference to the short-term (<60 years) rate of carbon sequestration by the ecosystem, but high DON losses resulted in much lower carbon sequestration in the long term than did low DON losses. In the short term, C sequestration was fueled by an internal redistribution of N from soils to vegetation and by increases in the C:N ratio of soils and vegetation. This sequestration was about three times larger with elevated CO2 and warming than with elevated CO2 alone. After year 60, C sequestration was fueled by a net accumulation of N in the ecosystem, and the rate of sequestration was about the same with elevated CO2 and warming as with elevated CO2 alone. With high DON losses, the ecosystem either sequestered C slowly after year 60 (when DON losses were constant or proportional to soil organic matter) or lost C (when DON losses were proportional to the soil C:N ratio or to decomposition). We conclude that changes in long-term C sequestration depend not only on the magnitude of N losses, but also on the form of those losses.

  16. Non-conservative behavior of fluorescent dissolved organic matter (FDOM) within a subterranean estuary

    NASA Astrophysics Data System (ADS)

    Suryaputra, I. G. N. A.; Santos, I. R.; Huettel, M.; Burnett, W. C.; Dittmar, T.

    2015-11-01

    The role of submarine groundwater discharge (SGD) in releasing fluorescent dissolved organic matter (FDOM) to the coastal ocean and the possibility of using FDOM as a proxy for dissolved organic carbon (DOC) was investigated in a subterranean estuary in the northeastern Gulf of Mexico (Turkey Point, Florida). FDOM was continuously monitored for three weeks in shallow beach groundwater and in the adjacent coastal ocean. Radon (222Rn) was used as a natural groundwater tracer. FDOM and DOC correlated in groundwater and seawater samples, implying that FDOM may be a proxy of DOC in waters influenced by SGD. A mixing model using salinity as a seawater tracer revealed FDOM production in the high salinity region of the subterranean estuary. This production was probably a result of infiltration and transformation of labile marine organic matter in the beach sediments. The non-conservative FDOM behavior in this subterranean estuary differs from most surface estuaries where FDOM typically behaves conservatively. At the study site, fresh and saline SGD delivered about 1800 mg d-1 of FDOM (quinine equivalents) to the coastal ocean per meter of shoreline. About 11% of this input was related to fresh SGD, while 89% were related to saline SGD resulting from FDOM production within the shallow aquifer. If these fluxes are representative of the Florida Gulf Coast, SGD-derived FDOM fluxes would be equivalent to at least 18% of the potential regional riverine FDOM inputs. To reduce uncertainties related to the scarcity of FDOM data, further investigations of river and groundwater FDOM inputs in Florida and elsewhere are necessary.

  17. Dissolved organic carbon concentrations and compositions, and trihalomethane formation potentials in waters from agricultural peat soils, Sacramento-San Joaquin Delta, California; implications for drinking-water quality

    USGS Publications Warehouse

    Fujii, Roger; Ranalli, Anthony J.; Aiken, George R.; Bergamaschi, Brian A.

    1998-01-01

    . Dissolved organic carbon concentration, trihalomethane formation potential, and ultraviolet absorbance were all highly correlated, showing that trihalomethane precursors increased with increasing dissolved organic carbon and ultraviolet absorbance for whole water samples. Contrary to the generally accepted conceptual model for trihalomethane formation that assumes that aromatic forms of carbon are primary precursors to trihalomethanes, results from this study indicate that dissolved organic carbon aromaticity appears unrelated to trihalomethane formation on a carbon-normalized basis. Thus, dissolved organic carbon aromaticity alone cannot fully explain or predict trihalomethane precursor content, and further investigation of aromatic and nonaromatic forms of carbon will be needed to better identify trihalomethane precursors.

  18. Coextracted dissolved organic carbon has a suppressive effect on the acetylcholinesterase inhibition assay.

    PubMed

    Neale, Peta A; Escher, Beate I

    2013-07-01

    The acetylcholinesterase (AChE) inhibition assay is frequently applied to detect organophosphates and carbamate pesticides in different water types, including dissolved organic carbon (DOC)-rich wastewater and surface water. The aim of the present study was to quantify the effect of coextracted DOC from different water samples on the commonly used enzyme-based AChE inhibition assay. Approximately 40% to 70% of DOC is typically recovered by solid-phase extraction, and this comprises not only organic micropollutants but also natural organic matter. The inhibition of the water extracts in the assay differed greatly from the expected mixture effects based on chemical analysis of organophosphates and carbamates. Binary mixture experiments with the known AChE inhibitor parathion and the water extracts showed reduced toxicity in comparison with predictions using the mixture models of concentration addition and independent action. In addition, the extracts and reference organic matter had a suppressive effect on a constant concentration of parathion. The present study thus indicated that concentrations of DOC as low as 2 mg carbon/L can impair the AChE inhibition assay and, consequently, that only samples with a final DOC concentration of less than 2 mgC /L are suitable for this assay. To check for potential suppression in environmental samples, standard addition experiments using an AChE-inhibiting reference compound are recommended.

  19. Relationships between land cover and dissolved organic matter change along the river to lake transition

    USGS Publications Warehouse

    Larson, James H.; Frost, Paul C.; Xenopoulos, Marguerite A.; Williams, Clayton J.; Morales-Williams, Ana M.; Vallazza, Jonathan M.; Nelson, J. C.; Richardson, William B.

    2014-01-01

    Dissolved organic matter (DOM) influences the physical, chemical, and biological properties of aquatic ecosystems. We hypothesized that controls over spatial variation in DOM quantity and composition (measured with DOM optical properties) differ based on the source of DOM to aquatic ecosystems. DOM quantity and composition should be better predicted by land cover in aquatic habitats with allochthonous DOM and related more strongly to nutrients in aquatic habitats with autochthonous DOM. Three habitat types [rivers (R), rivermouths (RM), and the nearshore zone (L)] associated with 23 tributaries of the Laurentian Great Lakes were sampled to test this prediction. Evidence from optical indices suggests that DOM in these habitats generally ranged from allochthonous (R sites) to a mix of allochthonous-like and autochthonous-like (L sites). Contrary to expectations, DOM properties such as the fluorescence index, humification index, and spectral slope ratio were only weakly related to land cover or nutrient data (Bayesian R 2 values were indistinguishable from zero). Strongly supported models in all habitat types linked DOM quantity (that is, dissolved organic carbon concentration [DOC]) to both land cover and nutrients (Bayesian R2 values ranging from 0.55 to 0.72). Strongly supported models predicting DOC changed with habitat type: The most important predictor in R sites was wetlands whereas the most important predictor at L sites was croplands. These results suggest that as the DOM pool becomes more autochthonous-like, croplands become a more important driver of spatial variation in DOC and wetlands become less important.

  20. Effects of pH, dissolved organic matter, and salinity on ibuprofen sorption on sediment.

    PubMed

    Oh, Sanghwa; Shin, Won Sik; Kim, Hong Tae

    2016-11-01

    Ibuprofen is well known as one of the most frequently detected pharmaceuticals and personal care products (PPCPs) in rivers. However, sorption of ibuprofen onto sediment has not been considered in spite of its high K ow (3.5). In this study, the effects of various environmental conditions such as pH (4, 5.3, and 7), the concentrations of dissolved organic matters (0 to 1.0 mM citrate and urea), salinity (0, 10, 20, and 30 part per thousand), and presence of other PPCP (salicylic acid) on ibuprofen sorption were investigated. Linear model mainly fitted the experimental data for analysis. The distribution coefficient (K d) in the linear model decreased from 6.76 at pH 4 to near zero at pH 7, indicating that neutral form of ibuprofen at pH below pKa (5.2) was easily sorbed onto the sediment whereas the sorption of anionic form at pH over pKa was not favorable. To investigate the effect of dissolved organic matters (DOMs) on ibuprofen sorption, citrate and urea were used as DOMs. As citrate concentration increased, the K d value decreased but urea did not interrupt the ibuprofen sorption. Citrate has three carboxyl functional groups which can attach easily ibuprofen and hinder its sorption onto sediment. Salinity also affected ibuprofen sorption due to decrease of the solubility of ibuprofen as salinity increased. In competitive sorption experiment, the addition of salicylic acid also led to enhance ibuprofen sorption. Conclusively, ibuprofen can be more easily sorbed onto the acidified sediments of river downstream, especially estuaries or near-shore environment with low DOM concentration.

  1. Inorganic and suspended/dissolved-organic nitrogen in Sierra Nevada soil core leachates

    SciTech Connect

    Marcus, J.A.; Miller, W.W.; Blank, R.R.

    1998-07-01

    Watershed disturbance has been suggested as a possible mechanism for accelerated nutrient input into Lake Tahoe, California/Nevada. However, little is known regarding how nutrient discharge is coupled to physicochemical watershed processes. Recent investigations in the Lake Tahoe Basin have suggested that suspended/dissolved-organic nutrient transport may play an important role in lake and tributary water quality. The mobility of inorganic and suspended/dissolved-organic N in soils of a Lake Tahoe watershed was assessed using constant head permeameter leaching experiments with intact soil cores. The authors evaluated the interaction of plot condition on magnitude and form of N discharge. Incremental leachate discharge was analyzed for concentrations of inorganic (NH{sub 4}-N and NO{sub 3}-N) and suspended/dissolved-organic N. Leachate from the riparian soil cores had significantly higher concentrations and total discharge NO{sub 3}-N than that from the nonforested or forested areas. Loading of NH{sub 4}-N was more consistent among vegetative cover types, but the riparian leachate again contributed a significantly greater amount. Suspended/dissolved-organic N was mobile and the most dominant form of N for nonforested and forested soil cores with discharge loading ratios of 17:1 and 7:1, respectively. Although the loading ratio was approximately 1:1 for the riparian soil cores, the amount of suspended/dissolved-organic N discharged was greatest. The mobility and presence of significant amounts of suspended/dissolved-organic N indicate that this once unrecognized nutrient form is an important component in at least one Sierra Nevada watershed, and should be more fully investigated elsewhere.

  2. Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

    USGS Publications Warehouse

    Ravichandran, Mahalingam; Aiken, George R.; Reddy, Michael M.; Ryan, Joseph N.

    1998-01-01

    Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca2+. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pHpzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

  3. Characteristics of dissolved organic matter (DOM) and relationship with dissolved mercury in Xiaoqing River-Laizhou Bay estuary, Bohai Sea, China.

    PubMed

    Jiang, Tao; Skyllberg, Ulf; Björn, Erik; Green, Nelson W; Tang, Jianhui; Wang, Dingyong; Gao, Jie; Li, Chuxian

    2017-04-01

    Because of heterogeneous properties, dissolved organic matter (DOM) is known to control the environmental fate of a variety of organic pollutants and trace metals in aquatic systems. Here we report absorptive and fluorescence properties of DOM, in concurrence with concentrations of dissolved mercury (Hg), along the Xiaoqing River-Laizhou Bay estuary system located in the Bohai Sea of China. A mixing model consisting of the two end-members terrestrial and aquatic DOM demonstrated that terrestrial signatures decreased significantly from the river into the estuary. Quasi-conservative mixing behavior of DOM sources suggests that the variations in the average DOM composition were governed by physical processes (e.g., dilution) rather than by new production and/or degradation processes. In contrast to some previous studies of river-estuary systems, the Xiaoqing River-Laizhou Bay estuary system displayed a non-significant correlation between DOM and Hg quantities. Based on this and the variation of Hg concentration along the salinity gradient, we concluded that Hg showed a non-conservative mixing behavior of suggested end-member sources. Thus, rather than mixing, Hg concentration variations seemed to be controlled by biogeochemical processes.

  4. The Fluorescent Properties of Dissolved Organic Matter and Assessment of Total Nitrogen in Overlying Water with Different Dissolved Oxygen Conditions.

    PubMed

    Zhang Hua; Kuan, Wang; Song, Jian; Zhang, Yong; Huang, Ming; Huang, Jian; Zhu, Jing; Huang, Shan; Wang, Meng

    2016-03-01

    This paper used excitation-emission matrix spectroscopy (EEMs) to probe the fluorescence properties of dissolved organic matter (DOM) in the overlying water with different dissolved oxygen (DO) conditions, investigating the relationship between protein-like fluorescence intensity and total nitrogen concentration. The resulting fluorescence spectra revealed three protein-like components (high-excitation wavelength tyrosine, low-excitation wavelength tyrosine, low-excitation wavelength tryptophan) and two fulvic-like components (ultraviolet fulvic-like components, visible fulvic-like components) in the overlying water. Moreover, the protein-like components were dominant in the overlying water's DOM. The fluorescence intensity of the protein-like components decreased significantly after aeration. Two of the protein-like components--the low-excitation wavelength tyrosine and the low-excitation wavelength tryptophan--were more susceptible to degradation by microorganisms within the degradable organic matter with respect to the high-excitation wavelength tyrosine. In contrast, the ultraviolet and visible fulvic-like fluorescence intensity increased along with increasing DO concentration, indicating that the fulvic-like components were part of the refractory organics. The fluorescence indices of the DOM in the overlying water were between 1.65-1.80, suggesting that the sources of the DOM were related to terrigenous sediments and microbial metabolic processes, with the primary source being the contribution from microbial metabolism. The fluorescence indices increased along with DO growth, which showed that microbial biomass and microbial activity gradually increased with increasing DO while microbial metabolism also improved, which also increased the biogenic components in the overlying water. The fluorescence intensity of the high-excitation wavelength tyrosine peak A showed a good linear relationship with the total nitrogen concentration at higher DO concentrations of 2

  5. Marine methane paradox explained by bacterial degradation of dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Repeta, Daniel J.; Ferrón, Sara; Sosa, Oscar A.; Johnson, Carl G.; Repeta, Lucas D.; Acker, Marianne; Delong, Edward F.; Karl, David M.

    2016-12-01

    Biogenic methane is widely thought to be a product of archaeal methanogenesis, an anaerobic process that is inhibited or outcompeted by the presence of oxygen and sulfate. Yet a large fraction of marine methane delivered to the atmosphere is produced in high-sulfate, fully oxygenated surface waters that have methane concentrations above atmospheric equilibrium values, an unexplained phenomenon referred to as the marine methane paradox. Here we use nuclear magnetic resonance spectroscopy to show that polysaccharide esters of three phosphonic acids are important constituents of dissolved organic matter in seawater from the North Pacific. In seawater and pure culture incubations, bacterial degradation of these dissolved organic matter phosphonates in the presence of oxygen releases methane, ethylene and propylene gas. Moreover, we found that in mutants of a methane-producing marine bacterium, Pseudomonas stutzeri, disrupted in the C-P lyase phosphonate degradation pathway, methanogenesis was also disabled, indicating that the C-P lyase pathway can catalyse methane production from marine dissolved organic matter. Finally, the carbon stable isotope ratio of methane emitted during our incubations agrees well with anomalous isotopic characteristics of seawater methane. We estimate that daily cycling of only about 0.25% of the organic matter phosphonate inventory would support the entire atmospheric methane flux at our study site. We conclude that aerobic bacterial degradation of phosphonate esters in dissolved organic matter may explain the marine methane paradox.

  6. Fluorescence Excitation-Emission Matrix Regional Integration to Quantify Spectra for Dissolved Organic Matter

    USGS Publications Warehouse

    Chen, W.; Westerhoff, P.; Leenheer, J.A.; Booksh, K.

    2003-01-01

    Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (??i,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (??T,n = ????i,n) was observed for hydrophobic neutral DOM fractions, followed by lower ??T,n values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

  7. Temporal patterns of dissolved organic matter biodegradability are similar across three rivers of varying size

    NASA Astrophysics Data System (ADS)

    Coble, Ashley A.; Marcarelli, Amy M.; Kane, Evan S.; Toczydlowski, David; Stottlemyer, Robert

    2016-06-01

    Dissolved organic matter (DOM) composition may be an important determinant of its fate in freshwaters, but little is known about temporal variability in DOM composition and the biodegradability of DOM in northern temperate watersheds. We measured biodegradable dissolved organic carbon (BDOC) via incubation assays and DOM composition using optical indices on 11 dates in three Lake Superior tributaries. Percent BDOC (%BDOC) and BDOC concentrations were seasonally synchronous across these watersheds, despite that they vary in size by orders of magnitude (1.7 to 3400 km2). Relative to %BDOC, BDOC concentrations were more tightly constrained among sites on any given date. BDOC also varied within seasons; for example, %BDOC on two different dates in winter were among the highest (29% and 54%) and lowest (0%) values observed for each site (overall %BDOC range: 0 to 72%). DOM composition varied the most among tributaries during a summer storm event when BDOC (both as percent and concentration) was elevated but was remarkably similar among tributaries during fall, spring, and winter. Multivariate models identified humic-like and tryptophan-like fluorophores as predictors of %BDOC, but DOM composition only described 21% of the overall variation in %BDOC. Collectively, these three rivers exported ~18 Gg C yr-1 as DOC and ~2 Gg C yr-1 as BDOC, which corresponded to 9 to 17% of annual DOC exported in biodegradable form. Our results suggest much of the C exported from these northern temperate watersheds may be biodegradable within 28 days and that large pulses of labile DOM can be exported during storm events and spring snowmelt.

  8. Contaminant transport in riverbank filtration in the presence of dissolved organic matter and bacteria: a kinetic approach

    NASA Astrophysics Data System (ADS)

    Kim, Song-Bae; Corapcioglu, M. Yavuz

    2002-09-01

    In riverbank filtration, the removal of organic contaminants is an important task for the production of good quality drinking water. The transport of an organic contaminant in riverbank filtration can be retarded by sorption on to the solid matrix and facilitated by the presence of mobile colloids. In the presence of dissolved organic matter (DOM) and bacteria, the subsurface environment can be modeled as a four-phase porous medium: two mobile colloidal phases, an aqueous phase, and a solid matrix. In this study, a kinetic model is developed to simulate the contaminant transport in riverbank filtration in the presence of DOM and bacteria. The bacterial deposition and the contaminant sorption on bacteria and DOM are expressed with kinetic expressions. The model equations are solved numerically with a fully implicit finite difference method. Simulation results show that the contaminant mobility increases greatly in riverbank filtration due to the presence of DOM. The mobility can be enhanced further when the bacteria and DOM are present together in the aquifer. In this system, the total aqueous phase contaminant concentration, Cct+, includes the contaminant dissolved in the aqueous phase, Cc+, the contaminant sorbed to DOM, σcd+, and the contaminant sorbed to mobile bacteria, Cb+σcbm+, (i.e. Cct+= Cc++ σcd++ Cb+σcbm+). Sensitivity analysis illustrates that the distribution of the total aqueous phase contaminants among the dissolved phase, DOM and bacteria is changed significantly with various Damköhler numbers related to the contaminant sorption on mobile colloids.

  9. Using 18O as a Tracer of Oxygen in the Photochemical Alteration of Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Davis, J. A.; Stubbins, A.; Helms, J.; Dias, R. F.; Mopper, K.

    2006-12-01

    The biogeochemical cycling of dissolved organic matter (DOM) in natural waters is affected by numerous processes, including photochemical alteration. Photochemical processes result in the net oxidation and mineralization of DOM concomitant with dissolved oxygen consumption and production of dissolved inorganic carbon (DIC; principally CO2). The photochemical oxygen budget is not well constrained while DIC production accounts for nearly all the dissolved oxygen consumed, conflicting data suggests that more than half of the oxygen consumed is required to account for observed DOM oxidation and hydrogen peroxide production. An alternate source of oxygen is required to balance this budget; water itself may provide the answer. In order to determine the source of oxygen, a number of time series irradiations were performed using Great Dismal Swamp water (southeast Virginia) with 18O enrichments as either dissolved oxygen or water. Early results, upon irradiation in a UV solar simulator, show significant incorporation of 18O-enriched oxygen into high molecular weight (HMW) DOM from both sources. While the majority of the incorporated oxygen originated from the dissolved oxygen, at least 5 percent originated from water. Data will be presented showing the rate and degree of incorporation of 18O-enriched oxygen from both sources as well as the production of 18O-enriched carbon dioxide. The movement of 18O label will be discussed in relation to shifts in spectral qualities, including photobleaching and spectral slope, of the irradiated samples and selective incorporation as detailed by FT-ICRMS.

  10. Interactions between dissolved organic matter and mercury in the Florida Everglades

    USGS Publications Warehouse

    Aiken, G.; Haitzer, M.; Ryan, J.N.; Nagy, K.; ,

    2003-01-01

    Experiments were conducted using organic matter isolated from various surface waters in the Florida Everglades to study the interactions between dissolved organic matter (DOM) and Hg(II). Conditional distribution coefficients (KDOM???), obtained using an equilibrium dialysis ligand exchange method, were strongly affected by the Hg/DOM concentration ratio. Very strong interactions (KDOM??? = 1023.2??0.5 L kg-1), indicative of Hg-thiol bonds, were observed at Hg/DOM ratios below approximately 1 ??g per mg DOM. Above approximately 10 ??g Hg per mg DOM much lower KDOM??? values (1010.7??0.5 L kg-1) were obtained DOM-Hg interactions were also studied by HgS (log Ksp = -52.4) dissolution and precipitation experiments. In the dissolution experiments, a significant amount of Hg was released from cinnabar in the presence of DOM, suggesting strong interactions. Conversely, precipitation of HgS was strongly inhibited in the presence of low concentrations (???3 mg C/L) of DOM. In both the dissolution and precipitation experiments, organic matter rich in aromatic moieties was more reactive with HgS than less aromatic fractions and sulfur-containing model compounds. These results suggest that DOM can influence the geochemistry of inorganic complexes of Hg in the Everglades, especially HgS, by strong Hg-DOM binding and colloidal stabilization.

  11. Dissolving efficacy of some organic solvents on gutta-percha.

    PubMed

    Magalhães, Bianca Silva; Johann, Julia Elis; Lund, Rafael Guerra; Martos, Josué; Del Pino, Francisco Augusto Burkert

    2007-01-01

    The aim of this study was to evaluate the solubility of gutta-percha in four organic solvents used in endodontics. The solubility of gutta-percha (Dentsply) was assessed in xylol, orange oil, eucalyptol, chloroform and distilled water. A hundred and fifty samples of gutta-percha were prepared using a standardized stainless steel mould and divided into five groups for immersion in the different solvents tested and in distilled water (control group) for 2, 5 and 10 minutes. The means of gutta-percha dissolution in the solvents were obtained by the difference between the pre-immersion original weight and the post-immersion weight in a digital analytical scale (Gehaka-AG2000). Data were statistically analyzed by Analysis of Variance (ANOVA) and multiple comparisons with Scheffes test (p<0.05). The best solvency capacity was obtained with xylol. Chloroform, orange oil and eucalyptol presented similar results, and distilled water did not promote alterations in the gutta-percha.

  12. Dissolving efficacy of organic solvents on root canal sealers.

    PubMed

    Martos, J; Gastal, M T; Sommer, L; Lund, R G; Del Pino, F A B; Osinaga, P W R

    2006-03-01

    The aim of this study was to evaluate the solubility of three types of root canal sealers in three organic solvents used in endodontics. The solubility of calcium-hydroxide-based (Sealer 26), silicon-polydimethylsiloxane-based (RoekoSeal), and zinc-oxide-eugenol based (Endofill and Intrafill) sealers was assessed in eucalyptol, xylol, orange oil, and distilled water. Eighty samples of each filling material were prepared according to the manufacturers' instructions and then divided into four groups for immersion in solvent for 2 or 10 min. The means of sealer dissolution in solvents were obtained by the difference between the original preimmersion weight and the postimmersion weight in a digital analytical scale. Data were statistically analyzed with the Student's t test, and multiple comparisons were performed with Student-Newman-Keuls. Xylol and orange oil showed similar effects, with significant solubilization (P<0.05) of the tested cements. Endofill and Sealer 26 did not show any significant difference in solubilization at the two immersion times, whereas RoekoSeal and Intrafill showed a more pronounced solubility at 10 min. The lowest levels of solubilization occurred in RoekoSeal, Sealer 26, Endofill, and Intrafill. It is concluded that xylol and orange oil presented similar solvent effects with a significant solubility of the tested cements.

  13. Fluorescence-based proxies for lignin in freshwater dissolved organic matter

    USGS Publications Warehouse

    Hernes, Peter J.; Bergamaschi, Brian A.; Eckard, Robert S.; Spencer, Robert G.M.

    2009-01-01

    Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

  14. Optical assessment of colored dissolved organic matter and its related parameters in dynamic coastal water systems

    NASA Astrophysics Data System (ADS)

    Shanmugam, Palanisamy; Varunan, Theenathayalan; Nagendra Jaiganesh, S. N.; Sahay, Arvind; Chauhan, Prakash

    2016-06-01

    Prediction of the curve of the absorption coefficient of colored dissolved organic matter (CDOM) and differentiation between marine and terrestrially derived CDOM pools in coastal environments are hampered by a high degree of variability in the composition and concentration of CDOM, uncertainties in retrieved remote sensing reflectance and the weak signal-to-noise ratio of space-borne instruments. In the present study, a hybrid model is presented along with empirical methods to remotely determine the amount and type of CDOM in coastal and inland water environments. A large set of in-situ data collected on several oceanographic cruises and field campaigns from different regional waters was used to develop empirical methods for studying the distribution and dynamics of CDOM, dissolved organic carbon (DOC) and salinity. Our validation analyses demonstrated that the hybrid model is a better descriptor of CDOM absorption spectra compared to the existing models. Additional spectral slope parameters included in the present model to differentiate between terrestrially derived and marine CDOM pools make a substantial improvement over those existing models. Empirical algorithms to derive CDOM, DOC and salinity from remote sensing reflectance data demonstrated success in retrieval of these products with significantly low mean relative percent differences from large in-situ measurements. The performance of these algorithms was further assessed using three hyperspectral HICO images acquired simultaneously with our field measurements in productive coastal and lagoon waters on the southeast part of India. The validation match-ups of CDOM and salinity showed good agreement between HICO retrievals and field observations. Further analyses of these data showed significant temporal changes in CDOM and phytoplankton absorption coefficients with a distinct phase shift between these two products. Healthy phytoplankton cells and macrophytes were recognized to directly contribute to the

  15. Dynamics and Biodegradability of Chromophoric Dissolved Organic Matter in a Severely Polluted River

    NASA Astrophysics Data System (ADS)

    Borisover, Mikhail; Laor, Yael; Saadi, Ibrahim; Lado, Marcos; Bukhanovsky, Nadezhda

    2010-05-01

    The 70-kilometer long Kishon River is one of Israel's largest rivers. Its annual discharge may vary substantially, e.g. between 47 and 10 million m3. The lower section of the river has been severely polluted for dozens of years, by industrial effluents containing heavy metals, radionuclides, nutrients, and diverse organic contaminants. The total volume of effluents discharged from the plants into the river stream may contribute as much as 30% of the total water volume. Dissolved organic matter (DOM) and specifically its chromophoric components (CDOM) including humic-like and proteinous substances may form water-soluble complexes with multiple organic and inorganic pollutants and, thus, enhance their release from the sediments and their mobility. The volatility of pollutants, their bioavailability, toxicity and potential to undergo bio-, abiotic and photodegradation may be affected by interactions with CDOM. Therefore, the dynamics of CDOM is important for understanding the fate of pollutants in aquatic environments. In this study, we intended (i) to characterize the seasonal and spatial variability of CDOM at the most contaminated lower section of the Kishon River and (ii) to assess the impact of biodegradation, dilution by seawater and contribution of discharged effluents on the overall dynamics of DOM and CDOM. For this purpose, water was sampled during 11 months at 8 locations distributed along Lower Kishon River. Samples were characterized for concentrations of dissolved organic carbon (DOC), UV- absorbance at 254 nm, electrical-conductivity, pH, concentration of dissolved oxygen and excitation emission matrices (EEM) of fluorescence. Parallel factor analysis of EEM enabled quantifying two major groups of riverine fluorescent CDOM: humic-like substances and components spectrally similar to those associated with phytoplankton productivity. CDOM (including fluorescent matter and components absorbing light at 254 nm) was found resistant to biodegradation by

  16. Removal of terrestrial dissolved organic carbon in aquatic ecosystems of a temperate river network.

    NASA Astrophysics Data System (ADS)

    Wollheim, W. M.; Stewart, R. J.; Aiken, G.; Butler, K. D.; Morse, N.; Salisbury, J.

    2015-12-01

    Surface waters play an important role in the global carbon balance. Dissolved organic carbon (DOC) fluxes are a major transfer of terrestrial carbon to river systems, and the net removal of terrestrial DOC in aquatic systems is poorly constrained. We used a combination of spatially distributed sampling of three DOC fractions, nitrate, and chloride in streams of different size throughout a river network and modeling to quantify the net removal of terrestrial DOC relative to other constituents during a summer base flow period. The approach was applied to the 400 km2 Ipswich River watershed, MA, USA. We found that aquatic reactivity of terrestrial DOC leading to net loss is low, closer to conservative chloride than to reactive nitrogen. Net removal of DOC occurred mainly from the hydrophobic organic acid fraction, while hydrophilic and transphilic acids showed no net change. Model fits were improved using the different DOC fractions than when using bulk DOC, indicating that partitioning of bulk DOC into different fractions is critical for understanding terrestrial DOC removal. These findings suggest that river systems may have only a modest ability to alter the amounts of terrestrial DOC delivered to coastal zones.

  17. Method for removing and decolorizing aqueous waste effluents containing dissolved or dispersed organic matter

    DOEpatents

    Case, F.N.; Ketchen, E.E.

    1975-10-14

    A method is provided for treating organic waste material dissolved or dispersed in an aqueous effluent, which comprises contacting the effluent with an inert particulate carbonaceous sorbent at an oxygen pressure up to 2000 psi, irradiating the resultant mixture with high energy radiation until a decolorized liquid is produced, and then separating the decolorized liquid.

  18. PHOTOCHEMICAL MINERALIZATION OF DISSOLVED ORGANIC NITROGEN TO AMMONIUM IN THE BALTIC SEA

    EPA Science Inventory

    Solar radiation-induced photochemistry can be considered as a new source of nutrients when photochemical reactions release bioavailable nitrogen from biologically non-reactive dissolved organic nitrogen (DON). Pretreatments of Baltic Sea waters in the dark indicated that >72% of ...

  19. INFLUENCE OF DISSOLVED ORGANIC MATTER ON AGROCHEMICAL PHOTOREACTIONS IN AQUATIC ENVIRONMENTS

    EPA Science Inventory

    Pioneering studies by Don Crosby and co-workers demonstrated that the sunlight-induced dissipation of agrochemicals in water often is strongly affected by natural constituents in the water such as nitrate and dissolved organic matter. In this presentation, the focus is on the rol...

  20. Organic carbon and dissolved oxygen budgets for a commerical-size, in-pond raceway system

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Intensive production of Ictalurid catfish in the United States has increased over the past several years and a better understanding of the amount of organic carbon (OC) and dissolved oxygen (DO) in these culture environments is needed. Budgets for OC and DO were estimated over a production season (M...

  1. Influence of Dissolved Organic Matter and Fe (II) on the Abiotic Reduction of Pentachloronitrobenzene

    EPA Science Inventory

    Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in n...

  2. Comment on "Dilution limits dissolved organic carbon utilization in the deep ocean".

    PubMed

    Jiao, Nianzhi; Legendre, Louis; Robinson, Carol; Thomas, Helmuth; Luo, Ya-Wei; Dang, Hongyue; Liu, Jihua; Zhang, Rui; Tang, Kai; Luo, Tingwei; Li, Chao; Wang, Xiaoxue; Zhang, Chuanlun

    2015-12-18

    Arrieta et al. (Reports, 17 April 2015, p. 331) propose that low concentrations of labile dissolved organic carbon (DOC) preclude prokaryotic consumption of a substantial fraction of DOC in the deep ocean and that this dilution acts as an alternative mechanism to recalcitrance for long-term DOC storage. Here, we show that the authors' data do not support their claims.

  3. Response to Comment on "Dilution limits dissolved organic carbon utilization in the deep ocean".

    PubMed

    Arrieta, Jesús M; Mayol, Eva; Hansman, Roberta L; Herndl, Gerhard J; Dittmar, Thorsten; Duarte, Carlos M

    2015-12-18

    Our recent finding that dilution limits dissolved organic carbon (DOC) utilization in the deep ocean has been criticized based on the common misconception that lability equates to rapid and complete utilization. Even when considering the redefinition of recalcitrant DOC recently proposed by Jiao et al., the dilution hypothesis best explains our experimental observations.

  4. ISOTOPIC BIOGEOCHEMISTRY OF DISSOLVED ORGANIC NITROGEN: A NEW TECHNIQUE AND APPLICATION. (R825151)

    EPA Science Inventory

    We present a new technique for isolating and isotopically characterizing dissolved organic nitrogen (DON) for non-marine waters, 15N values for DON from lacustrine samples and data suggesting that this technique will be a...

  5. TREATMENT OF URBAN STORMWATER FOR DISSOLVED POLLUTANTS: A COMPARATIVE STUDY OF THREE NATURAL ORGANIC MEDIA

    EPA Science Inventory

    The feasibility of using hard and soft wood tree mulch and processed jute fiber, as filter media, for treating mixtures of dissolved pollutants (toxic organic compounds and heavy metals) in urban stormwater (SW) runoff was evaluated. Copper (Cu), cadmium (Cd), chromium (Cr+6), l...

  6. Pyrolysis temperature-dependent release of dissolved organic carbon from plant, manure, and biorefinery wastes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Limited information is available to understand the chemical structure of biochar’s labile dissolved organic carbon (DOC) fraction that will change amended soil’s DOC composition. This study utilized the high sensitivity of fluorescence excitation-emission (EEM) spectrophotometry to understand the s...

  7. PRODUCTION OF HYDRATED ELECTRONS FROM PHOTOIONIZATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS

    EPA Science Inventory

    Under UV irradiation, an important primary photochemical reaction of colored dissolved organic matter (CDOM) is electron ejection, producing hydrated electrons (e-aq). The efficiency of this process has been studied in both fresh and seawater samples with both steady-state scave...

  8. PHOTOCHEICAL PRODUCTION OF HYDROXYL RADICAL IN NATURAL WATER - THE ROLE OF IRON AND DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    Photochemical hydroxyl radical (OH) production was measured in several natural waters to investigate the importance of colored dissolved organic matter (CDOM) and iron-CDOM complexes as sources of OH. High rates of OH photoproduction in highly colored, iron-rich, acidic waters a...

  9. CONSTANTS FOR MERCURY BINDING BY DISSOLVED ORGANIC MATTER ISOLATES FROM THE FLORIDA EVERGLADES. (R827653)

    EPA Science Inventory

    Dissolved organic matter (DOM) has been implicated as an important complexing agent for Hg that can affect its mobility and bioavailability in aquatic ecosystems. However, binding constants for natural Hg-DOM complexes are not well known. We employed a competitive ligand appro...

  10. Production of Chromophoric Dissolved Organic Matter from Mangrove Leaf Litter and Floating Sargassum Colonies

    EPA Science Inventory

    Chromophoric dissolved organic matter (CDOM) strongly absorbs solar radiation in the blue-green and serves as the primary attenuator of water column ultraviolet radiation (UV-R). CDOM interferes with remote sensing of ocean chlorophyll and can control UV-R-induced damage to light...

  11. Dissolved organic matter dynamics in surface waters affected by oil spill pollution: Results from the Serious Game exercise

    NASA Astrophysics Data System (ADS)

    Gonnelli, M.; Galletti, Y.; Marchetti, E.; Mercadante, L.; Retelletti Brogi, S.; Ribotti, A.; Sorgente, R.; Vestri, S.; Santinelli, C.

    2016-11-01

    Dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM, respectively) surface distribution was studied during the Serious Game exercise carried out in the Eastern Ligurian Sea, where an oil spill was localized by using satellite images and models. This paper reports the first DOC, CDOM and FDOM data for this area together with an evaluation of fluorescence as a fast and inexpensive tool for early oil spill detection in marine waters. The samples collected in the oil spill showed a fluorescence intensity markedly higher ( 5 fold) than all the other samples. The excitation-emission matrixes, coupled with parallel factor analysis (PARAFAC), allowed for the identification in the FDOM pool of a mixture of polycyclic aromatic hydrocarbons, humic-like and protein-like fluorophores.

  12. Photochemical and microbial transformation of terrestrial dissolved organic matter - Lena River vs. rivers in mid and low latitudes

    NASA Astrophysics Data System (ADS)

    Vähätalo, A. V.; Aarnos, H.; Paolucci, E. M.; Musibono, D. E.; Khan, S. R.; Gelinas, Y.; Shantz, A.; Huang, Q.; Schneider, W.; Rezende, C. E.; Petrescu, E.; Reader, H. E.

    2012-04-01

    The aim of this study was to assess the fate of riverine dissolved organic matter (DOM) in coastal ocean. In that environment after the sedimentation of terrestrial particulate matter and the advective mixing of river water to optically clear marine water, the photochemical transformation of riverine DOM has a large potential for decomposing riverine DOM. For this study, we collected water samples from ten large rivers and carried out laboratory experiments with the river water samples. The potential for the photochemical decomposition of riverine dissolved organic matter was assessed by exposing sterile-filtered river waters to simulated solar radiation. Dark control samples we treated similarly but were not irradiated. The exposures were designed to decompose photochemically chromophoric dissolved organic matter, the major absorber of UV-vis radiation and the primary initiator of the direct photoreactions of DOM. In the end of irradiation, the difference in the concentration of dissolved organic carbon between the irradiated and the dark control sample corresponded to that portion of dissolved organic carbon (DOC) decomposable through direct photoreactions to carbon dioxide. In order to assess the amount of DOC phototransformed into biologically available forms, the irradiated and the dark control water samples received indigenous inoculums of riverine microbes and were incubated in the darkness. After a month, the difference in the concentration of DOC between the irradiated and dark control sample was considered to represent the photoreactive portion of DOC, while the residual DOC made up the DOC resistant to photochemical reactions. The photoreactive portion of DOC varied among rivers and was related to the amount of chromophoric dissolved organic matter in the water samples. The biological decomposition experiments were extended to last up to one year and predictions about the biodegradability of irradiated and dark control DOM were made by fitting a

  13. Cross-scale ensemble projections of dissolved organic carbon dynamics in boreal forest streams

    NASA Astrophysics Data System (ADS)

    Oni, Stephen K.; Futter, Martyn N.; Teutschbein, Claudia; Laudon, Hjalmar

    2014-05-01

    Climate is an important driver of dissolved organic carbon (DOC) dynamics in boreal catchments characterized by networks of streams within forest-wetland landscape mosaics. In this paper, we assess how climate change may affect stream DOC concentrations ([DOC]) and export from boreal forest streams with a multi-model ensemble approach. First, we apply an ensemble of regional climate models (RCMs) to project soil temperatures and stream-flows. These data are then used to drive two biogeochemical models of surface water DOC: (1) The Integrated Catchment model for Carbon (INCA-C), a detailed process-based model of DOC operating at the catchment scale, and (2) The Riparian Integration Model (RIM), a simple dynamic hillslope scale model of stream [DOC]. All RCMs project a consistent increase in temperature and precipitation as well as a shift in spring runoff peaks from May to April. However, they present a considerable range of possible future runoff conditions with an ensemble median increase of 31 % between current and future (2061-2090) conditions. Both biogeochemical models perform well in describing the dynamics of present-day stream [DOC] and fluxes, but disagree in their future projections. Here, we assess possible futures in three boreal catchments representative of forest, mire and mixed landscape elements. INCA-C projects a wider range of stream [DOC] due to its temperature sensitivity, whereas RIM gives consistently larger inter-annual variation and a wider range of exports due to its sensitivity to hydrological variations. The uncertainties associated with modeling complex processes that control future DOC dynamics in boreal and temperate catchments are still the main limitation to our understanding of DOC mechanisms under changing climate conditions. Novel, currently overlooked or unknown drivers may appear that will present new challenges to modelling DOC in the future.

  14. Biodegradability of dissolved organic carbon within and among hillslopes along a chronosequence of landscape age in arctic Alaska

    NASA Astrophysics Data System (ADS)

    Whittinghill, K. A.; Finlay, J. C.; Hobbie, S. E.

    2009-12-01

    A thorough understanding of the influence of landscape heterogeneity on arctic soil organic matter processing is necessary to predict how arctic carbon cycling will change with future climate. Large variation in geology, topography, vegetation, and permafrost extent exists throughout the circumpolar region. In the Kuparuk River region of northern Alaska, significant differences in mineralization of soil organic matter and production of dissolved organic carbon exist among landscapes with different glaciation histories which cannot be explained entirely by geochemical differences among these landscapes. In addition to variation among landscape ages, previous research in the region has demonstrated significant differences in soil water dissolved organic carbon concentrations within hillslope toposequences. We hypothesized that differences in biodegradability of dissolved organic matter within hillslopes or across landscapes of different age may drive observed variability in soil water dissolved organic carbon concentrations, dissolved organic carbon production, and soil respiration. To test this hypothesis we examined dissolved organic carbon extracted (with water) from soils within hillslopes across a chronosequence of landscapes with different glacial histories using four direct and indirect indices of dissolved organic matter biodegradability: 1) specific UV absorbance, 2) fluorescence index, 3) respiration measured by oxygen consumption rates, and 4) a long-term incubation of dissolved organic mater consumption. We selected three replicate hillslopes within four distinct landscape ages near the Kuparuk River. Within each hillslope we extracted dissolved organic matter from three organic soil samples collected from each of three transects: a) adjacent to the stream, b) along the vegetation boundary between upslope and streamside vegetation, and c) within upslope tussock tundra vegetation. Soil extract dissolved organic carbon concentrations were significantly

  15. Investigation of organic carbon transformation in soils of dominant dissolved organic carbon source zones

    NASA Astrophysics Data System (ADS)

    Pissarello, Anna; Miltner, Anja; Oosterwoud, Marieke; Fleckenstein, Jan; Kästner, Matthias

    2014-05-01

    Over the past 20 years both a decrease in soil organic matter (SOM) and an increase in the dissolved organic carbon (DOC) concentrations in surface water bodies, including drinking water reservoirs, have been recorded in the northern hemisphere. This development has severe consequences for soil fertility and for drinking water purification. As both processes occur simultaneously, we assume that microbial SOM degradation, which transforms SOM into CO2 and DOC, is a possible source of the additional DOC in the surface water. In addition we speculate that both processes are initially triggered by physical mechanisms, resulting in a modification of the organic matter solubility equilibria and thus in higher SOM availability and DOC mobilization. The general hypothesis of the study is therefore that SOM loss and DOC increase are combined consequences of enhanced microbial degradation of SOM and that this is a result of climate variations and global change, e.g. the increase of the temperature, the alteration of the water regime (i.e. increase of the frequency of drying and rewetting cycles and a higher number of heavy rain events), but also the decrease of the atmospheric acid deposition resulting in an increase of soil pH values. The general goal of the study is the identification of the dominant processes and controlling factors involved in soil microbial carbon turnover and mobilization of DOC in soils from catchment areas that contribute DOC to the receiving waters and the downstream Rappbode reservoir, which showed a pronounced increase in DOC concentration in recent years. This reservoir is the source of drinking water for about one million people in northern Germany. Preliminary screening experiments, consisting of 65-day soil batch incubation experiments, have been conducted in order to select the parameters (and the parameter ranges) of relevance for further in-depth experiments. During the experiments, different soil systems were exposed to different

  16. Continuous Dissolved Oxygen Measurements and Modelling Metabolism in Peatland Streams.

    PubMed

    Dick, Jonathan J; Soulsby, Chris; Birkel, Christian; Malcolm, Iain; Tetzlaff, Doerthe

    2016-01-01

    Stream water dissolved oxygen was monitored in a 3.2km2 moorland headwater catchment in the Scottish Highlands. The stream consists of three 1st order headwaters and a 2nd order main stem. The stream network is fringed by peat soils with no riparian trees, though dwarf shrubs provide shading in the lower catchment. Dissolved oxygen (DO) is regulated by the balance between atmospheric re-aeration and the metabolic processes of photosynthesis and respiration. DO was continuously measured for >1 year and the data used to calibrate a mass balance model, to estimate primary production, respiration and re-aeration for a 1st order site and in the 2nd order main stem. Results showed that the stream was always heterotrophic at both sites. Sites were most heterotrophic in the summer reflecting higher levels of stream metabolism. The 1st order stream appeared more heterotrophic which was consistent with the evident greater biomass of macrophytes in the 2nd order stream, with resulting higher primary productivity. Comparison between respiration, primary production, re-aeration and potential physical controls revealed only weak relationships. However, the most basic model parameters (e.g. the parameter linking light and photosynthesis) controlling ecosystem processes resulted in significant differences between the sites which seem related to the stream channel geometry.

  17. Continuous Dissolved Oxygen Measurements and Modelling Metabolism in Peatland Streams

    PubMed Central

    Dick, Jonathan J.; Soulsby, Chris; Birkel, Christian; Malcolm, Iain; Tetzlaff, Doerthe

    2016-01-01

    Stream water dissolved oxygen was monitored in a 3.2km2 moorland headwater catchment in the Scottish Highlands. The stream consists of three 1st order headwaters and a 2nd order main stem. The stream network is fringed by peat soils with no riparian trees, though dwarf shrubs provide shading in the lower catchment. Dissolved oxygen (DO) is regulated by the balance between atmospheric re-aeration and the metabolic processes of photosynthesis and respiration. DO was continuously measured for >1 year and the data used to calibrate a mass balance model, to estimate primary production, respiration and re-aeration for a 1st order site and in the 2nd order main stem. Results showed that the stream was always heterotrophic at both sites. Sites were most heterotrophic in the summer reflecting higher levels of stream metabolism. The 1st order stream appeared more heterotrophic which was consistent with the evident greater biomass of macrophytes in the 2nd order stream, with resulting higher primary productivity. Comparison between respiration, primary production, re-aeration and potential physical controls revealed only weak relationships. However, the most basic model parameters (e.g. the parameter linking light and photosynthesis) controlling ecosystem processes resulted in significant differences between the sites which seem related to the stream channel geometry. PMID:27556278

  18. Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

    SciTech Connect

    Ravichandran, M.; Ryan, J.N.; Aiken, G.R.; Reddy, M.M.

    1998-11-01

    Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca{sup 2+}. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in Dl water had no detectable dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates correlated positively with enhanced cinnabar dissolution. {zeta}-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

  19. Predicting Copper Speciation in Estuarine Waters-Is Dissolved Organic Carbon a Good Proxy for the Presence of Organic Ligands?

    PubMed

    Pearson, Holly B C; Comber, Sean D W; Braungardt, Charlotte; Worsfold, Paul J

    2017-02-21

    A new generation of speciation-based aquatic environmental quality standards (EQS) for metals have been developed using models to predict the free metal ion concentration, the most ecologically relevant form, to set site-specific values. Some countries such as the U.K. have moved toward this approach by setting a new estuarine and marine water EQS for copper, based on an empirical relationship between copper toxicity to mussels (Mytilus sp.) and ambient dissolved organic carbon (DOC) concentrations. This assumes an inverse relationship between DOC and free copper ion concentration owing to complexation by predominantly organic ligands. At low DOC concentrations, the new EQS is more stringent, but above 162 μM DOC it is higher than the previous value. However, the relationship between DOC and copper speciation is poorly defined in estuarine waters. This research discusses the influence of DOC from different sources on copper speciation in estuaries and concludes that DOC is not necessarily an accurate predictor of copper speciation. Nevertheless, the determination of ligand strength and concentrations by Competitive Ligand Exchange Adsorptive Cathodic Stripping Voltammetry enabled the prediction of the free metal ion concentration within an order of magnitude for estuarine waters by using a readily available metal speciation model (Visual MINTEQ).

  20. The Effects of Acid Rock Drainage (ARD) on Fluorescent Dissolved Organic Matter (DOM)

    NASA Astrophysics Data System (ADS)

    Lee, R. H.; Gabor, R. S.; SanClements, M.; McKnight, D. M.

    2011-12-01

    Located in the Rocky Mountains of central Colorado, the catchments drained by the headwaters of the Snake River are dominated by metal- and sulfide-rich bedrock. The breakdown of these minerals results in acidic metal-rich waters in the Snake (pH ~3) that persist until the confluence with Deer Creek (pH ~7). Previous research has been conducted examining the interactions of acid-rock drainage (ARD) and dissolved organic matter (DOM), but the effects of ARD on DOM production is not as well understood. In a synoptic study, samples of creek water were collected at evenly spaced intervals along the length of a tributary to the Snake River which drains an area with ARD. At each sampling location, water samples were collected and pH, conductivity, and temperature were measured. Water samples were analyzed for metal chemistry, and the DOM was analyzed with UV-Vis and fluorescence spectroscopy. The character of the DOM was described using PARAFAC and index calculations. This work demonstrates that the introduction of acid and dissolved metal species has notable effects on DOM composition. Preliminary data suggests that the introduction of acid drainage is responsible for the formation of a fluorophore not accounted for in the Cory and McKnight PARAFAC model. Both high concentrations of heavy metals (e.g. zinc) and the novel fluorophore are present downstream from a mining site, which indicates it as a possible source of both species. The data suggest a link between the introduction of fluorophores in acidic waters and acidophile populations at the source of the acid rock drainage.

  1. Linked changes in marine dissolved organic carbon molecular size and radiocarbon age

    NASA Astrophysics Data System (ADS)

    Walker, B. D.; Primeau, F. W.; Beaupré, S. R.; Guilderson, T. P.; Druffel, E. R. M.; McCarthy, M. D.

    2016-10-01

    Marine dissolved organic carbon (DOC) is a major global carbon reservoir, yet its cycling remains poorly understood. Previous work suggests that DOC molecular size and chemical composition can significantly affect its bioavailability. Thus, DOC size and composition may control DOC cycling and radiocarbon age (via Δ14C). Here we show that DOC molecular size is correlated to DOC Δ14C in the Pacific Ocean. Our results, based on a series of increasing molecular size fractions from three depths in the Pacific, show increasing DOC Δ14C with increasing molecular size. We use a size-age distribution model to predict the DOC and Δ14C of ultrafiltered DOC. The model predicts both large and small surface DOC with high Δ14C and a narrow range (200-500 Da) of low Δ14C DOC. Deep model offsets suggest different size distributions and/or Δ14C sources at 670-915 m. Our results suggest that molecular size and composition are linked to DOC reactivity and storage in the ocean.

  2. Biodegradation kinetics of dissolved organic matter chromatographic fractions in an intermittent river

    NASA Astrophysics Data System (ADS)

    Catalán, N.; Casas-Ruiz, J. P.; Schiller, D.; Proia, L.; Obrador, B.; Zwirnmann, E.; Marcé, R.

    2017-01-01

    Controls on the degradation of dissolved organic matter (DOM) are complex but key to understand the role of freshwaters in the carbon cycle. Both the origin and previous degradation history have been suggested to determine DOM reactivity, but it is still a major challenge to understand the links between DOM composition and biodegradation kinetics. An appropriate context to study these links are intermittent rivers, as summer drought naturally diversifies DOM sources and sinks. Here we investigated the biodegradation kinetics of DOM in the main aquatic environments present in a temporary river. During dark incubations we traced the dynamics of bulk DOM and its main chromatographic fractions defined using LC-OCD: high molecular weight substances (HMWS), low molecular weight substances (LMWS), and humic substances and building blocks. Bulk DOM decay patterns were successfully fitted to the reactivity continuum (RC) biodegradation model. The RC parameters depicted running waters as the sites presenting a more reactive DOM, and temporary pools, enriched in leaf litter, as the ones with slowest DOM decay. The decay patterns of each DOM fraction were consistent throughout sites. LMWS and HMWS decayed in all cases and could be modeled using the RC model. Notably, the dynamics of LMWS controlled the bulk DOM kinetics. We discuss the mechanistic basis for the chromatographic fractions' kinetics during biodegradation and the implications that preconditioning and summer drought can have for DOM biodegradation in intermittent rivers.

  3. Quantifying tropical peatland dissolved organic carbon (DOC) using UV-visible spectroscopy.

    PubMed

    Cook, Sarah; Peacock, Mike; Evans, Chris D; Page, Susan E; Whelan, Mick J; Gauci, Vincent; Kho, Lip Khoon

    2017-02-27

    UV-visible spectroscopy has been shown to be a useful technique for determining dissolved organic carbon (DOC) concentrations. However, at present we are unaware of any studies in the literature that have investigated the suitability of this approach for tropical DOC water samples from any tropical peatlands, although some work has been performed in other tropical environments. We used water samples from two oil palm estates in Sarawak, Malaysia to: i) investigate the suitability of both single and two-wavelength proxies for tropical DOC determination; ii) develop a calibration dataset and set of parameters to calculate DOC concentrations indirectly; iii) provide tropical researchers with guidance on the best spectrophotometric approaches to use in future analyses of DOC. Both single and two-wavelength model approaches performed well with no one model significantly outperforming the other. The predictive ability of the models suggests that UV-visible spectroscopy is both a viable and low cost method for rapidly analyzing DOC in water samples immediately post-collection, which can be important when working at remote field sites with access to only basic laboratory facilities.

  4. DISSOLVED ORGANIC MATTER AND METALS: EFFECTS OF PH ON PARTITIONING NATURAL ORGANIC MATTER IN SOILS AND WATER

    EPA Science Inventory

    Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb, and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was fractionated into three operationally defined fractions: hydrophilic acids (Hyd), fulvic acids (FA), an...

  5. Deepwater Horizon oil in Gulf of Mexico waters after 2 years: transformation into the dissolved organic matter pool.

    PubMed

    Bianchi, Thomas S; Osburn, Christopher; Shields, Michael R; Yvon-Lewis, Shari; Young, Jordan; Guo, Laodong; Zhou, Zhengzhen

    2014-08-19

    Recent work has shown the presence of anomalous dissolved organic matter (DOM), with high optical yields, in deep waters 15 months after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico (GOM). Here, we continue to use the fluorescence excitation-emission matrix (EEM) technique coupled with parallel factor analysis (PARAFAC) modeling, measurements of bulk organic carbon, dissolved inorganic carbon (DIC), oil indices, and other optical properties to examine the chemical evolution and transformation of oil components derived from the DWH in the water column of the GOM. Seawater samples were collected from the GOM during July 2012, 2 years after the oil spill. This study shows that, while dissolved organic carbon (DOC) values have decreased since just after the DWH spill, they remain higher at some stations than typical deep-water values for the GOM. Moreover, we continue to observe fluorescent DOM components in deep waters, similar to those of degraded oil observed in lab and field experiments, which suggest that oil-related fluorescence signatures, as part of the DOM pool, have persisted for 2 years in the deep waters. This supports the notion that some oil-derived chromophoric dissolved organic matter (CDOM) components could still be identified in deep waters after 2 years of degradation, which is further supported by the lower DIC and partial pressure of carbon dioxide (pCO2) associated with greater amounts of these oil-derived components in deep waters, assuming microbial activity on DOM in the current water masses is only the controlling factor of DIC and pCO2 concentrations.

  6. Isotopic analysis of dissolved organic carbon in produced water brines by wet chemical oxidation and cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Thomas, Randal; Conaway, Christopher; Saad, Nabil; Kharaka, Yousif

    2013-04-01

    Identification of fluid migration and escape from intentionally altered subsurface geologic systems, such as in hydraulic fracturing, enhanced oil recovery, and carbon sequestration activities, is an important issue for environmental regulators based on the traction that the "fracking" process is gathering across the United States. Given diverse injected fluid compositions and the potential for toxic or regulated compounds to be released, one of the most important steps in the process is accurately identifying evidence of injected fluid escape during and after injection processes. An important tool in identifying differences between the natural groundwater and injected fluid is the isotopic composition of dissolved constituents including inorganic components such as Sr and carbon isotopes of the dissolved organic compounds. Since biological processes in the mesothermal subsurface can rapidly alter the organic composition of a fluid, stable carbon isotopes of the dissolved organic compounds (DOC) are an effective means to identify differences in the origin of two fluids, especially when coupled with inorganic compound analyses. The burgeoning field of cavity ring-down spectroscopy (CRDS) for isotopic analysis presents an opportunity to obtain rapid, reliable and cost-effective isotopic measurements of DOC in potentially affected groundwater for the identification of leakage or the improvement of hydrogeochemical pathway models. Here we adapt the use of the novel hyphenated TOC-CRDS carbon isotope analyzer for the analysis of DOC in produced water by wet oxidation and describe the methods to evaluate performance and obtain useful information at higher salinities. Our methods are applied to a specific field example in a CO2-enhanced EOR field in Cranfield, Mississippi (USA) as a means to demonstrate the ability to distinguish natural and injected DOC using the stable isotopic composition of the dissolved organic carbon when employing the novel TOC-CRDS instrumentation

  7. Organic amendments' dissolved organic carbon influences bioavailability of agricultural soil DOC

    NASA Astrophysics Data System (ADS)

    Straathof, Angela L.; Chincarini, Riccardo; Hoffland, Ellis; Comans, Rob N. J.

    2013-04-01

    Agricultural soils benefit from additions of organic amendments because they improve soil structure, are a source of plant nutrients, and increase concentrations of soil organic carbon (SOC). The latter fuels microbial processes important for plant growth, including nutrient mineralization and the suppression of plant diseases. However, these amendment additions range in quality and quantity of C and little is known about how their properties interact with native soil C and affect turnover. The dissolved pool of SOC (DOC) may be the most important C source for these processes as it is more biologically available and thus relatively easily turned over by the soil microbial biomass. Using a rapid-batch DOC fractionation procedure, we studied the composition of different organic amendments' DOC pools and measured how their additions change the quantity and turnover of soil DOC. Fractions isolated and quantified with this procedure include humic and fulvic acids, hydrophobic neutral and hydrophilic compounds. We hypothesized that these range from biologically recalcitrant to readily available, respectively. Amendments analysed included composts of different source materials and maturation stages collected from two different compost facilities in the Netherlands. Both total DOC concentrations and proportions of the aforementioned fractions ranged highly between composts. Composts cured for >10 days had a lower proportion of hydrophilic C compounds, suggesting that these are the most bioavailable and released as CO2 via microbial activity during maturation. To measure the effects of compost DOC on soil DOC, we extracted the former and added it to a sandy soil in an incubation experiment. The amendment increased soil total DOC, CO2 production from the soil, and the pools of humic and fulvic acids as a proportion of total DOC. Turnover of C from the incubated soil was measured by substrate-induced CO2 production (an indicator of microbial activity) from a 96-well

  8. Artificial neural network modeling of dissolved oxygen in reservoir.

    PubMed

    Chen, Wei-Bo; Liu, Wen-Cheng

    2014-02-01

    The water quality of reservoirs is one of the key factors in the operation and water quality management of reservoirs. Dissolved oxygen (DO) in water column is essential for microorganisms and a significant indicator of the state of aquatic ecosystems. In this study, two artificial neural network (ANN) models including back propagation neural network (BPNN) and adaptive neural-based fuzzy inference system (ANFIS) approaches and multilinear regression (MLR) model were developed to estimate the DO concentration in the Feitsui Reservoir of northern Taiwan. The input variables of the neural network are determined as water temperature, pH, conductivity, turbidity, suspended solids, total hardness, total alkalinity, and ammonium nitrogen. The performance of the ANN models and MLR model was assessed through the mean absolute error, root mean square error, and correlation coefficient computed from the measured and model-simulated DO values. The results reveal that ANN estimation performances were superior to those of MLR. Comparing to the BPNN and ANFIS models through the performance criteria, the ANFIS model is better than the BPNN model for predicting the DO values. Study results show that the neural network particularly using ANFIS model is able to predict the DO concentrations with reasonable accuracy, suggesting that the neural network is a valuable tool for reservoir management in Taiwan.

  9. Advanced Residuals Analysis for Determining the Number of PARAFAC Components in Dissolved Organic Matter.

    PubMed

    Cuss, Chad W; Guéguen, Céline; Andersson, Per; Porcelli, Don; Maximov, Trofim; Kutscher, Liselott

    2016-02-01

    Parallel factor analysis (PARAFAC) has facilitated an explosion in research connecting the fluorescence properties of dissolved organic matter (DOM) to its functions and biogeochemical cycling in natural and engineered systems. However, the validation of robust PARAFAC models using split-half analysis requires an oft unrealistically large number (hundreds to thousands) of excitation-emission matrices (EEMs), and models with too few components may not adequately describe differences between DOM. This study used self-organizing maps (SOM) and comparing changes in residuals with the effects of adding components to estimate the number of PARAFAC components in DOM from two data sets: MS (110 EEMs from nine leaf leachates and headwaters) and LR (64 EEMs from the Lena River). Clustering by SOM demonstrated that peaks clearly persisted in model residuals after validation by split-half analysis. Plotting the changes to residuals was an effective method for visualizing the removal of fluorophore-like fluorescence caused by increasing the number of PARAFAC components. Extracting additional PARAFAC components via residuals analysis increased the proportion of correctly identified size-fractionated leaf leachates from 56.0 ± 0.8 to 75.2 ± 0.9%, and from 51.7 ± 1.4 to 92.9 ± 0.0% for whole leachates. Model overfitting was assessed by considering the correlations between components, and their distributions amongst samples. Advanced residuals analysis improved the ability of PARAFAC to resolve the variation in DOM fluorescence, and presents an enhanced validation approach for assessing the number of components that can be used to supplement the potentially misleading results of split-half analysis.

  10. CARBON LOSS AND OPTICAL PROPERTY CHANGES DURING LONG-TERM PHOTOCHEMICAL AND BIOLOGICAL DEGRADATION OF ESTUARINE DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    Terrestrially derived dissolved organic matter (DOM) impacts the optical properties of coastal seawater and affects carbon cycling on a global scale. We studied sequential long-term photochemical and biological degradation of estuarine dissolved organic matter from the
    Satilla...

  11. Method development for measuring biodegradable dissolved organic nitrogen in treated wastewater.

    PubMed

    Khan, Eakalak; Awobamise, Mayo; Jones, Kimberly; Murthy, Sudhir

    2009-08-01

    A method for determining biodegradable dissolved organic nitrogen (BDON) in treated wastewater was developed. The method adopts the approaches used in the biochemical oxygen demand and biodegradable dissolved organic carbon tests to make it usable as a routine procedure at wastewater treatment plants (WWTPs). The development focused on various aspects of the procedure, including inoculum type and concentration, incubation period, and the need for sample filtration after incubation. The method was tested with filtered effluent samples from two nutrient removal WWTPs and standard organic nitrogen solutions. Accurate and precise BDON results were obtained with 2 mL of acclimated mixed-liquor suspended solids diluted to a concentration of 240 mg/L as an inoculum and an incubation period of 20 days. Sample filtration after incubation was not required.

  12. Coupled ocean-atmosphere loss of marine refractory dissolved organic carbon

    NASA Astrophysics Data System (ADS)

    Kieber, David J.; Keene, William C.; Frossard, Amanda A.; Long, Michael S.; Maben, John R.; Russell, Lynn M.; Kinsey, Joanna D.; Tyssebotn, Inger Marie B.; Quinn, Patricia K.; Bates, Timothy S.

    2016-03-01

    The oceans hold a massive quantity of organic carbon, nearly all of which is dissolved and more than 95% is refractory, cycling through the oceans several times before complete removal. The vast reservoir of refractory dissolved organic carbon (RDOC) is a critical component of the global carbon cycle that is relevant to our understanding of fundamental marine biogeochemical processes and the role of the oceans in climate change with respect to long-term storage and sequestration of atmospheric carbon dioxide. Here we show that RDOC includes surface-active organic matter that can be incorporated into primary marine aerosol produced by bursting bubbles at the sea surface. We propose that this process will deliver RDOC from the sea surface to the atmosphere wherein its photochemical oxidation corresponds to a potentially important and hitherto unknown removal mechanism for marine RDOC.

  13. Seasonal and event-scale controls on dissolved organic carbon and nitrate flushing from catchments

    NASA Astrophysics Data System (ADS)

    Sebestyen, S. D.; Boyer, E. W.; Shanley, J. B.; Doctor, D. H.

    2005-05-01

    To explore terrestrial and aquatic linkages controlling nutrient dynamics in forested catchments, we collected high-frequency samples from 2002 to 2004 at the Sleepers River Research Watershed in northeastern Vermont USA. We measured DOC (dissolved organic carbon), SUVA (specific UV absorbance), nitrate, and major ion concentrations over a wide range of flow conditions. In addition, weekly samples since 1991 provide a longer term record of stream nutrient fluxes. During events, DOC concentrations increased with flow consistent with the flushing of a large reservoir of mobile organic carbon from forest soils. Higher concentrations of DOC and SUVA in the growing versus dormant season illustrated seasonal variation in sources, characteristics (i.e. reactivity), availability, and controls on the flushing response of organic matter from the landscape to streams. In contrast, stream nitrate concentrations increased with flow but only when catchments "wetted-up" after baseflow periods. Growing season stream nitrate responses were dependent on short-term antecedent moisture conditions indicating rapid depletion of the soil nitrate reservoir when source areas became hydrologically connected to streams. While the different response patterns emphasized variable source and biogeochemical controls in relation to flow patterns, coupled carbon and nitrogen biogeochemical processes were also important controls on stream nutrient fluxes. In particular, leaf fall was a critical time when reactive DOC from freshly decomposing litter fueled in-stream consumption of nitrate leading to sharp declines of stream nitrate concentrations. Our measurements highlight the importance of "hot spots" and "hot moments" of biogeochemical and hydrological processes that control stream responses. Furthermore, our work illustrates how carbon, nitrogen, and water cycles are coupled in catchments, and provides a conceptual model for future work aimed at modeling forest stream hydrochemistry at the

  14. Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

    USGS Publications Warehouse

    Mann, Paul J.; Spencer, Robert G.M.; Hernes, Peter J.; Six, Johan; Aiken, George R.; Tank, Suzanne E.; McClelland, James W.; Butler, Kenna; Dyda, Rachael Y.; Holmes, Robert M.

    2016-01-01

    Climate change is causing extensive warming across Arctic regions resulting in permafrost degradation, alterations to regional hydrology and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest Arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275–295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of “terrestrial humic-like” vs. “marine humic-like” fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in

  15. Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

    NASA Astrophysics Data System (ADS)

    Mann, Paul; Spencer, Robert; Hernes, Peter; Six, Johan; Aiken, George; Tank, Suzanne; McClelland, James; Butler, Kenna; Dyda, Rachael; Holmes, Robert

    2016-03-01

    Climate change is causing extensive warming across arctic regions resulting in permafrost degradation, alterations to regional hydrology, and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275-295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of 'terrestrial humic-like' versus 'marine humic-like' fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in

  16. The "Flushing" of Dissolved Organic Carbon from Hillslope Soils to a Headwater Stream

    NASA Astrophysics Data System (ADS)

    Mei, Y.; Hornberger, G.; Kaplan, L. A.; Aufdenkampe, A. K.; Newbold, J. D.

    2012-12-01

    Event export of dissolved organic carbon (DOC) from terrestrial sources to streams was found to account for a significant portion of annual export of DOC. Thus, determining the first-order control on DOC export is of great importance in terms of carbon cycling and budget. In this work, the well-known DOC "flushing hypothesis" was tested mechanically using field data and a physically-based model in a combined approach. Field hydrological data collection and DOC sampling were conducted within the White Clay Creek (WCC) watershed in southeastern Pennsylvania in 2010. A two dimensional saturated-unsaturated finite element model was then developed to describe the soil and groundwater flow, DOC, BDOC responses to the precipitation events. The flow and reactive transport models was calibrated in sequence after the model was built. Simulation results showed that the calibrated model can reproduce the pattern of the stream DOC variation during the storm for three precipitation events from July12, 2010 to July19, 2010, and give a reasonable understanding of field DOC data. The model captured the details of the process put forth in the "flushing hypothesis": DOC was leached from near-surface layers by a rising water table followed by a quick lateral transport of these leached nutrients to the stream via near-surface. A rapid decline of DOC flux in the saturated zone was found from the selected vertical cross section of the model from riparian zone to up hillslope. This is consistent with our previous study that indicated a significant role for the riparian zone in DOC export.

  17. Exchanges and photo-biogeochemical transformation of dissolved organic compounds in Eastern US tidal marsh ecosystems.

    NASA Astrophysics Data System (ADS)

    Tzortziou, Maria; Neale, Patrick; Megonigal, Patrick; Butterworth, Megan; Jaffe, Rudolf

    2010-05-01

    The role of tidal marshes as sources, sinks and/or transformers of biologically important nutrients, carbon and pollutants has been studied in various marsh-estuarine environments and geomorphological settings. Although there is no consensus on the magnitude and direction of marsh-estuary net (particulate and dissolved) organic fluxes, most previous studies suggest that salt marshes export dissolved organic carbon (DOC) to the surrounding estuarine waters. There has been less attention, however, to the influence of transformations on marsh-exported organic carbon composition or "quality". Yet, carbon composition affects a wide variety of estuarine processes, including microbial respiration and photochemistry. Our objectives in this study were to quantify the photo-reactivity and bio-availability of dissolved organic carbon compounds exported from tidal wetlands of the Chesapeake Bay and determine their effects on the optical properties of colored organic matter (CDOM). We quantified DOC bioavailability with two assays of microbial mineralization: the traditional batch incubation approach in which a suspension of DOM and microbial cells (1 µm filtrate) was incubated in bottles for 7 d, and a continuous-flow bioreactor approach in which DOC (0.2 µm filtrate) was passed through a microbial community that had been pre-established on glass beads from the same source water. Photochemical degradation was measured after a 10h exposure to filtered xenon irradiance simulating midday surface exposure. We measured decreases in CDOM absorption and fluorescence spectra, DOC concentrations, changes in molecular weight distribution, and increases in dissolved inorganic carbon (DIC) and CO2. Results provide important insights on the transformation, fate and cycling of marsh-exported organic compounds, and the role of tidal marsh systems as major regulators of short-scale biological, optical and biogeochemical variability in highly dynamic coastal margins and catchment areas.

  18. Effects of soil dissolved organic matter inputs on high-elevation lake metabolism

    NASA Astrophysics Data System (ADS)

    Sadro, S.; De La Rosa, G. T.; Nelson, C. E.; Homyak, P. M.; Sickman, J. O.

    2015-12-01

    Concentrations of dissolved organic matter (DOM) have been increasing in many aquatic ecosystems. In snow-dominated systems, longer growing seasons and shifts in precipitation from snow to rain are expected to increase terrestrial DOM loading in lakes. In particular, high-elevation lakes are susceptible to the effects of rain-induced loading because they are often located in steep catchments with thin soils and impermeable rock outcrops that rapidly channel runoff. Observational studies have linked rain-induced loading with increased lake DOM and nutrient concentrations, altering ecosystem metabolic rates. However, the aquatic ecosystem response to different magnitudes of terrestrial DOM loading remains unclear. We hypothesize that low levels of DOM loading will stimulate rates of primary production to a greater extent than heterotrophic respiration as phytoplankton in these oligotrophic lakes exploit increased inorganic nutrient availability, ultimately increasing net ecosystem production. In contrast, we expect high levels of loading to suppress rates of gross primary production through reduced transparency of photosynthetically active radiation, while stimulating heterotrophic respiration through increased DOM substrate availability for bacterioplankton. We predict there will be a threshold DOM-loading level above which net ecosystem metabolism becomes heterotrophic. To test these hypotheses we conducted a series of in situ incubations of lake water amended with soil DOM extracted from catchment Entisols and Inceptisols. Background concentrations of dissolved organic carbon (DOC) in these lakes are typically ~60 - 80 μM during the ice-free season. Incubation treatments included a control with ambient DOC concentration, soil DOM additions targeting +10 μM, +20 μM, +60 μM, +190 μM, +440 μM, and +940 μM DOC, and a nutrient amendment matching inorganic N and P concentrations in the highest soil DOM treatment. We develop models that predict phytoplankton and

  19. High fluvial export of dissolved organic nitrogen from a peatland catchment with elevated inorganic nitrogen deposition.

    PubMed

    Edokpa, D A; Evans, M G; Rothwell, J J

    2015-11-01

    This study investigates seasonal concentrations and fluxes of nitrogen (N) species under stormflow and baseflow conditions in the peat dominated Kinder River catchment, south Pennines, UK. This upland region has experienced decades of high atmospheric inorganic N deposition. Water samples were collected fortnightly over one year, in combination with high resolution stormflow sampling and discharge monitoring. The results reveal that dissolved organic nitrogen (DON) constitutes ~54% of the estimated annual total dissolved nitrogen (TDN) flux (14.3 kg N ha(-1) yr(-1)). DON cycling in the catchment is influenced by hydrological and biological controls, with greater concentrations under summer stormflow conditions. Dissolved organic carbon (DOC) and DON are closely coupled, with positive correlations observed during spring, summer and autumn stormflow conditions. A low annual mean DOC:DON ratio (<25) and elevated dissolved inorganic N concentrations (up to 63μmoll(-1) in summer) suggest that the Kinder catchment is at an advanced stage of N saturation. This study reveals that DON is a significant component of TDN in peatland fluvial systems that receive high atmospheric inputs of inorganic N.

  20. Enhanced availability of mercury bound to dissolved organic matter for methylation in marine sediments

    NASA Astrophysics Data System (ADS)

    Mazrui, Nashaat M.; Jonsson, Sofi; Thota, Sravan; Zhao, Jing; Mason, Robert P.

    2016-12-01

    The forms of inorganic mercury (HgII) taken up and methylated by bacteria in sediments still remain largely unknown. From pure cultures studies, it has been suggested that dissolved organic matter (DOM) may facilitate the uptake either by acting as a shuttle molecule, transporting the HgII atom to divalent metal transporters, or by binding HgII and then being transported into the cell as a carbon source. Enhanced availability of Hg complexed to DOM has however not yet been demonstrated in natural systems. Here, we show that HgII complexed with DOM of marine origin was up to 2.7 times more available for methylation in sediments than HgII added as a dissolved inorganic complex (HgII(aq)). We argue that the DOM used to complex HgII directly facilitated the bacterial uptake of HgII whereas the inorganic dissolved HgII complex adsorbed to the sediment matrix before forming bioavailable dissolved HgII complexes. We further demonstrate that differences in net methylation in sediments with high and low organic carbon content may be explained by differences in the availability of carbon to stimulate the activity of Hg methylating bacteria rather than, as previously proposed, be due to differences in HgII binding capacities between sediments.

  1. Influence of dissolved organic matter on the toxicity of copper to Ceriodaphnia dubia: Effect of complexation kinetics

    SciTech Connect

    Kim, S.D.; Ma, H.; Allen, H.E.; Cha, D.K.

    1999-11-01

    The reaction kinetics of copper interaction with dissolved organic matter (DOM) in water were studied in order to determine the effect of equilibration period on the toxicity of copper to aquatic organisms. The changes in physical and chemical forms of the copper during four reaction times were examined in four completely mixed reactors in series; the bioavailability of the copper as a function of these new forms was then determined with a flow-through bioassay system, using Ceriodaphnia dubia as a test organism. This study showed that the toxicity of copper to C. dubia decreased with increasing copper-DOM reaction time, which demonstrated that the copper reaction rate with dissolved organic components in the test water was slow. The toxicity of copper to C. dubia was closely related to the measured free-copper concentration (CU{sup 2+}) rather than to the total copper concentrations, a fact that supports the free ion activity model. The authors found that the LC50 of copper for C. dubia increased linearly with increasing total available binding sites. Although a similar trend was observed in both natural DOM and commercial humic acid, their results indicated that for a given copper-organic carbon ratio, copper binds more strongly to humic acid than to the natural DOM. This difference may be attributed to the greater copper binding affinity of humic acid (greater than that of other metal-binding organic fractions present in DOM, i.e., fulvic acid).

  2. Variation of dissolved organic carbon transported by two Chinese rivers: The Changjiang River and Yellow River.

    PubMed

    Liu, Dong; Pan, Delu; Bai, Yan; He, Xianqiang; Wang, Difeng; Zhang, Lin

    2015-11-15

    Real-time monitoring of riverine dissolved organic carbon (DOC) and the associated controlling factors is essential to coastal ocean management. This study was the first to simulate the monthly DOC concentrations at the Datong Hydrometric Station for the Changjiang River and at the Lijin Hydrometric Station for the Yellow River from 2000 to 2013 using a multilayer back-propagation neural network (MBPNN), along with basin remote-sensing products and river in situ data. The average absolute error between the modeled values and in situ values was 9.98% for the Changjiang River and 10.84% for the Yellow River. As an effect of water dilution, the variations of DOC concentrations in the two rivers were significantly negatively affected by discharge, with lower values reported during the wet season. Moreover, vegetation growth status and agricultural activities, represented by the gross primary product (GPP) and cropland area percent (CropPer) in the river basin, respectively, also significantly affected the DOC concentration in the Changjiang River, but not the Yellow River. The monthly riverine DOC flux was calculated using modeled DOC concentrations. In particular, the riverine DOC fluxes were affected by discharge, with 71.06% being reported for the Changjiang River and 90.71% for the Yellow River. Over the past decade, both DOC concentration and flux in the two rivers have not shown significant changes.

  3. Transport of dissolved organic macromolecules and their effect on the transport of phenanthrene in porous media

    SciTech Connect

    Magee, B.R.; Lion, L.W.; Lemley, A.T. )

    1991-02-01

    The retardation factor (R) of phenanthrene in a sand column was reduced by an average factor of 1.8 in the presence of dissolved organic matter (DOM) derived from soil, suggesting that a phenanthrene-DOM complex enhanced the transport of phenanthrene. Distribution coefficients (K{sub d}'s) were determined in batch and column studies for combinations of phenanthrene and DOM with sand. The retardation factor in the advective-dispersive transport equation was modified to reflect the pressure of a carrier by incorporating both the retardation and pore exclusion of the carrier itself. The best prediction of phenanthrene transport in the presence of DOM was provided by modeling the retardation by using two K{sub d}'s derived from column experiments of DOM alone and phenanthrene alone, along with the K{sub d} for phenanthrene binding to DOM. Sensitivity analyses indicated that the critical model parameters are the distribution coefficients for the hydrophobic pollutant binding to the stationary phase and binding to the carrier, as well as the carrier concentration.

  4. Temperature dependence of the photochemical formation of hydroxyl radical from dissolved organic matter.

    PubMed

    McKay, Garrett; Rosario-Ortiz, Fernando L

    2015-04-07

    The temperature dependence of the photochemical production of the hydroxyl radical (•OH) from dissolved organic matter (DOM) was investigated by measuring the apparent temperature dependence of the quantum yield (Φa) for this process. Temperature dependent Φa values were analyzed using the Arrhenius equation. Apparent activation energies obtained for DOM isolates purchased from the International Humic Substances Society ranged from 16 to 34 kJ mol(-1). Addition of 40 units mL(-1) catalase, used to hinder the hydrogen peroxide (H2O2)-dependent pathway to •OH, did not impact the observed activation energy. However, an increase in activation energy was observed in lower molecular weight DOM obtained by size fractionation. We also measured the temperature dependence of p-benzoquionone photolysis as a model compound for DOM and observed no temperature dependence (slope p = 0.41) for the formation of phenol from oxidation of benzene (the •OH probe used), but a value of about 10 kJ mol(-1) for p-benzoquinone loss, which is consistent with formation of a quinone-water exciplex. These data provide insight into DOM photochemistry as well as provide parameters useful for modeling steady state •OH concentrations in natural systems.

  5. Correlations between dissolved organic matter optical properties and quantum yields of singlet oxygen and hydrogen peroxide.

    PubMed

    Dalrymple, Renée M; Carfagno, Amy K; Sharpless, Charles M

    2010-08-01

    Various aquatic dissolved organic matter (DOM) samples produce singlet oxygen (1O2) and hydrogen peroxide (H2O2) with quantum yields of 0.59 to 4.5% (1O2 at 365 nm) and 0.017 to 0.053% (H2O2, 300-400 nm integrated). The two species' yields have opposite pH dependencies and strong, but opposite, correlations with the E2/E3 ratio (A254 divided by A365). Linear regressions allow prediction of both quantum yields from E2/E3 in natural water samples with errors ranging from -3% to 60%. Experimental evidence and kinetic calculations indicate that less than six percent of the H2O2 is produced by reaction between 1O2 and DOM. The inverse relationship between the 1O2 and H2O2 yields is thus best explained by a model in which precursors to these species are populated competitively. A model is presented, which proposes that important precursors to H2O2 may be either charge-transfer or triplet states of DOM.

  6. Application of passive sampling for measuring dissolved concentrations of organic contaminants in the water column at three marine superfund sites

    EPA Science Inventory

    At contaminated sediment sites, including U.S. EPA Superfund sites, it is critical to measure water column concentrations of freely dissolved contaminants to understand the complete exposure of aquatic organisms to hydrophobic organic contaminants (HOCs). However, historically a...

  7. PHOTOREACTIVITY OF CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) DERIVED FROM DECOMPOSITION OF VARIOUS VASCULAR PLANT AND ALGAL SOURCES

    EPA Science Inventory

    Chromophoric dissolved organic matter (CDOM) in aquatic environments is derived from the microbial decomposition of terrestrial and microbial organic matter. Here we present results of studies of the spectral properties and photoreactivity of the CDOM derived from several organi...

  8. Dissolved organic carbon uptake in streams: A review and assessment of reach-scale measurements

    NASA Astrophysics Data System (ADS)

    Mineau, Madeleine M.; Wollheim, Wilfred M.; Buffam, Ishi; Findlay, Stuart E. G.; Hall, Robert O.; Hotchkiss, Erin R.; Koenig, Lauren E.; McDowell, William H.; Parr, Thomas B.

    2016-08-01

    Quantifying the role that freshwater ecosystems play in the global carbon cycle requires accurate measurement and scaling of dissolved organic carbon (DOC) removal in river networks. We reviewed reach-scale measurements of DOC uptake from experimental additions of simple organic compounds or leachates to inform development of aquatic DOC models that operate at the river network, regional, or continental scale. Median DOC uptake velocity (vf) across all measurements was 2.28 mm min-1. Measurements using simple compound additions resulted in faster vf (2.94 mm min-1) than additions of leachates (1.11 mm min-1). We also reviewed published data of DOC bioavailability for ambient stream water and leaf leachate DOC from laboratory experiments. We used these data to calculate and apply a correction factor to leaf leachate uptake velocity to estimate ambient stream water DOC uptake rates at the reach scale. Using this approach, we estimated a median ambient stream DOC vf of 0.26 mm min-1. Applying these DOC vf values (0.26, 1.11, 2.28, and 2.94 mm min-1) in a river network inverse model in seven watersheds revealed that our estimated ambient DOC vf value is plausible at the network scale and 27 to 45% of DOC input was removed. Applying the median measured simple compound or leachate vf in whole river networks would require unjustifiably high terrestrial DOC inputs to match observed DOC concentrations at the basin mouth. To improve the understanding and importance of DOC uptake in fluvial systems, we recommend using a multiscale approach coupling laboratory assays, with reach-scale measurements, and modeling.

  9. Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

    NASA Astrophysics Data System (ADS)

    Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

    2014-12-01

    Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

  10. Examining the coupling of carbon and nitrogen cycles in Southern Appalachian streams: Understanding the role of dissolved organic nitrogen

    SciTech Connect

    Lutz, Brian D; Bernhardt, Emily; Roberts, Brian; Mulholland, Patrick J

    2011-01-01

    Although regional and global models of nitrogen (N) cycling typically focus on nitrate, dissolved organic nitrogen (DON) is the dominant form of nitrogen export from many watersheds and thus the dominant form of dissolved N in many streams. Our understanding of the processes controlling DON export from temperate forests is poor. In pristine systems, where biological N limitation is common, N contained in recalcitrant organic matter (OM) can dominate watershed N losses. This recalcitrant OM often has moderately constrained carbon:nitrogen (C:N) molar ratios ({approx}25-55) and therefore, greater DON losses should be observed in sites where there is greater total dissolved organic carbon (DOC) loss. In regions where anthropogenic N pollution is high, it has been suggested that increased inorganic N availability can reduce biological demand for organic N and therefore increase watershed DON losses. This would result in a positive correlation between inorganic and organic N concentrations across sites with varying N availability. In four repeated synoptic surveys of stream water chemistry from forested watersheds along an N loading gradient in the southern Appalachians, we found surprisingly little correlation between DON and DOC concentrations. Further, we found that DON concentrations were always significantly correlated with watershed N loading and stream water [NO{sub 3}{sup -}] but that the direction of this relationship was negative in three of the four surveys. The C:N molar ratio of dissolved organic matter (DOM) in streams draining watersheds with high N deposition was very high relative to other freshwaters. This finding, together with results from bioavailability assays in which we directly manipulated C and N availabilities, suggests that heterotrophic demand for labile C can increase as a result of dissolved inorganic N (DIN) loading, and that heterotrophs can preferentially remove N-rich molecules from DOM. These results are inconsistent with the two

  11. Molecular weight distribution of phosphorus fraction of aquatic dissolved organic matter.

    PubMed

    Ged, Evan C; Boyer, Treavor H

    2013-05-01

    This study characterized dissolved organic phosphorus (DOP) that is discharged from the Everglades Agricultural Area as part of the larger pool of aquatic dissolved organic matter (DOM). Whole water samples collected at the Everglades stormwater treat area 1 West (STA-1 W) were fractionated using a batch ultrafiltration method to separate organic compounds based on apparent molecular weight (AMW). Each AMW fraction of DOM was characterized for phosphorus, carbon, nitrogen, UV absorbance, and fluorescence. The DOP content of the Everglades water matrix was characteristically variable constituting 4-56% of total phosphorus (TP) and demonstrated no correlation with dissolved organic carbon (DOC). Measured values for DOP exceeded 14μgL(-1) in four out of five sampling dates making phosphorus load reductions problematic for the stormwater treatment areas (STAs), which target inorganic phosphorus and have a goal of 10μgL(-1) as TP. The molecular weight distributions revealed 40% of DOP is high molecular weight, aromatic-rich DOM. The results of this research are expected to be of interest to environmental chemists, environmental engineers, and water resources managers because DOP presents a major obstacle to achieving TP levels <10μgL(-1).

  12. Anthropogenic aerosols as a source of ancient dissolved organic matter in glaciers

    USGS Publications Warehouse

    Stubbins, Aron; Hood, Eran; Raymond, Peter A.; Aiken, George R.; Sleighter, Rachel L.; Hernes, Peter J.; Butman, David; Hatcher, Patrick G.; Striegl, Rob; Schuster, Paul F.; Abdulla, Hussain A.N.; Vermilyea, Andrew W.; Scott, Durelle T.; Spencer, Robert G.M.

    2012-01-01

    Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, yet highly bioavailable carbon to downstream ecosystems. This finding runs counter to logical perceptions of age–reactivity relationships, in which the least reactive material withstands degradation the longest and is therefore the oldest. The remnants of ancient peatlands and forests overrun by glaciers have been invoked as the source of this organic matter. Here, we examine the radiocarbon age and chemical composition of dissolved organic matter in snow, glacier surface water, ice and glacier outflow samples from Alaska to determine the origin of the organic matter. Low levels of compounds derived from vascular plants indicate that the organic matter does not originate from forests or peatlands. Instead, we show that the organic matter on the surface of the glaciers is radiocarbon depleted, consistent with an anthropogenic aerosol source. Fluorescence spectrophotometry measurements reveal the presence of protein-like compounds of microbial or aerosol origin. In addition, ultrahigh-resolution mass spectrometry measurements document the presence of combustion products found in anthropogenic aerosols. Based on the presence of these compounds, we suggest that aerosols derived from fossil fuel burning are a source of pre-aged organic matter to glacier surfaces. Furthermore, we show that the molecular signature of the organic matter is conserved in snow, glacier water and outflow, suggesting that the anthropogenic carbon is exported relatively unchanged in glacier outflows.

  13. Plant diversity effects on leaching of nitrate, ammonium, and dissolved organic nitrogen from an experimental grassland

    NASA Astrophysics Data System (ADS)

    Leimer, Sophia; Oelmann, Yvonne; Wirth, Christian; Wilcke, Wolfgang

    2014-05-01

    Leaching of nitrogen (N) from soil represents a resource loss and, in particular leaching of nitrate, can threaten drinking water quality. As plant diversity leads to a more exhaustive resource use, we investigated the effects of plant species richness, functional group richness, and the presence of specific functional groups on nitrate, ammonium, dissolved organic N (DON), and total dissolved N (TDN) leaching from an experimental grassland in the first 4 years after conversion from fertilized arable land to unfertilized grassland. The experiment is located in Jena, Germany, and consists of 82 plots with 1, 2, 4, 8, 16, or 60 plant species and 1-4 functional groups (legumes, grasses, non-leguminous tall herbs, non-leguminous small herbs). Nitrate, ammonium, and TDN concentrations in soil solution in the 0-0.3 m soil layer were measured every second week during 4 years on 62 plots and DON concentrations were calculated as difference between TDN and inorganic N. Missing concentrations in soil solution were estimated using a Bayesian statistical model. Downward water fluxes (DF) per plot from the 0-0.3 m soil layer were simulated in weekly resolution with a water balance model in connection with a Bayesian model for simulating missing soil water content measurements. To obtain annual nitrate, ammonium, and DON leaching from the 0-0.3 m soil layer per plot, we multiplied the respective concentrations in soil solution with DF and aggregated the data to annual sums. TDN leaching resulted from summation of nitrate, ammonium, and DON leaching. DON leaching contributed most to TDN leaching, particularly in plots without legumes. Dissolved inorganic N leaching in this grassland was dominated by nitrate. The amount of annual ammonium leaching was small and little influenced by plant diversity. Species richness affected DON leaching only in the fourth and last investigated year, possibly because of a delayed soil biota effect that increased microbial transformation of organic

  14. Probing the oxidation reduction properties of terrestrially and microbially derived dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Fimmen, Ryan L.; Cory, Rose M.; Chin, Yu-Ping; Trouts, Tamara D.; McKnight, Diane M.

    2007-06-01

    Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by 13C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of p Ka values.

  15. Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

    USGS Publications Warehouse

    Davis, J.A.; Gloor, R.

    1981-01-01

    Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

  16. Climate change and dissolved organic carbon export to the Gulf of Maine

    USGS Publications Warehouse

    Huntington, Thomas G.; Balch, William M.; Aiken, George R.; Sheffield, Justin; Luo, Lifeng; Roesler, Collin S.; Camill, Philip

    2016-01-01

    Ongoing climate change is affecting the concentration, export (flux), and timing of dissolved organic carbon (DOC) exported to the Gulf of Maine (GoM) through changes in hydrologic regime. DOC export was calculated for water years 1950 through 2013 for 20 rivers and for water years 1930 through 2013 for 14 rivers draining to the GoM. DOC export was also estimated for the 21st century based on climate and hydrologic modeling in a previously published study. DOC export was calculated by using the regression model LOADEST to fit seasonally adjusted concentration discharge (C-Q) relations. Our results are an analysis of the sensitivity of DOC export to changes in hydrologic conditions over time since land cover and vegetation were held constant over time. Despite large interannual variability, all rivers had increasing DOC export during winter and these trends were significant (p < 0.05) in 10 out of 20 rivers for 1950 to 2013 and in 13 out of 14 rivers for 1930 to 2013. All rivers also had increasing annual export of DOC although fewer trends were statistically significant than for winter export. Projections for DOC export during the 21st century were variable depending on the climate model and greenhouse gas emission scenario that affected future river discharge through effects on precipitation and evapotranspiration. The most consistent result was a significant increase in DOC export in winter in all model-by-emission scenarios. DOC export was projected to decrease during the summer in all model-by-emission scenarios, with statistically significant decreases in half of the scenarios.

  17. Climate change and dissolved organic carbon export to the Gulf of Maine

    NASA Astrophysics Data System (ADS)

    Huntington, Thomas G.; Balch, William M.; Aiken, George R.; Sheffield, Justin; Luo, Lifeng; Roesler, Collin S.; Camill, Philip

    2016-10-01

    Ongoing climate change is affecting the concentration, export (flux), and timing of dissolved organic carbon (DOC) exported to the Gulf of Maine (GoM) through changes in hydrologic regime. DOC export was calculated for water years 1950 through 2013 for 20 rivers and for water years 1930 through 2013 for 14 rivers draining to the GoM. DOC export was also estimated for the 21st century based on climate and hydrologic modeling in a previously published study. DOC export was calculated by using the regression model LOADEST to fit seasonally adjusted concentration discharge (C-Q) relations. Our results are an analysis of the sensitivity of DOC export to changes in hydrologic conditions over time since land cover and vegetation were held constant over time. Despite large interannual variability, all rivers had increasing DOC export during winter and these trends were significant (p < 0.05) in 10 out of 20 rivers for 1950 to 2013 and in 13 out of 14 rivers for 1930 to 2013. All rivers also had increasing annual export of DOC although fewer trends were statistically significant than for winter export. Projections for DOC export during the 21st century were variable depending on the climate model and greenhouse gas emission scenario that affected future river discharge through effects on precipitation and evapotranspiration. The most consistent result was a significant increase in DOC export in winter in all model-by-emission scenarios. DOC export was projected to decrease during the summer in all model-by-emission scenarios, with statistically significant decreases in half of the scenarios.

  18. Photodegradation of dissolved organic matter in two contrasting reaches of a regulated river

    NASA Astrophysics Data System (ADS)

    Oliver, A. A.; Dahlgren, R. A.; Spencer, R. G.

    2010-12-01

    standard plating and colony count methods. Water was analyzed for dissolved organic carbon (DOC), nutrients, and pH, UV-absorbance properties, including specific UV absorbance (SUVA) and selected spectral slopes (275-295 nm slope and 350-400 nm slope), were used to investigate changes in DOM characteristics. Spectrofluorometric techniques were used to determine the fluorescence index (emission at wavelength 450 nm to 500 nm at an excitation wavelength of 370 nm) for investigation of source material and transformations. Preliminary results suggest little to no change in DOC or nutrient concentrations. However, shifts in SUVA, spectral slope, and fluorescence index were apparent in both reservoir and river samples incubated at both sites, with larger changes observed for river samples incubated within the river reach at 70% light transmittance. These results provide information on how photodegradation may affect DOM recycling and regeneration as an energy source within different compartmentalized reaches of the Klamath River. This information will subsequently aid in developing models for predicting DOM dynamics over larger spatial and temporal scales, including predictions and implications for conditions following dam removal.

  19. Effects of dissolved organic matter (DOM) on the bioconcentration of organic chemicals in aquatic organisms--a review.

    PubMed

    Haitzer, M; Höss, S; Traunspurger, W; Steinberg, C

    1998-09-01

    Current knowledge on the effects of dissolved organic matter (DOM) on the bioconcentration of organic chemicals in aquatic animals (water fleas, mussels, amphipods and fish) is summarized. A graphical representation of the available data gives an overview of the magnitude of the observed effects. Most of the studies have shown decreases in bioconcentration in the presence of DOM (2 to 98% relative to DOM-free controls). However, at low DOM levels, up to 10 mg/L, also enhancements of bioconcentration due to DOM, ranging from 2 to 303% have been reported. Generally, the change in BCFW (Bioconcentration factor on a wet weight basis) per mg/L DOC was most pronounced at low levels of DOC. The data also show that DOM from different sources with different characteristics and quality can lead to substantial variations in the bioconcentration of organic compounds at comparable levels of DOC. While decreases in bioconcentration have generally been attributed to a lack of bioavailability of DOM-bound chemical, no mechanisms have been proposed to explain increased uptake of xenobiotics caused by DOM.

  20. Effects of dissolved organic matter size fractions on trihalomethanes formation in MBR effluents during chlorine disinfection.

    PubMed

    Ma, Defang; Gao, Baoyu; Sun, Shenglei; Wang, Yan; Yue, Qinyan; Li, Qian

    2013-05-01

    In this study, effects of dissolved organic matter (DOM) size fractions on trihalomethanes (THMs) formation in MBR effluents during chlorination were investigated by fractionating DOM into >100, 30-100, 10-30, 5-10 and <5 kDa fractions using ultrafiltration (UF) membranes based on molecular weight (MW). Fractions of MW>30 kDa constituted 87% of DOM and were the main THMs precursors, which exhibited higher specific ultraviolet absorbance (SUVA) and THMs formation potential (THMFP) and should be reduced to control THMs formation. For these fractions, THMs formation was mostly attributed to slow chlorine decay, and THMs yield coefficients were low because halogenated intermediates derived from the macromolecular DOM were difficult to decompose to produce THMs. Moreover, there was a strong linear correlation between dissolved organic carbon (DOC) concentration and THMFP (R(2)=0.981), as well as between the SUVA and specific THMFP (R(2)=0.993) in all fractions.

  1. Positive priming of terrestrially derived dissolved organic matter in a freshwater microcosm system

    NASA Astrophysics Data System (ADS)

    Bianchi, Thomas S.; Thornton, Daniel C. O.; Yvon-Lewis, Shari A.; King, Gary M.; Eglinton, Timothy I.; Shields, Michael R.; Ward, Nicholas D.; Curtis, Jason

    2015-07-01

    The role of priming processes in the remineralization of terrestrially derived dissolved organic carbon (TDOC) in aquatic systems has been overlooked. We provide evidence for TDOC priming using a lab-based microcosm experiment in which TDOC was primed by the addition of 13C-labeled algal dissolved organic carbon (ADOC) or a 13C-labeled disaccharide (trehalose). The rate of TDOC remineralization to carbon dioxide (CO2) occurred 4.1 ± 0.9 and 1.5 ± 0.3 times more rapidly with the addition of trehalose and ADOC, respectively, relative to experiments with TDOC as the sole carbon source over the course of a 301 h incubation period. Results from these controlled experiments provide fundamental evidence for the occurrence of priming of TDOC by ADOC and a simple disaccharide. We suggest that priming effects on TDOC should be considered in carbon budgets for large-river deltas, estuaries, lakes, hydroelectric reservoirs, and continental shelves.

  2. Importance of within-lake processes in affecting the dynamics of dissolved organic carbon and dissolved organic and inorganic nitrogen in an Adirondack forested lake/watershed

    NASA Astrophysics Data System (ADS)

    Kang, Phil-Goo; Mitchell, Myron J.; McHale, Patrick J.; Driscoll, Charles T.; Inamdar, Shreeram; Park, Ji-Hyung

    2016-05-01

    Lakes nested in forested watersheds play an important role in mediating the concentrations and fluxes of dissolved organic matter. We compared long-term patterns of concentrations and fluxes of dissolved organic carbon (DOC) and dissolved organic (DON) and inorganic nitrogen (DIN) in aquatic ecosystems of the Arbutus Lake watershed to evaluate how a lake nested in a forested watershed affects the sources (e.g., production) and sinks (e.g., retention) of DOC and DON in the Adirondack Mountains of New York, USA. We observed no significant long-term changes of DOC and DON in the lake outlet since 1983 and 1994, respectively. However, the temporal patterns of DOC and DON concentrations in the lake inlet showed significant seasonality such as increases during the vegetation-growing season along with notable decreases in the dormant season. A comparison of mass balances between inlet and outlet for the period from 2000 to 2009 suggested that the lake was a sink of DOC (mean of influx minus outflux: +1140 mol C ha-1 yr-1). In contrast, the difference of discharge-weighted DON concentrations (mean of inlet minus outlet: -1.0 µmol N L-1) between inlet and outlet was much smaller than the discharge-weighted DOC concentrations (average of inlet minus outlet: + 87 µmol C L-1). DON fluxes showed considerable variation among years (mean of influx minus outflux: +8 mol N ha-1 yr-1; range of differences: -15 to 27 mol N ha-1 yr-1). DON exhibited low percent retention ((influx-outflux)/influx) (mean: 6.9 %, range: -34.8 to +31.2) compared to DOC (mean: 30.1 %, range: +9.2 to +44.1). The resultant increase of DON within the lake was closely linked with a net decrease of DIN through monthly Pearson correlation analysis, suggesting the importance of biotic factors in mediating lake DON dynamics. Our results show different relative retentions of DOC compared with DON, along with a larger retention of DIN than DON, suggesting that DOC and DON might display substantially different

  3. Dissolved rhenium in river waters: Insight into the chemical weathering of fossil organic carbon?

    NASA Astrophysics Data System (ADS)

    Hilton, Robert; Gaillardet, Jerome

    2010-05-01

    The store of carbon in rock as fossil organic matter represents ~15x1021 g, which is almost 400 times the total amount of carbon present in the oceans and atmosphere. Oxidation of fossil organic carbon (FOC) during chemical weathering returns CO2 that was sequestered from the atmosphere in the geological past, back into the contemporary carbon cycle. Despite this recognition, the natural rates of FOC weathering are poorly constrained in the modern environment, as are the precise controls on its variability. This is primarily due to the difficultly in tracking the dissolved and gaseous carbon produced during FOC weathering, where biology and carbonate weathering mask its influence at a catchment-scale. Here we investigate the use of rhenium (Re) as a tracer of FOC weathering, focusing on a series of mountain catchments in Taiwan. We present dual methodology for determining dissolved Re content in river waters by ICP-MS, using pre-concentration and matrix removal via anion exchange chemistry and by direct analysis through standard-addition. Precision (2sigma) and accuracy at the ppt level are found to be better than 7%. In the 16 sampled catchments, the dissolved Re concentrations span the entire range from the published literature. We investigate the source of dissolved Re in the catchments using measurements of bedrocks and river sediments, and the comparative behavior of Re to major dissolved phases. A preliminary estimate of the Re budget derived from the weathering of FOC is presented, and the implications for the rates of FOC weathering discussed.

  4. Hydrological and biogeochemical controls on watershed dissolved organic matter transport: pulse-shunt concept.

    PubMed

    Raymond, Peter A; Saiers, James E; Sobczak, William V

    2016-01-01

    Hydrological precipitation and snowmelt events trigger large "pulse" releases of terrestrial dissolved organic matter (DOM) into drainage networks due to an increase in DOM concentration with discharge. Thus, low-frequency large events, which are predicted to increase with climate change, are responsible for a significant percentage of annual terrestrial DOM input to drainage networks. These same events are accompanied by marked and rapid increases in headwater stream velocity; thus they also "shunt" a large proportion of the pulsed DOM to downstream, higher-order rivers and aquatic ecosystems geographically removed from the DOM source of origin. Here we merge these ideas into the "pulse-shunt concept" (PSC) to explain and quantify how infrequent, yet major hydrologic events may drive the timing, flux, geographical dispersion, and regional metabolism of terrestrial DOM. The PSC also helps reconcile long-standing discrepancies in C cycling theory and provides a robust framework for better quantifying its highly dynamic role in the global C cycle. The PSC adds a critical temporal dimension to linear organic matter removal dynamics postulated by the river continuum concept. It also can be represented mathematically through a model that is based on stream scaling approaches suitable for quantifying the important role of streams and rivers in the global C cycle. Initial hypotheses generated by the PSC include: (1) Infrequent large storms and snowmelt events account for a large and underappreciated percentage of the terrestrial DOM flux to drainage networks at annual and decadal time scales and therefore event statistics are equally important to total discharge when determining terrestrial fluxes. (2) Episodic hydrologic events result in DOM bypassing headwater streams and being metabolized in large rivers and exported to coastal systems. We propose that the PSC provides a framework for watershed biogeochemical modeling and predictions and discuss implications to

  5. Abiotic Dissolved Organic Matter-Mineral Interaction in the Karstic Floridan Aquifer

    NASA Astrophysics Data System (ADS)

    Jin, J.; Zimmerman, A.

    2007-12-01

    Dissolved organic matter (DOM)-mineral interaction (e.g. adsorption, desorption, mineral dissolution) in groundwater is a significant factor controlling geochemical, environmental and microbial processes and may be helpful in efforts to track groundwater sources or contaminant fate. Despite its importance, the dynamics and consequences of these abiotic interactions remain poorly understood, largely due to the inaccessibility and heterogeneity of the subsurface, as well as the chemical complexity of DOM. This study models the OM-mineral interactions that takes place in the Floridan aquifer through laboratory adsorption-desorption experiments using DOM (groundwater, river water, soil extracts) and carbonate minerals (calcite, dolomite) collected in north Florida. High performance liquid chromatography-size exclusion chromatography (HPLC-SEC) and UV-fluorescence excitation-emission matrix (EEM) spectrophotometry was used to examine the organic compound types exhibiting preferential affinity for carbonate minerals. Our results show that the DOM-carbonate adsorption/desorption isotherms are well described by the Freundlich model. Freundlich exponents (average value: 0.6488) less than one indicated a filling of adsorption sites. Minerals from Ocala tend to have higher adsorption affinity as well as adsorption capacity than those from Suwannee River Basin; however, both were found to have mineral dissolution. Two fluorescent signals, indicative of a fulvic-like (at excitation wavelength 295-310 nm, emission 400-420 nm) and a protein-like (275/345nm) moiety, were detected in DOM. A reduction in the fulvic-like peak intensity occurred following carbonate adsorption while the protein-like peaks remain almost unchanged indicating the preferential adsorption of fulvic acids. HPLC-SEC results (DOM properties as a function of molecular weight) will be discussed. The chemical properties of DOM in environmental groundwater samples will also be presented and evaluated in light of

  6. Seasonal variations in production and consumption rates of dissolved organic carbon in an organic-rich coastal sediment

    NASA Astrophysics Data System (ADS)

    Alperin, M. J.; Albert, D. B.; Martens, C. S.

    1994-11-01

    Dissolved organic carbon (DOC) concentrations in anoxic marine sediments are controlled by at least three processes: (1) production of nonvolatile dissolved compounds, such as peptides and amino acids, soluble saccharides and fatty acids, via hydrolysis of particulate organic carbon (POC). (2) conversion of these compounds to volatile fatty acids and alcohols by fermentative bacteria. (3) consumption of volatile fatty acids and alcohols by terminal bacteria, such as sulfate reducers and methanogens. We monitored seasonal changes in concentration profiles of total DOC, nonacid-volatile (NAV) DOC and acid-volatile (AV) DOC in anoxic sediment from Cape Lookout Bight, North Carolina, USA, in order to investigate the factors that control seasonal variations in rates of hydrolysis, fermentation, and terminal metabolism. During the winter months, DOC concentrations increased continuously from 0.2 mM in the bottomwater to ~4 mM at a depth of 36 cm in the sediment column. During the summer, a large DOC maximum developed between 5 and 20 cm, with peak concentrations approaching 10 mM. The mid-depth summertime maximum was driven by increases in both NAV- and AV-DOC concentrations. Net NAV-DOC reaction rates were estimated by a diagenetic model applied to NAV-DOC concentration profiles. Depth-integrated production rates of NAV-DOC increased from February through July, suggesting that net rates of POC hydrolysis during this period are controlled by temperature. Net consumption of NAV-DOC during the late summer and early fall suggests reduced gross NAV-DOC production rates, presumably due to a decline in the availability of labile POC. A distinct subsurface peak in AV-DOC concentration developed during the late spring, when the sulfate depletion depth shoaled from 25 to 10 cm. We hypothesize that the AV-DOC maximum results from a decline in consumption by sulfate-reducing bacteria (due to sulfate limitation) and a lag in the development of an active population of methanogenic

  7. Characterization of Optical and Associated Properties of Marine Colored Dissolved Organic Material (CDOM)

    DTIC Science & Technology

    2000-09-30

    Characterization of Optical and Associated Properties of Marine Colored Dissolved Organic Material (CDOM) Principal Investigator: Dr. Rod G. Zika Co...of the FFFF on the ship. A nitrogen purification system, that eliminates our dependence on and the cost of liquid nitrogen dewers as a N2 source, has...Catherine D., Erik R. Stabenau, Eliete Zanardi-Lamardo, Cynthia A. Moore, and Rod G. Zika (1999) “Photochemical Effects on the Structural Properties

  8. The effect of dissolved organic matter on soybean peroxidase-mediated removal of triclosan in water.

    PubMed

    Li, Jianhua; Zhang, Ya; Peng, Jianbiao; Wu, Xinan; Gao, Shixiang; Mao, Liang

    2017-04-01

    Dissolved organic matter (DOM) is ubiquitous in water and involved in numerous important chemical processes in aqueous systems, enabling it a unique challenge for a variety of water treatment processes. Soybean peroxidase (SBP)-based enzymatic process, as a promising treatment technique, has been successfully applied to remove pollutants in wastewaters such as coal-tar and refinery wastewater. In this study, the effect of DOM on the removal of polychlorinated aromatic antimicrobials triclosan (TCS) by SBP was investigated. Our results suggested that DOM significantly suppressed the catalytic performance of SBP to TCS, presumably resulting from the competition of the phenolic moiety in DOM structure as the active substrate of SBP via the analysis of excitation emission matrix (EEM) spectra of DOM. Although the product species of TCS in SBP-mediated system with DOM has no change compared with the system without DOM, the yields of self-coupling products relative to total transformed TCS were remarkably reduced in the presence of DOM, suggesting that DOM participated in the oxidative coupling reactions. Cross-coupling between TCS and DOM was also verified using guaiacol as a model DOM constituent. Moreover, the products including self-coupling products and co-polymers in SBP-mediated TCS reaction system with DOM were innocuous through growth inhibition assay of S. obliquus.

  9. Effect of dissolved organic matter on ammonium sorption kinetics and equilibrium to Chinese clinoptilolite.

    PubMed

    Zhang, Ying; Bi, Erping

    2012-01-01

    In the in-situ remediation of ammonium (NH4+) in groundwater by a sequential reactive barrier filled with zeolite, it is of great importance to understand the mechanisms of NH4+ sorption to zeolite. In this study, the effect of dissolved natural organic matter on NH4+ sorption to natural Chinese clinoptilolite was studied by batch experiments taking humic acid (HA) as a model substance. The surface of clinoptilolite was characterized by scanning electronic microscopy (SEM). A needle cluster of sorbed HA could be observed on the surface of the clinoptilolite. The negative effect of HA on NH4+ sorption is thought to be their competition for sorption sites, the surface coverage and blockage of the pores of clinoptilolite by HA. The fitting results of kinetic sorption data indicated that the rate-controlling step for NH4+ sorption by clinoptilolite in both NH4+ and NH4+ + HA systems is the heterogeneous chemisorption. The existence of HA (10 mg/L) significantly reduced the initial sorption rate of NH4+, but the effect of a further concentration increase of HA was slight. The effect of HA on maximum sorption capacity was found to be insignificant in the experiments. A high aqueous Ca2+ concentration can decrease the negative effect of HA on NH4+ sorption by precipitation of calcium humate.

  10. Comparative examination of effects of binding of different metals on chromophores of dissolved organic matter.

    PubMed

    Yan, Mingquan; Korshin, Gregory V

    2014-03-18

    This study quantified the binding of dissolved organic matter (DOM) from Suwannee River with nine metals, Ca(II), Mg(II), Fe(III), Al(III), Cu(II), Cd(II), Cr(III), Eu(III), and Th(IV), using a differential absorbance approach. The differential spectra of DOM were closely fitted with six Gaussian bands that were present for all of the metals at varying pH values. Their maxima were located at ca. 200, 240, 276, 316, 385, and 547 nm (denoted as A0, A1, A2, A3, A4, and A5, respectively). The relative contributions and signs of the Gaussian bands were metal-specific and correlated to some degree with the covalent-bonding index of the ions and applicable complexation constants of the NICA-Donnan model. The intensity of band A4 was linearly proportional to the concentration of DOM-complexed metal, although these correlations formed two groups with different slopes, reflecting the nature of DOM-metal interactions. The results demonstrate that differential spectra yield results indicative of the nature and extent of metal and DOM interactions.

  11. Impact of Chromophoric Dissolved Organic Matter on UV Inhibition of Primary Productivity in the Sea

    NASA Technical Reports Server (NTRS)

    Arrigo, Kevin R.; Brown, Christopher W.

    1996-01-01

    A model was developed to assess the impact of chromophoric dissolved organic matter (CDOM) on phytoplankton production within the euphotic zone. The rate of depth-integrated daily gross primary productivity within the euphotic zone was evaluated as a function of date, latitude, CDONI absorption characteristics, chlorophyll a (chl a) concentration, vertical stratification, and phytoplankton sensitivity to UV radiation (UVR). Results demonstrated that primary production was enhanced in the upper 30 m of the water column by the presence of CDOM, where predicted increases in production due to the removal of damaging UVR more than offset its reduction resulting from the absorption of photosynthetically usable radiation. At greater depths, where little UVR remained, primary production was always reduced due to removal by CDOM of photosynthetically usable radiation. When CDOM was distributed homogeneously within the euphotic zone, the integral over z [(GPP)(sub ez)], was reduced under most bio-optical (i.e. solar zenith angle, and CDOM absorption, and ozone concentration) and photophysiological production at depth was greater than the enhancement of production at the surface.

  12. Effects of dissolved organic carbon and salinity on bioavailability of mercury.

    PubMed Central

    Barkay, T; Gillman, M; Turner, R R

    1997-01-01

    Hypotheses that dissolved organic carbon (DOC) and electrochemical charge affect the rate of methylmercury [CH3Hg(I)] synthesis by modulating the availability of ionic mercury [Hg(II)] to bacteria were tested by using a mer-lux bioindicator (O. Selifonova, R. Burlage, and T. Barkay, Appl. Environ. Microbiol. 59:3083-3090, 1993). A decline in Hg(II)-dependent light production was observed in the presence of increasing concentrations of DOC, and this decline was more pronounced at pH 7 than at pH 5, suggesting that DOC is a factor controlling the bioavailability of Hg(II). A thermodynamic model (MINTEQA2) was used to select assay conditions that clearly distinguished among various Hg(II) species. By using this approach, it was shown that negatively charged forms of mercuric chloride (HgCl3-/HgCl(4)2-) induced less light production than the electrochemically neutral form (HgCl2), and no difference was observed between the two neutral forms, HgCl2 and Hg(OH)2. These results suggest that the negative charge of Hg(II) species reduces their availability to bacteria and may be one reason why accumulation of CH3Hg(I) is more often reported to occur in freshwater than in estuarine and marine biota. PMID:9361413

  13. Reductive transformation of dioxins: An assessment of the contribution of dissolved organic matter to dechlorination reactions

    SciTech Connect

    Fu, Q.S.; Barkovskii, A.L.; Adriaens, P.

    1999-11-01

    The susceptibility of dioxins to dissolved organic carbon (DOC)-mediated dechlorination reactions was investigated using 1,2,3,4,6,7,9-heptachlorodibenzo-p-dioxin (HpCDD), Aldrich humic acid (AHA), and polymaleic acid (PMA) as model compounds. The dechlorination yields were on the order of 4--20% which, when normalized to phenolic acidity, was comparable to yields observed in the presence of the humic constituents catechol and resorcinol. Based on the ratio of dechlorination yields as a function of phenolic acidity and electron transfer capacity, differences in electron transfer efficiency to dioxins are likely combined effects of specific interactions with the functional groups and nonspecific hydrophobic interactions. Hexa- and pentaCDD homologues were dominant in all incubations, and diCDD constituted the final product of dechlorination. The rates of appearance of lesser chlorinated products were similar to those observed in sediment systems and followed thermodynamic considerations as they decreased with a decrease in level of chlorination. Generally, both absolute and phenolic acidity-normalized rate constants for AHA-mediated reactions were up to 2-fold higher than those effected by PMA. These results indicate that the electron shuttling capacity of sediment DOC may significantly affect the fate of dioxins, in part through dechlorination reactions.

  14. Phase partitioning and solubility of iron in natural seawater controlled by dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Chen, Min; Wang, Wen-Xiong; Guo, Laodong

    2004-12-01

    The phase partitioning and solubility of Fe as well as its relationship with marine dissolved organic matter (DOM) in different natural seawater and phytoplankton cultures were examined using radiotracer and ultrafiltration techniques to better understand Fe biogeochemical cycling and its biological availability in the ocean. Fe solubility in seawaters was related to the filter's cutoff, with the Fe solubility in the <3 × 103 amu fraction being about one third of that in the <10 × 103 amu filtrate. The Fe solubility decreased from estuarine to coastal to oceanic seawater and then to DOM-free seawater. There was a significant linear relationship between Fe solubility or [FeL] concentration and the dissolved organic carbon concentration for the seawater of different origins tested, suggesting that Fe solubility was largely controlled by the amount of dissolved organic matter. In addition, Fe solubility was significantly enhanced by the presence of fresh phytoplankton exudates, indicating that the nature of organic ligands also plays an important role in controlling the Fe solubility in seawater. Most of the Fe-bound organic ligands were in the size fraction <10 × 103 amu and decreased from the estuarine to the coastal and then to the oceanic seawater. Among the standard macromolecular organic compounds examined, siderophores (deferoxamine mesylate and ferrichrome) showed the highest binding capacity for Fe, and carrageenan (a high molecular weight-sulfated acid polysaccharide) also slightly increased Fe solubility. Complexation of organic ligands with Fe appeared to be Fe-specific or Fe preferential. Our results highlight quantitatively the importance of DOM in controlling Fe solubility in seawater. Further studies are needed to elucidate the interrelationship between the biogeochemical cycles of Fe and the chemistry of DOM in the ocean.

  15. Dissolved Gases and Ice Fracturing During the Freezing of a Multicellular Organism: Lessons from Tardigrades

    PubMed Central

    Kletetschka, Gunther; Hruba, Jolana

    2015-01-01

    Abstract Three issues are critical for successful cryopreservation of multicellular material: gases dissolved in liquid, thermal conductivity of the tissue, and localization of microstructures. Here we show that heat distribution is controlled by the gas amount dissolved in liquids and that when changing the liquid into solid, the dissolved gases either form bubbles due to the absence of space in the lattice of solids and/or are migrated toward the concentrated salt and sugar solution at the cost of amount of heat required to be removed to complete a solid-state transition. These factors affect the heat distribution in the organs to be cryopreserved. We show that the gas concentration issue controls fracturing of ice when freezing. There are volumetric changes not only when changing the liquid into solid (volume increases) but also reduction of the volume when reaching lower temperatures (volume decreases). We discuss these issues parallel with observations of the cryosurvivability of multicellular organisms, tardigrades, and discuss their analogy for cryopreservation of large organs. PMID:26309797

  16. Chemical characterization of high molecular weight dissolved organic matter in fresh and marine waters

    NASA Astrophysics Data System (ADS)

    Repeta, Daniel J.; Quan, Tracy M.; Aluwihare, Lihini I.; Accardi, AmyMarie

    2002-03-01

    The high molecular weight fraction of dissolved organic matter in a suite of lakes, rivers, seawater, and marine sediment interstitial water samples was collected by ultrafiltration and characterized by molecular level and spectroscopic techniques. Proton nuclear magnetic resonance spectra of all samples show a high degree of similarity, with major contributions from carbohydrates, bound acetate, and lipids. Molecular level analyses of neutral sugars show seven monosaccharides, rhamnose, fucose, arabinose, xylose, mannose, glucose, and galactose, to be abundant, and to occur in comparable relative amounts in each sample. Previous studies have emphasized the distinctive composition of dissolved humic substances in fresh and marine waters, and have attributed these differences to sources and transformations of organic matter unique to each environment. In contrast we find a large fraction of freshwater high molecular weight dissolved organic matter (HMWDOM; > 1kD) to be indistinguishable from marine HMWDOM in bulk and molecular-level chemical properties. Aquatic HMWDOM is similar in chemical composition to biologically derived acylated heteropolysaccharides isolated from marine algal cultures, suggesting a biological source for some fraction of persistent HMWDOM. High molecular weight DOC contributes 51 ± 26% of the total DOC, and monosaccharides 18 ± 8% of the total HMWDOC in our freshwater samples. These contributions are on average higher and more variable, but not significantly different than for surface seawater (30% and 16% respectively). Biogeochemical processes that produce, accumulate, and recycle DOM may therefore share important similarities and be broadly comparable across a range of environmental settings.

  17. Dissolved Gases and Ice Fracturing During the Freezing of a Multicellular Organism: Lessons from Tardigrades.

    PubMed

    Kletetschka, Gunther; Hruba, Jolana

    2015-01-01

    Three issues are critical for successful cryopreservation of multicellular material: gases dissolved in liquid, thermal conductivity of the tissue, and localization of microstructures. Here we show that heat distribution is controlled by the gas amount dissolved in liquids and that when changing the liquid into solid, the dissolved gases either form bubbles due to the absence of space in the lattice of solids and/or are migrated toward the concentrated salt and sugar solution at the cost of amount of heat required to be removed to complete a solid-state transition. These factors affect the heat distribution in the organs to be cryopreserved. We show that the gas concentration issue controls fracturing of ice when freezing. There are volumetric changes not only when changing the liquid into solid (volume increases) but also reduction of the volume when reaching lower temperatures (volume decreases). We discuss these issues parallel with observations of the cryosurvivability of multicellular organisms, tardigrades, and discuss their analogy for cryopreservation of large organs.

  18. Contrasting UV-Vis Spectra of Terrestrial and Algal Derived Dissolved Organic Matter.

    NASA Astrophysics Data System (ADS)

    Adams, Jessica; Tipping, Edward; Scholefield, Paul; Feuchtmayr, Heidrun; Carter, Heather; Keenan, Patrick

    2016-04-01

    Dissolved organic matter (DOM) is an important freshwater component. It controls aquatic ecological and biochemical cycling, and can be problematic in industrial water treatment. Thus, the demand for effective and reliable monitoring is growing. The heterogeneity of the spectroscopic properties of DOM are such that measurements of absorbance at a single wavelength cannot provide accurate predictions of [DOC]. Previous construction of a two-component model, based on the combination of absorbance at two wavelengths and a constant accountable for non-absorbing DOM, resulted in good predictions of [DOC] across approximately 1800 different freshwater systems (R2=0.99). However, there were isolated cases where the model appreciably underestimated [DOC], including shallow lakes and reservoirs in the Yangtze basin, China where waters were deemed to be highly eutrophic. Here, we used a revised series of samples, from small scale algal dominated microcosms, mesocosms and catchment scale field samples to explore the capability of the two component model in situations where algae may be the dominant producer of aquatic DOC. Absorbances were measured using a laboratory based UV-Vis spectrometer and subsamples were also analysed through combustion and infra-red detection. In both the microcosms and mesocosms, the model failed to provide a reliable fit, and [DOC] was considerably underestimated. At the field scale, analysis of 55 samples from a combination of reservoirs, arable ponds, streams and rivers produced mostly reliable predictions of [DOC] (R2=0.96), which can be attributed to the dominant input of terrestrial DOM. Samples of shallow, enclosed meres from the North-West of the UK showed hints of similar behaviour to that of the Chinese lakes, suggesting some influences from algal DOM. Our results therefore provide evidence that algae may produce complex forms of DOM that harbour different spectroscopic properties to terrestrially derived material, in the UV spectral range.

  19. Dissolved Organic Matter Quality in a Shallow Aquifer of Bangladesh: Implications for Arsenic Mobility.

    PubMed

    Mladenov, Natalie; Zheng, Yan; Simone, Bailey; Bilinski, Theresa M; McKnight, Diane M; Nemergut, Diana; Radloff, Kathleen A; Rahman, M Moshiur; Ahmed, Kazi Matin

    2015-09-15

    In some high arsenic (As) groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems, such relationships are absent. The role of labile DOM as the main driver of microbial reductive dissolution is not sufficient to explain the variation in DOM-As relationships. Other processes that may also influence As mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic DOM influences, we characterized the optical properties of filtered surface water (n = 10) and groundwater (n = 24) samples spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed large volume fulvic acid (FA) isolates (n = 6) for optical properties, C and N content, and (13)C NMR spectroscopic distribution. Old groundwater (>30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved As concentration than groundwater that was younger than 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved As, iron (Fe), and FA concentration and fluorescence properties of isolated FA in this field study suggest that aromatic, terrestrially derived FAs promote As-Fe-FA complexation reactions that may enhance As mobility.

  20. The contribution of dissolved organic nitrogen and chloramines to nitrogenous disinfection byproduct formation from natural organic matter.

    PubMed

    Chuang, Yi-Hsueh; Lin, Angela Yu-Chen; Wang, Xiao-huan; Tung, Hsin-hsin

    2013-03-01

    The direct incorporation of chloramines and dissolved organic nitrogen (DON) may provide the nitrogen for nitrogenous disinfection byproducts (N-DBPs). This study explores the contributions of natural DON and chloramine incorporation to the formation of N-DBPs during chloramination. This study also evaluates the relationship between N-DBPs and carbonaceous DBPs by investigating four sources of dissolved organic matter with different DON-to-dissolved organic carbon (DOC) ratios. During chloramination, dihaloacetonitrile (DXAN) formation is correlated with the summation of trihalomethanes (THMs) and dichloroacetic acids (DXAAs) yield in molar basis at pH > 6. This study tests the formation kinetics of THMs, DXAAs, and DXANs during chloramination, explores the changes in DBP formation potential before and after a sequence of ozonation and chloramination, and tracks the nitrogen source of dichloroacetonitrile. The results support the hypothesis that THMs, DXAAs, and DXANs mainly derive from similar precursors upon chloramination. In addition, the precursor of HANs was approximately 10% (on a molar basis) of that of THMs and HAAs combined. The N-nitrosodimethylamine (NDMA) formation potential is correlated with DON/DOC in hydrophilic and transphilic fractions. Isotope (15)N-labeled monochloramine coupled with LC-electrospray ionization-tandem mass spectrometry was used to explore the nitrogen source of NDMA formed in chloraminated organic fractions. The results indicate that the nitroso group of the formed NDMA originates mainly from chloramines.

  1. Secondary organic aerosol formation from cyclohexene ozonolysis in the presence of water vapor and dissolved salts

    NASA Astrophysics Data System (ADS)

    Warren, Bethany; Malloy, Quentin G. J.; Yee, Lindsay D.; Cocker, David R.

    A series of 90 experiments were conducted in the UC Riverside/CE-CERT environmental chamber to evaluate the impact of water vapor and dissolved salts on secondary organic aerosol formation for cyclohexene ozonolysis. Water vapor (low - 30 ± 2% RH, medium - 46 ± 2% RH, high - 63 ± 2% RH) was found to directly participate in the atmospheric chemistry altering the composition of the condensing species, thus increasing total organic aerosol formation by ˜22% as compared to the system under dry (<0.1% RH) conditions. Hygroscopicity measurements also indicate that the organic aerosol composition is altered in the presence of gaseous water. These results are consistent with water vapor reacting with the crigee intermediate in the gas phase resulting in increased aldehyde formation. The addition of dissolved salts ((NH 4) 2SO 4, NH 4HSO 4, CaCl 2, NaCl) had minimal effect; only the (NH 4) 2SO 4 and NaCl were found to significantly impact the system with ˜10% increase in total organic aerosol formation. These results indicate that the organics may be partitioning to an outer organic shell as opposed to into the aqueous salt. Hygroscopicity measurements indicate that the addition of salts does not alter the aerosol composition for the dry or water vapor system.

  2. Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater

    PubMed Central

    Hunter, W. R.; Battin, T. J.

    2016-01-01

    Sorption of organic molecules to mineral surfaces is an important control upon the aquatic carbon (C) cycle. Organo-mineral interactions are known to regulate the transport and burial of C within inland waters, yet the mechanisms that underlie these processes are poorly constrained. Streamwater contains a complex and dynamic mix of dissolved organic compounds that coexists with a range of organic and inorganic particles and microorganisms. To test how microbial metabolism and organo-mineral complexation alter amino acid and organic carbon fluxes we experimented with 13C-labelled amino acids and two common clay minerals (kaolinite and montmorillonite). The addition of 13C-labelled amino acids stimulated increased microbial activity. Amino acids were preferentially mineralized by the microbial community, concomitant with the leaching of other (non-labelled) dissolved organic molecules that were removed from solution by clay-mediated processes. We propose that microbial processes mediate the formation of organo-mineral particles in streamwater, with potential implications for the biochemical composition of organic matter transported through and buried within fluvial environments. PMID:27481013

  3. Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater.

    PubMed

    Hunter, W R; Battin, T J

    2016-08-02

    Sorption of organic molecules to mineral surfaces is an important control upon the aquatic carbon (C) cycle. Organo-mineral interactions are known to regulate the transport and burial of C within inland waters, yet the mechanisms that underlie these processes are poorly constrained. Streamwater contains a complex and dynamic mix of dissolved organic compounds that coexists with a range of organic and inorganic particles and microorganisms. To test how microbial metabolism and organo-mineral complexation alter amino acid and organic carbon fluxes we experimented with (13)C-labelled amino acids and two common clay minerals (kaolinite and montmorillonite). The addition of (13)C-labelled amino acids stimulated increased microbial activity. Amino acids were preferentially mineralized by the microbial community, concomitant with the leaching of other (non-labelled) dissolved organic molecules that were removed from solution by clay-mediated processes. We propose that microbial processes mediate the formation of organo-mineral particles in streamwater, with potential implications for the biochemical composition of organic matter transported through and buried within fluvial environments.

  4. Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater

    NASA Astrophysics Data System (ADS)

    Hunter, W. R.; Battin, T. J.

    2016-08-01

    Sorption of organic molecules to mineral surfaces is an important control upon the aquatic carbon (C) cycle. Organo-mineral interactions are known to regulate the transport and burial of C within inland waters, yet the mechanisms that underlie these processes are poorly constrained. Streamwater contains a complex and dynamic mix of dissolved organic compounds that coexists with a range of organic and inorganic particles and microorganisms. To test how microbial metabolism and organo-mineral complexation alter amino acid and organic carbon fluxes we experimented with 13C-labelled amino acids and two common clay minerals (kaolinite and montmorillonite). The addition of 13C-labelled amino acids stimulated increased microbial activity. Amino acids were preferentially mineralized by the microbial community, concomitant with the leaching of other (non-labelled) dissolved organic molecules that were removed from solution by clay-mediated processes. We propose that microbial processes mediate the formation of organo-mineral particles in streamwater, with potential implications for the biochemical composition of organic matter transported through and buried within fluvial environments.

  5. Association of dissolved mercury with dissolved organic carbon in U.S. rivers and streams: The role of watershed soil organic carbon

    NASA Astrophysics Data System (ADS)

    Stoken, Olivia M.; Riscassi, Ami L.; Scanlon, Todd M.

    2016-04-01

    Streams and rivers are important pathways for the export of atmospherically deposited mercury (Hg) from watersheds. Dissolved Hg (HgD) is strongly associated with dissolved organic carbon (DOC) in stream water, but the ratio of HgD to DOC is highly variable between watersheds. In this study, the HgD:DOC ratios from 19 watersheds were evaluated with respect to Hg wet deposition and watershed soil organic carbon (SOC) content. On a subset of sites where data were available, DOC quality measured by specific ultra violet absorbance at 254 nm, was considered as an additional factor that may influence HgD:DOC . No significant relationship was found between Hg wet deposition and HgD:DOC, but SOC content (g m-2) was able to explain 81% of the variance in the HgD:DOC ratio (ng mg-1) following the form: HgD:DOC=17.8*SOC-0.41. The inclusion of DOC quality as a secondary predictor variable explained only an additional 1% of the variance. A mathematical framework to interpret the observed power-law relationship between HgD:DOC and SOC suggests Hg supply limitation for adsorption to soils with relatively large carbon pools. With SOC as a primary factor controlling the association of HgD with DOC, SOC data sets may be utilized to predict stream HgD:DOC ratios on a more geographically widespread basis. In watersheds where DOC data are available, estimates of HgD may be readily obtained. Future Hg emissions policies must consider soil-mediated processes that affect the transport of Hg and DOC from terrestrial watersheds to streams for accurate predictions of water quality impacts.

  6. Dissolved organic matter release and retention in ultisols in relation to land use patterns.

    PubMed

    Zhang, Qichun; Hou, Changping; Liang, Yingying; Feng, Ying

    2014-07-01

    The application of organic fertilizer to maintain soil fertility and crop yield has been practiced for thousands of years in China. This practice improves soil carbon sequestration, due to the high level of dissolved organic matter (DOM) in organic manure. In this study, batch equilibrium studies were conducted to examine the capacity of three ultisols from areas under different land use patterns to retain dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) extracted from rape cake and chicken manure. The results showed that the amount of DOM removed or released in solution by the soil was a linear function of the initial amount added to the soil-water system; therefore, analysis of sorption isotherms was best conducted using the initial mass isotherm IM method. The ultisol retained, on average, 19.9% of the total DOC and 41.7% of the total DON in solution, suggesting that ultisol has a relatively low DOC adsorption capacity. The ultisol from a bamboo forest was found to have a higher capacity than that from a pear orchard to retain DOC and DON. The adsorption affinities of DOM according to soil type were in the following order: bamboo forest (BF)>tea garden (TG)>pear orchard (PO). These results suggested that the continuous application of high doses of organic manure, particularly rape cake, may saturate the DOC adsorptive sites, thereby permitting increased leaching of DOC and the possibility of ground water contamination. Furthermore, we note that amorphous Fe and Al oxides play an important role in the adsorption capacity of both DOC and DON in ultisols.

  7. Sources, behaviors and degradation of dissolved organic matter in the East China Sea

    NASA Astrophysics Data System (ADS)

    Chen, Yan; Yang, Gui-Peng; Liu, Li; Zhang, Peng-Yan; Leng, Wei-Song

    2016-03-01

    Concentrations of dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN), dissolved organic nitrogen (DON) and its major compound classes-total hydrolysable amino acids (THAA) were measured at 4 cross-shelf transects of the East China Sea in July 2011. Surface concentrations of DOC, DIN, DON and THAA at the nearshore stations were mostly in excess of those found at the offshore sites, indicating either substantial autochthonous production or allochthonous inputs from the Changjiang River. The vertical distributions of DOC, DON and THAA showed similar trends with higher values in the surface layer, whereas the elevated concentrations of DIN were observed in the bottom layer. Major constituents of THAA presented in the study area were glycine, serine, alanine, glutamic acid, aspartic acid and valine. The mole percentages of neutral amino acids increased from surface water to bottom water, whereas acidic and hydroxy amino acids decreased with the water depth. Concentrations of DOC and THAA were negatively correlated to the ΔDIN values (the difference between the real concentration and theoretical concentration), respectively, indicating the coupling relation between dissolved organic matter (DOM) remineralization and nutrient regeneration in the water column. The C/N ratios in the water column exhibited different characteristics with elevated values appearing in the surface and bottom layers. Box and whisker plots showed that both degradation index (DI) values and THAA yields displayed a decreasing trend from the surface layer to the bottom layer, implying increasing degradation with the water depth. Our data revealed that glycine and alanine increased in relative abundance with decreasing DI, while tyrosine, valine, phenylalanine and isoleucine increased with increasing DI.

  8. Abundance and Characterization of Dissolved Organic Carbon in Suburban Streams of Baltimore, Maryland, USA

    NASA Astrophysics Data System (ADS)

    Mora, G.; Fazekas, M.

    2014-12-01

    The contribution of streams and rivers to the carbon cycle is significant, transporting to the oceans ~1.4 Pg C/yr, with dissolved carbon corresponding to as much as 0.7 Pg C/yr. Changes in land use have the potential effect of modifying this flux, particularly in urban areas where impervious areas are common. To investigate the effect of urbanization on riverine carbon transport, we studied four first-order streams in Towson, a suburb of Baltimore, Maryland, USA. The watersheds from the studied streams exhibit different levels of urbanization as measured by the percentage of impervious areas. Samples from these four streams were taken weekly, and several chemical constituents were measured either in the field or in the laboratory. These constituents included nitrate, dissolved organic nitrogen, pH, dissolved organic carbon (DOC), total carbon, dissolved inorganic carbon (DIC), phosphate, the carbon isotopic compositions of DOC and DIC, and fluorescence intensity of the DOC. Results show that DOC concentrations were consistently below 5 mg C/L regardless of the level of imperviousness of the watershed. Similarly, carbon isotope ratios were consistent across the studied streams, with values centered around -26.4 per mil, thus suggesting a significant influx of soil-derived organic carbon originated from C3 plants that are common in the watersheds. Confirming this interpretation, fluorescence spectroscopy data suggest a humic-like origin for the DOC of the streams, thus pointing to the heterotrophic nature of the streams. The combined results suggest that the studied streams exhibit similar DOC concentrations, carbon isotopic values, and fluorescence spectra, despite their level of impervious surfaces in their watersheds.

  9. Effect of disinfection upon dissolved organic carbon (DOC) in wastewater: bacterial bioassays.

    PubMed

    Arana, I; Santorum, P; Muela, A; Barcina, I

    2000-08-01

    Quantitative and qualitative changes in organic matter content of wastewater effluents attributable to chlorination and ozonation have been analysed using bioassays as well as organic carbon direct measures. Bioassays were carried out using the bacterial populations of wastewater and two Escherichia coli strains as test micro-organisms. Our results indicate that pure strains present some advantages over indigenous bacteria. Although wastewater bacterial populations are better adapted to growth in wastewater, E. coli strains are more sensitive to changes in dissolved organic carbon (DOC) content. Moreover, the use of pure cultures allows estimation of the portion of DOC which can be converted in cell biomass, the assimilable organic carbon (AOC). Finally, the results obtained using prototrophic and the auxotrophic strains of E. coli suggested that ozonation alters the amino acid composition of wastewater while chlorination does not change the quantity nor the quality of the DOC present in effluents.

  10. Colored dissolved organic matter inversion based on the spectral reflectance data of the Yuqiao Reservoir

    NASA Astrophysics Data System (ADS)

    Zhou, YaMing; Li, JunSheng; Shen, Qian; Zhang, FangFang

    2014-11-01

    Colored Dissolved Organic Matter (CDOM, or yellow substance) exists in all natural waters. It can be used as evaluation indexes for inland water pollution condition. Remote sensing data used for CDOM inversion has its significant advantages, but the inversion method usually has obvious regional limitations. At present, there is little CDOM studies have been carried out to the waters in north China. Yuqiao Reservoir, which is in northern Tianjin, was chosen as the study area, and CDOM was inverted through empirical method for the first time. The data used in this paper was the spectral reflectance data collected on September 24 and 25, 2013 over the 23 sampling points in Yuqiao Reservoir and CDOM concentrations (which is represented by the absorption coeffiecnet of CDOM at 440nm, aCDOM(440)) of each sampling points. Among the 23 sampling points, 16 points were selected randomly as training samples, and the remaining 7 points were for accuracy test. Four ratios, as Rrs(412)/Rrs(551), Rrs(443)/Rrs(551), Rrs(490)/Rrs(551) and Rrs(531)/Rrs(551) were used to carry out linear regression with aCDOM(440). At the same time, the linear regression was also taken between the logs base 10 of the four ratios and log(aCDOM(440)).Then 8 inversion models were built. The performance of the model based on log(Rrs(490)/Rrs(551)) and log(aCDOM(440)) was the best. The correlation coefficient R was 0.65. The Root Mean Square Error (RMSE) was 0.088 and the average relative error (σ) was 11.9%. It showed that the precision of using the ratio of the Remote sensing reflectance of the blue and green band to build inversion models for Yuqiao Reservoir was good, and the method was worth popularization and utilization.

  11. Sulfamethazine Sorption to Soil: Vegetative Management, pH, and Dissolved Organic Matter Effects.

    PubMed

    Chu, Bei; Goyne, Keith W; Anderson, Stephen H; Lin, Chung-Ho; Lerch, Robert N

    2013-01-01

    Elucidating veterinary antibiotic interactions with soil is important for assessing and mitigating possible environmental hazards. The objectives of this study were to investigate the effects of vegetative management, soil properties, and >1000 Da dissolved organic matter (DOM) on sulfamethazine (SMZ) behavior in soil. Sorption experiments were performed over a range of SMZ concentrations (2.5-50 μmol L) using samples from three soils (Armstrong, Huntington, and Menfro), each planted to one of three vegetation treatments: agroforestry buffers strips (ABS), grass buffer strips (GBS), and row crops (RC). Our results show that SMZ sorption isotherms are well fitted by the Freundlich isotherm model (log = 0.44-0.93; Freundlich nonlinearity parameter = 0.59-0.79). Further investigation of solid-to-solution distribution coefficients () demonstrated that vegetative management significantly ( < 0.05) influences SMZ sorption (ABS > GBS > RC). Multiple linear regression analyses indicated that organic carbon (OC) content, pH, and initial SMZ concentration were important properties controlling SMZ sorption. Study of the two most contrasting soils in our sample set revealed that increasing solution pH (pH 6.0-7.5) reduced SMZ sorption to the Armstrong GBS soil, but little pH effect was observed for the Huntington GBS soil containing 50% kaolinite in the clay fraction. The presence of DOM (150 mg L OC) had little significant effect on the Freundlich nonlinearity parameter; however, DOM slightly reduced SMZ values overall. Our results support the use of vegetative buffers to mitigate veterinary antibiotic loss from agroecosystems, provide guidance for properly managing vegetative buffer strips to increase SMZ sorption, and enhance understanding of SMZ sorption to soil.

  12. Sources and fate of bioavailable dissolved organic nitrogen in the Neuse River Estuary, North Carolina

    NASA Astrophysics Data System (ADS)

    Paerl, H. W.; Peierls, B. L.; Hounshell, A.; Osburn, C. L.

    2015-12-01

    Eutrophication is a widespread problem affecting the structure and function of estuaries and is often linked to anthropogenic nitrogen (N) enrichment, since N is the primary nutrient limiting algal production. Watershed management actions typically have ignored dissolved organic nitrogen (DON) loading because of its perceived refractory nature and instead focused on inorganic N as targets for loading reductions. A fluorescence-based model indicated that anthropogenic sources of DON near the head of the microtidal Neuse River Estuary (NRE), NC were dominated by septic systems and poultry waste. A series of bioassays were used to determine the bioavailability of river DON and DON-rich sources to primary producers and whether those additions promoted the growth of certain phytoplankton taxa, particularly harmful species. Overall, at time scales up to two to three weeks, estuarine phytoplankton and bacteria only showed limited responses to additions of high molecular weight (HMW, >1 kDa) river DON. When increases in productivity and biomass did occur, they were quite small compared with the response to inorganic N. Low molecular weight (LMW) river DON, waste water treatment plant effluent, and poultry litter extract did have a positive effect on phytoplankton and bacterial production, indicating a bioavailable fraction. High variability of bulk DON concentration suggested that bioavailable compounds added in the experimental treatments were low in concentration and turned over quite rapidly. Some phytoplankton taxa, as measured by diagnostic photopigments, appeared to be selectively enhanced by the HMW and specific source DON additions, although the taxa could not be positively identified as harmful species. Preliminary tests show that labile autochthonous organic matter may act as a primer for the mineralization of the HMW DON. These and other, longer-term bioavailability studies will be needed to adequately address the fate of watershed DON in estuarine ecosystems.

  13. The mysteriously variable half-life of dissolved organic matter in aquatic ecosystems: artefact or insight?

    NASA Astrophysics Data System (ADS)

    Evans, Chris; Fovet, Ophelie; Jones, Tim; Jones, Davey; Moldan, Filip; Futter, Martyn

    2016-04-01

    Dissolved organic matter (DOM) fluxes from land to water represent an important loss term in the terrestrial carbon balance, a major pathway in the global carbon cycle, a significant influence on aquatic light, nutrient and energy regimes, and an important concern for drinking water production. Although freshwaters are now recognised as zones of active carbon cycling, rather than passive conduits for carbon transport, evidence regarding the magnitude of, and controls on, DOM cycling in aquatic systems is incomplete and in some cases seemingly contradictory, with DOM 'half-lives' ranging from a few days to many years. Bringing together experimental, isotopic, catchment mass balance and modelling data, we suggest that apparently conflicting results can be reconciled through understanding of differences in: i) the terrestrial sources of DOM within heterogeneous landscapes, and consequent differences in its reactivity and stoichiometry; ii) experimental methodologies (i.e. which reactions are actually being measured), and iii) the extent of prior transformation of DOM upstream of the point of study. We argue that rapid photo-degradation, particularly of peat-derived DOM, is a key process in headwaters, whilst apparently slow DOM turnover in downstream, agriculturally-influenced lakes and rivers can partly be explained by the offsetting effect of in situ DOM production. This production appears to be strongly constrained by nutrient supply, thus linking DOM turnover and composition to the supply of inorganic nutrient inputs from diffuse agricultural pollution, and also providing a possible mechanistic link between aquatic DOM production and terrestrial DOM breakdown via the mineralisation and re-assimilation of organic nutrients. A more complete conceptual understanding of these interlinked processes will provide an improved understanding of the sources and fate of aquatic DOM, its role in the global carbon cycle, and the impact of anthropogenic activities, for example

  14. Mobility of Dissolved Organic Matter from the Suwannee River (Georgia, USA) in Sand-Packed Columns

    PubMed Central

    McInnis, Daniel P.; Bolster, Diogo; Maurice, Patricia A.

    2015-01-01

    Abstract Transport of dissolved organic matter (DOM) from the Suwannee River and of synthetic polystyrene sulfonates (PSSs) was investigated in columns packed with naturally Fe/Al-oxide-coated sands from Oyster, Virginia. Surface-water samples were collected in May 2012 and processed by XAD-8 (humic substances; HPOA), XAD-4 (transphilic acids [TPIAs]), and reverse osmosis (broad range of components; NOM). Median transport time (Ro) of PSSs increased with molecular weight (MW) from 1,000 to 8,000 Da but decreased for the largest PSS (18,000 Da), which is consistent with previous observations of MW effects on DOM adsorption and transport. Breakthrough curves (BTCs) of HPOAs and NOM were similar whereas TPIA transport was distinct; although all DOM samples had similar Ro values, BTC asymmetry and dispersivity were greater for TPIAs. All samples exhibited power-law tailing that is characteristic of heterogeneous sorbent/sorbate interactions, potentially including kinetic effects. The one-dimensional advection-dispersion equation was unable to capture the tailing but it was captured well using a continuous-time random walk (CTRW) model. CTRW parameters were similar for the NOM and HPOA samples but distinctly different for TPIAs, which had more pronounced tailing. While retardation of organics generally tends to increase with MW, the lower average MW of TPIAs did not result in decreased overall retardation, which suggests the importance of compositional differences. Results suggest that while TPIAs tend to be a relatively minor component of DOM, their transport behavior differs from that of the predominant HPOA fraction, and they might thus have different impacts on pollutant transport. PMID:25565760

  15. Microbial assimilation of dissolved organic matter in shallow aquitards constrained using organic speciation and stable carbon isotopes

    NASA Astrophysics Data System (ADS)

    Hartland, Adam; Timms, Wendy

    2016-04-01

    Low-permeability aquifer sediments (aquitards) are globally widespread and exert important controls on groundwater quality by decreasing flow rates and limiting gas exchange. Dissolved organic matter (DOM) in aquitards is likely to be a prime substrate for anaerobic microbial metabolism, with potential to facilitate the reduction of important groundwater contaminants, such as nitrate (NO3-). However, it is difficult to estimate microbial assimilation based solely on DOM stable isotope composition (d13C) because interactions with the aquifer matrix (e.g. DOM adsorption/desorption) also alter d13C values. We constrained the extent of microbial fractionation of DOM by modelling the proportion of DOM fractionation due to changes in (13C enriched) hydrophilic DOM (HiDOM) and (13C depleted) hydrophobic DOM (HoDOM) in two shallow aquitard systems (0 to ~40 m depth) with contrasting vadose zone (VZ) thicknesses, overlying deep gravel aquifers (~40 to ~150 m depth). Results indicate that adsorption of HoDOM was most important in the aquitard with a 20m VZ, but minimally important in the system with 1-2m VZ. Microbial fractionation of DOM in deep, anaerobic groundwater coincided with decreases in terminal electron acceptor concentrations at the same depth. The availability of reactive DOM, influenced by unsaturated zone thickness and flow rates, is therefore likely to be an important control on aquitard redox chemistry.

  16. Dissolved organic matter composition and bioavailability reflect ecosystem productivity in the Western Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Shen, Y.; Fichot, C. G.; Benner, R.

    2012-07-01

    Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the Western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting DOM was of limited bioavailability. Yields of TDAA in the upper halocline of slope and basin waters were also low, suggesting the Beaufort is not a major source of bioavailable DOM to slope and basin waters. In shelf waters of both systems, elevated concentrations and yields of TDAA were often observed in waters with higher chlorophyll concentrations and productivity. Surface concentrations of DOC were similar (p > 0.05) in the two systems despite the contrasting productivity, but concentrations and yields of TDAA were significantly higher (p < 0.0001) in the Chukchi than in the Beaufort. Unlike bulk DOC, TDAA concentrations and yields reflect ecosystem productivity in the Western Arctic. The occurrence of elevated bioavailable DOM concentrations in the Chukchi implies an uncoupling between the biological production and utilization of DOM and has important implications for sustaining heterotrophic microbial growth and diversity in oligotrophic waters of the Central Arctic basins.

  17. Tracing origins of sewage and organic matter using dissolved sterols in Masan and Haengam Bay, Korea

    NASA Astrophysics Data System (ADS)

    Lee, Hyo Jin; Hong, Sang Hee; Kim, Moonkoo; Ha, Sung Yong; An, Soon Mo; Shim, Won Joon

    2011-06-01

    Masan and Haengam Bays in Korea are highly polluted and semi-enclosed. Domestic and industrial effluents are directly or indirectly discharged into the bays through sewage treatment plants (STP) and creeks. In this study, 15 dissolved sterol compounds were determined in order to understand their sources and relative contribution. Freshwater samples were taken from 13 creeks and at two STP sites on a monthly basis. Total dissolved sterol concentrations ranged from 993 to 4158 ng/L. The concentrations of sterols in winter were higher than in summer. Among the sterols analyzed, cholesterol, β-sitosterol, coprostanol and cholestanone were major compounds in creek water. Seawater samples were concurrently collected at 21 stations in Masan Bay. Total sterol concentrations ranged 118-6,956 ng/L. Inner bay showed high concentrations of sterols in summer, while outer bay showed high sterol concentrations in winter. Among the sterols, cholesterol, β-sitosterol and brassicasterol were major compounds in seawater. In order to examine the contribution of urban sewage, the concentration of coprostanol and fecal sterol ratios were calculated. Most of the creek water, inner bay and near STP outlet samples were affected by sewage. Terrestrial organic matters accounted for a high proportion of dissolved organic matter origin. Fecal origins were relatively high in the inner bay areas and in the STP outlet, while sterols of marine origin were high in the outer bay areas.

  18. Groundwater contributions of flow, nitrate, and dissolved organic carbon to the lower San Joaquin River, California, 2006-08

    USGS Publications Warehouse

    Zamora, Celia; Dahlgren, Randy A.; Kratzer, Charles R.; Downing, Bryan D.; Russell, Ann D.; Dileanis, Peter D.; Bergamaschi, Brian A.; Phillips, Steven P.

    2013-01-01

    The influence of groundwater on surface-water quality in the San Joaquin River, California, was examined for a 59-mile reach from the confluence with Salt Slough to Vernalis. The primary objective of this study was to quantify the rate of groundwater discharged to the lower San Joaquin River and the contribution of nitrate and dissolved organic carbon concentrations to the river. Multiple lines of evidence from four independent approaches were used to characterize groundwater contributions of nitrogen and dissolved organic carbon. Monitoring wells (in-stream and bank wells), streambed synoptic surveys (stream water and shallow groundwater), longitudinal profile surveys by boat (continuous water-quality parameters in the stream), and modeling (MODFLOW and VS2DH) provided a combination of temporal, spatial, quantitative, and qualitative evidence of groundwater contributions to the river and the associated quality. Monitoring wells in nested clusters in the streambed (in-stream wells) and on both banks (bank wells) along the river were monitored monthly from September 2006 to January 2009. Nitrate concentrations in the bank wells ranged from less than detection—that is, less than 0.01 milligrams per liter (mg/L) as nitrogen (N)—to approximately 13 mg/L as N. Nitrate was not detected at 17 of 26 monitoring wells during the study period. Dissolved organic carbon concentrations among monitoring wells were highly variable, but they generally ranged from 1 to 4 mg/L. In a previous study, 14 bank wells were sampled once in 1988 following their original installation. With few exceptions, specific conductivity and nitrate concentrations measured in this study were virtually identical to those measured 20 years ago. Streambed synoptic measurements were made by using a temporarily installed drive-point piezometer at 113 distinct transects across the stream during 4 sampling events. Nitrate concentrations exceeded the detection limit of 0.01 mg/L as N in 5 percent of

  19. Poultry manure runoff and its influence on fluorescence characteristics of dissolved organic matter (DOM)

    NASA Astrophysics Data System (ADS)

    Singh, S.; Dutta, S.; Inamdar, S. P.

    2013-12-01

    Land application of poultry manure as a substitute for synthetic fertilizer is a common practice in states like Delaware which have a surplus of this animal waste. However, this practice can generate large amounts of labile DOM and nutrients in agricultural runoff that can cause eutrophication of downstream aquatic ecosystems. We determined the concentrations of dissolved organic carbon (DOC) and dissolved inorganic nitrogen (DIN) and the quality of DOM for a cropland receiving poultry manure in the coastal plain soils of Delaware. Manure was applied at the rate of 9 Mg ha-1 in the spring (March 10) of 2010 to an agricultural field planted in corn. Sampling was performed for surface runoff and soil waters at four landscape positions - field edge, upper and lower riparian zones and the stream. Sampling was conducted for eight storm events, one before manure application and seven after (March through July spanning over 100 days). DOM quality was characterized using spectrofluorometric techniques and the development of a site-specific PARAFAC model. DOC and DIN concentrations in surface runoff ranged from 18.1 to 77.2 mg/l and 4.2 to 22.6 mg/l, respectively. The percent of protein-like and humic-like DOM in surface runoff ranged between 3.9 to 23.5% and 12.3 to 41.6%, respectively. Highest concentrations of DOC and DIN were observed at the field edge and lowest in the stream. Protein-like and humic-like DOM decreased from the field edge to stream in surface runoff and soil waters. Temporally, both humic-like and protein-like DOM showed significant increases in storm runoff following manure application. After manure application, humic-like DOM increased by 70% while protein-like DOM increased by more than 200% in surface runoff indicating elevated content of labile DOM in poultry manure. These concentrations remained high for more than 60 days following manure application. Protein-like DOM was significantly correlated with nitrate-nitrogen (r = 0.43; p < 0

  20. Atmospheric pressure mass spectrometry: a new analytical chemical characterization method for dissolved organic matter in rainwater.

    PubMed

    Seitzinger, Sybil P; Styles, Renée M; Lauck, Ron; Mazurek, Monica A

    2003-01-01

    The complex mixture of organic compounds in the atmosphere influences climate, air quality, and ecosystem processes. Atmospheric pressure electrospray ionization mass spectrometry (APESI-MS) was evaluated as a potential tool for direct measurement of the total suite of individual dissolved organic matter (DOM) compounds in rainwater. The APESI-MS response was linear to all DOM compounds of atmospheric significance examined as standard solutions. Urban precipitation samples from New Brunswick, NJ (USA) were analyzed by APESI-MS over the mass-to-charge (m/z) range 50-3,000. Over 95% of the m/z ions detected were in the low m/z range (50-500). Over 300 unique m/z ions were detected across the 11 rainwater samples indicating the complexity of the mixture of DOM in rainwater. Forty percent of the organic bases (positive mode detection) and 22% of the organic acids (negative mode) occurred in at least 6 of the 11 rainwater samples. Ions corresponding to the m/z of carboxylic acids standards (nonanedioic acid; 1,4-butanedicarboxylic acid; pentanedioic acid; hydroxybutanedioic acid; and butanedioic acid) and to reduced N standards (allylurea; caffeine; imidazole; and N-2-propenylurea) occurred in at least one of the 11 rainwater samples. Total dissolved organic carbon (DOC) estimated from the APESI-MS analysis and measured by standard DOC methods were not statistically different.

  1. Effect of past peat cultivation practices on present dynamics of dissolved organic carbon.

    PubMed

    Frank, S; Tiemeyer, B; Bechtold, M; Lücke, A; Bol, R

    2017-01-01

    Peatlands are a major source of dissolved organic carbon (DOC) for aquatic ecosystems. Naturally high DOC concentrations in peatlands may be increased further by drainage. For agricultural purposes, peat has frequently been mixed with sand, but the effect of this measure on the release and cycling of DOC has rarely been investigated. This study examined the effects of (i) mixing peat with sand and (ii) water table depth (WTD) on DOC concentrations at three grassland sites on shallow organic soils. The soil solution was sampled bi-weekly for two years with suction plates at 15, 30 and 60cm depth. Selected samples were analysed for dissolved organic nitrogen (DON), δ(13)CDOM and δ(15)NDOM. Average DOC concentrations were surprisingly high, ranging from 161 to 192mgl(-1). There was no significant impact of soil organic carbon (SOC) content or WTD on mean DOC concentrations. At all sites, DOC concentrations were highest at the boundary between the SOC-rich horizon and the mineral subsoil. In contrast to the mean concentrations, the temporal patterns of DOC concentrations, their drivers and the properties of dissolved organic matter (DOM) differed between peat-sand mixtures and peat. DOC concentrations responded to changes in environmental conditions, but only after a lag period of a few weeks. At the sites with a peat-sand mixture, temperature and therefore probably biological activity determined the DOC concentrations. At the peat site, the contribution of vegetation-derived DOM was higher. The highest concentrations occurred during long, cool periods of waterlogging, suggesting a stronger physicochemical-based DOC mobilisation. Overall, these results indicate that mixing peat with sand does not improve water quality and may result in DOC losses of around 200kg DOCha(-1)a(-1).

  2. Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?

    NASA Astrophysics Data System (ADS)

    Koch, B. P.; Kattner, G.; Witt, M.; Passow, U.

    2014-02-01

    The degradation of marine dissolved organic matter (DOM) is an important control variable in the global carbon cycle and dependent on the DOM composition. For our understanding of the kinetics of organic matter cycling in the ocean, it is therefore crucial to achieve a mechanistic and molecular understanding of its transformation processes. A long-term microbial experiment was performed to follow the production of non-labile DOM by marine bacteria. Two different glucose concentrations and dissolved algal exudates were used as substrates. We monitored the bacterial abundance, concentrations of dissolved and particulate organic carbon (DOC, POC), nutrients, amino acids, and transparent exopolymer particles (TEP) for two years. Ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) allowed the molecular characterization of extracted DOM after 70 days and after ∼2 years of incubation. Although glucose was quickly degraded, a DOC background was generated in glucose incubations. Only 20% of the organic carbon from algal exudate was degraded within the 2 years of incubation. TEP, which are released by micro-organisms, were produced during glucose degradation but decreased within less than three weeks back to half of the maximum concentration and were below detection in all treatments after 2 years. The molecular analysis demonstrated that DOM generated during glucose degradation differed appreciably from DOM produced during the degradation of the algal exudates. Our results led to several conclusions: (i) Higher substrate levels result in a higher level of non-labile DOC which is an important prerequisite for carbon sequestration in the ocean; (ii) TEP are generated by bacteria but are also degraded rapidly, thus limiting their potential contribution to carbon sequestration; (iii) The molecular signatures of DOM derived from algal exudates or glucose after 70 days of incubation differed strongly from refractory DOM. After 2 years

  3. Bioavailable dissolved organic matter and biological hot spots during austral winter in Antarctic waters

    NASA Astrophysics Data System (ADS)

    Shen, Yuan; Benner, Ronald; Murray, Alison E.; Gimpel, Carla; Greg Mitchell, B.; Weiss, Elliot L.; Reiss, Christian

    2017-01-01

    Primary production and heterotrophic bacterial activity in the Antarctic Ocean are generally low during the austral winter. Organic carbon is considered to be a major factor limiting bacterial metabolism, but few studies have investigated the bioavailability of organic matter during winter. Herein, the chemical composition and bioavailability of dissolved organic matter (DOM) were investigated in surface (5-100 m) and mesopelagic (200-750 m) waters off the northwestern Antarctic Peninsula during August 2012. Concentrations of dissolved organic carbon (DOC) were low (42 ± 4 µmol L-1) and showed no apparent spatial patterns. By contrast, the composition of DOM exhibited significant spatial trends that reflected varying ecosystem productivity and water masses. Surface distributions of chlorophyll-a and particulate organic carbon depicted a southward decline in primary productivity from open waters (60.0°S-61.5°S) to ice-covered regions (61.5°S-62.5°S). This trend was evident from concentrations and DOC-normalized yields of dissolved amino acids in the surface waters, indicating decreasing DOM bioavailability with increasing latitude. A different pattern of DOM bioavailability was observed in the mesopelagic water masses, where amino acids indicated highly altered DOM in the Circumpolar Deep Water and bioavailable DOM in the Transitional Weddell Water. Depth distributions of amino acid yields and compositions revealed hot spots of elevated bioavailable DOM at ˜75 m relative to surrounding waters at most ice-free stations. Relatively low mole percentages of bacterially derived D-amino acids in hot spots were consistent with an algal source of bioavailable DOM. Overall, these results reveal the occurrence and spatial heterogeneity of bioavailable substrates in Antarctic waters during winter.

  4. Effect of algal flocculation on dissolved organic matters using cationic starch modified soils.

    PubMed

    Shi, Wenqing; Bi, Lei; Pan, Gang

    2016-07-01

    Modified soils (MSs) are being increasingly used as geo-engineering materials for the sedimentation removal of cyanobacterial blooms. Cationic starch (CS) has been tested as an effective soil modifier, but little is known about its potential impacts on the treated water. This study investigated dissolved organic matters in the bloom water after algal removal using cationic starch modified soils (CS-MSs). Results showed that the dissolved organic carbon (DOC) could be decreased by CS-MS flocculation and the use of higher charge density CS yielded a greater DOC reduction. When CS with the charge density of 0.052, 0.102 and 0.293meq/g were used, DOC was decreased from 3.4 to 3.0, 2.3 and 1.7mg/L, respectively. The excitation-emission matrix fluorescence spectroscopy and UV254 analysis indicated that CS-MS exhibits an ability to remove some soluble organics, which contributed to the DOC reduction. However, the use of low charge density CS posed a potential risk of DOC increase due to the high CS loading for effective algal removal. When CS with the charge density of 0.044meq/g was used, DOC was increased from 3.4 to 3.9mg/L. This study suggested, when CS-MS is used for cyanobacterial bloom removal, the content of dissolved organic matters in the treated water can be controlled by optimizing the charge density of CS. For the settled organic matters, other measures (e.g., capping treatments using oxygen loaded materials) should be jointly applied after algal flocculation.

  5. Analyzing sediment dissolved oxygen based on microprofile modeling.

    PubMed

    Wang, Chao; Shan, Baoqing; Zhang, Hong; Rong, Nan

    2014-09-01

    Sediment plays a key role in controlling the oxygen demand of aquatic systems. The reaction rate, penetration depth, and flux across the sediment-water interface (SWI) are important factors in sediment oxygen consumption. However, there were few methods to collect these data until recently. In this study, methods were developed to simulate the oxygen microprofile and calculate the sediment oxygen consumption rate, oxygen penetration depth, and oxygen flux across the SWI. We constructed a sediment oxygen measuring system using an oxygen microelectrode and a control device. The simulation equations were derived from both zero and first-order kinetic models, while the penetration depth and the oxygen flux were calculated from the simulation results. The method was tested on four prepared sediment samples. Decreases in dissolved oxygen in surface sediment were clearly detected by the microelectrode. The modeled data were a good fit for the observed data (R (2) > 0.95), and zero-order kinetics were more suitable than first-order kinetics. The values for penetration depth (1.3-3.9 mm) and oxygen fluxes (0.061-0.114 mg/cm(2)/day) calculated by our methods are comparable with those from other studies.

  6. Hydro-climatic control of stream dissolved organic carbon in headwater catchment

    NASA Astrophysics Data System (ADS)

    Humbert, Guillaume; Jaffrezic, Anne; Fovet, Ophélie; Gruau, Gérard; Durand, Patrick

    2014-05-01

    Dissolved organic matter (DOM) is a key form of the organic matter linking together the water and the carbon cycles and interconnecting the biosphere (terrestrial and marine) and the soil. At the landscape scale, land use and hydrology are the main factors controlling the amount of DOM transferred from soils to the stream. In an intensively cultivated catchment, a recent work using isotopic composition of DOM as a marker has identified two different sources of DOM. The uppermost soil horizons of the riparian wetland appear as a quasi-infinite source while the topsoil of the hillslope forms a limited one mobilized by water-table rise and exported to the stream across the upland-riparian wetland-stream continuum. In addition to the exportation of DOM via water fluxes, climatic factors like temperature and precipitation regulate the DOM production by influencing microbial activity and soil organic matter degradation. The small headwater catchment (5 km²) of Kervidy-Naizin located in Brittany is part of the Environment Research Observatory (ORE) AgrHys. Weather and the hydro-chemistry of the stream, and the groundwater levels are daily recorded since 1993, 2000 and 2001 respectively. Over 13 contrasted hydrological years, the annual flow weighted mean concentration of dissolved organic carbon (DOC) is 5.6 mg.L-1 (sd = 0.7) for annual precipitation varying from 488mm to 1327mm and annual mean temperatures of 11°C (sd = 0.6). Based on this considerable dataset and this annual variability, we tried to understand how the hydro-climatic conditions determinate the stream DOC concentrations along the year. From the fluctuations of water table depth, each hydrologic year has been divided into three main period: i) progressive rewetting of the riparian wetland soils, ii) rising and holding high of the water table in the hillslope, iii) drawdown of the water-table, with less and less topsoil connected to the stream. Within each period base flow and storm flow data were first

  7. [Spectral characteristics of dissolved organic matter released during the metabolic process of small medusa].

    PubMed

    Guo, Dong-Hui; Yi, Yue-Yuan; Zhao, Lei; Guo, Wei-Dong

    2012-06-01

    The metabolic processes of jellyfish can produce dissolved organic matter (DOM) which will influence the functioning of the aquatic ecosystems, yet the optical properties of DOM released by jellyfish are unknown. Here we report the absorption and fluorescence properties of DOM released by a medusa species Black fordia virginica during a 24 h incubation experiment. Compared with the control group, an obvious increase in the concentrations of dissolved organic carbon (DOC), absorption coefficient (a280) and total dissolved nitrogen (TDN) was observed in incubation group. This clearly demonstrated the release of DOM, chromophoric DOM (CDOM) and dissolved nutrients by B. virginica which feed on enough of Artemia sp. before the experiment. The increase in spectral slope ratio (SR) and decrease in humification index (HIX) indicated that the released DOM was less-humified and had relatively lower molecular weight. Parallel factor analysis (PARAFAC) decomposed the fluorescence matrices of DOM into three humic-like components (C1-C3) and one protein-like component (C4). The Fmax of two components (C2: < 250, 295/386 nm; C4: 275/334 nm) with the emission wavelength < 400 nm increased significantly during the metabolic process of B. virginica. However, the Fmax of the other two components with the emission wavelength > 400 nm showed little changes. Thus, we suggested a zooplankton index (ZIX) to trace and characterize the DOM excreted by metabolic activity of zooplankton, which is calculated as the ratio of the sum of Fmax of all fluorescence components with the emission wavelength < 400 nm to the sum of Fmax of the other components with the emission wavelength > 400 nm.

  8. Export of Dissolved Organic Matter, Nutrients and Carbon from Himalayan River System in Central Nepal

    NASA Astrophysics Data System (ADS)

    Bhatt, M. P.

    2014-12-01

    Chemical weathering is a vital ecosystem process and plays a central role in regulation of global carbon cycles. Weathering from Himalayan landscape supply high amount of major ions, nutrients and suspended sediments to the oceans. Surface water samples were collected from sixteen stations at different altitude along the Langtnag-Narayani Himalayan river system in central Nepal on a monthly basis for one year. This study aims to investigate spatiotemporal variations of dissolved organic matter, nutrients and carbonic species and to evaluate their controlling factors within the basin. The fluxes of these species appeared several fold higher at low elevation than at mid mountains and high elevation Himalaya sites. Seasonality appeared to exert major control on concentrations and fluxes of major solutes along the drainage network. The highest export rate of chemical species corresponded to the monsoon season, followed by the ones corresponding to post-monsoon and pre-monsoon seasons. Carbonate has major control on the flux of major solutes within the basin. The export rate of dissolved organic carbon and total dissolved nitrogen were about three and seventeen times higher respectively at the Narayani basin than its headwater at Langtang basin within the high Himalaya. Nitrate and phosphate export rates in the Narayani basin were 5.07 and 0.34 tons km-2 yr-1 respectively which is several fold higher than the rates in the high Himalaya probably due to input from agricultural activities. The export of dissolved inorganic carbon from the Narayani basin was 101.87 tons km-2 yr-1 of which bicarbonate appeared to be the dominant fraction (94.9%) followed by carbonic acid (4.7%) and carbonate (0.4%). Partial pressure of carbon dioxide (pCO2) resulted under-saturated in the high elevation Himalayan basin and supersaturated at the low elevation Narayani basin. The concentration of pCO2 is considered to be an important factor for regulating weathering rates of any landscape.

  9. Fate of Allochthonous Dissolved Organic Carbon in Lakes: A Quantitative Approach

    PubMed Central

    Hanson, Paul C.; Hamilton, David P.; Stanley, Emily H.; Preston, Nicholas; Langman, Owen C.; Kara, Emily L.

    2011-01-01

    Inputs of dissolved organic carbon (DOC) to lakes derived from the surrounding landscape can be stored, mineralized or passed to downstream ecosystems. The balance among these OC fates depends on a suite of physical, chemical, and biological processes within the lake, as well as the degree of recalcintrance of the allochthonous DOC load. The relative importance of these processes has not been well quantified due to the complex nature of lakes, as well as challenges in scaling DOC degradation experiments under controlled conditions to the whole lake scale. We used a coupled hydrodynamic-water quality model to simulate broad ranges in lake area and DOC, two characteristics important to processing allochthonous carbon through their influences on lake temperature, mixing depth and hydrology. We calibrated the model to four lakes from the North Temperate Lakes Long Term Ecological Research site, and simulated an additional 12 ‘hypothetical’ lakes to fill the gradients in lake size and DOC concentration. For each lake, we tested several mineralization rates (range: 0.001 d−1 to 0.010 d−1) representative of the range found in the literature. We found that mineralization rates at the ecosystem scale were roughly half the values from laboratory experiments, due to relatively cool water temperatures and other lake-specific factors that influence water temperature and hydrologic residence time. Results from simulations indicated that the fate of allochthonous DOC was controlled primarily by the mineralization rate and the hydrologic residence time. Lakes with residence times <1 year exported approximately 60% of the DOC, whereas lakes with residence times >6 years mineralized approximately 60% of the DOC. DOC fate in lakes can be determined with a few relatively easily measured factors, such as lake morphometry, residence time, and temperature, assuming we know the recalcitrance of the DOC. PMID:21779347

  10. Evidence for production and lateral transport of dissolved organic phosphorus in the eastern subtropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Reynolds, Sarah; Mahaffey, Claire; Roussenov, Vassil; Williams, Richard G.

    2014-08-01

    The concentration of phosphate and dissolved organic phosphorus (DOP) is chronically low and limits phytoplankton growth in the subtropical North Atlantic relative to other ocean basins. Transport of phosphate and DOP from the productive flanks of the gyre to its interior has been hypothesized as an important phosphorus supply pathway. During a cruise in the eastern Atlantic in spring 2011, the rates of phosphate uptake, alkaline phosphatase activity (APA), and DOP production were measured in the northwest African shelf region, subtropics, and tropics. Rates of DOP production were sixfold higher in the shelf region (43 ± 41 nM d-1) relative to the subtropics (6.9 ± 4.4 nM d-1). In contrast, APA was threefold higher in the subtropics (8.0 ± 7.3 nM d-1), indicative of enhanced DOP utilization, relative to the shelf region (2.6 ± 2.1 nM d-1). Hence, observations suggest net production of DOP in the shelf region and either net consumption of DOP or a near balance in DOP production and consumption in the gyre interior. Eddy-permitting model experiments demonstrate that (i) DOP accounts for over half the total phosphorus in surface waters, (ii) DOP is transported westward from the shelf region by a combination of gyre and eddy circulations, and (iii) advected DOP supports up to 70% of the particle export over much of the subtropical gyre. Our combined observational and modeling study supports the view that the horizontal transport of DOP from the shelf region is an important mechanism supplying phosphorus to the surface subtropical North Atlantic.

  11. Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

    NASA Astrophysics Data System (ADS)

    Eckard, Robert S.; Hernes, Peter J.; Bergamaschi, Brian A.; Stepanauskas, Ramunas; Kendall, Carol

    2007-12-01

    Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L -1 within the Sacramento River to 39.9 mg L -1 at the outfall from an island drain (median 3.0 mg L -1), while lignin concentrations ranged from 3.0 μg L -1 within the Sacramento River to 111 μg L -1 at the outfall from an island drain (median 11.6 μg L -1). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC) -1 at an island drain to 0.84 mg (100 mg OC) -1 for a wetland (median 0.36 mg (100 mg OC) -1), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of

  12. Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

    USGS Publications Warehouse

    Eckard, Robert S.; Hernes, Peter J.; Bergamaschi, Brian A.; Stepanauskas, Ramunas; Kendall, Carol

    2007-01-01

    Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L-1 within the Sacramento River to 39.9 mg L-1 at the outfall from an island drain (median 3.0 mg L-1), while lignin concentrations ranged from 3.0 μL-1 within the Sacramento River to 111 μL-1 at the outfall from an island drain (median 11.6 μL-1). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC)-1 at an island drain to 0.84 mg (100 mg OC)-1 for a wetland (median 0.36 mg (100 mg OC)-1), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized

  13. Using water chemistry time series to model dissolved inorganic carbon dynamics in the western Amazon basin

    NASA Astrophysics Data System (ADS)

    Vihermaa, Leena; Waldron, Susan; Newton, Jason

    2013-04-01

    Two small streams (New Colpita and Main Trail) and two rivers (Tambopata and La Torre), in the Tambopata National Reserve, Madre de Dios, Peru, were sampled for water chemistry (conductivity, pH and dissolved oxygen) and hydrology (stage height and flow velocity). In the small streams water chemistry and hydrology variables were logged at 15 minute intervals from Feb 2011 to November 2012. Water samples were collected from all four channels during field campaigns spanning different seasons and targeting the hydrological extremes. All the samples were analysed for dissolved inorganic carbon (DIC) concentration and δ13C (sample size ranging from 77 to 172 depending on the drainage system) and a smaller subset for dissolved organic carbon (DOC) and particulate organic carbon (POC) concentrations. Strong positive relationships were found between conductivity and both DIC concentration and δ13C in the New Colpita stream and the La Torre river. In Tambopata river the trends were less clear and in the Main Trail stream there was very little change in DIC and isotopic composition. The conductivity data was used to model continuous DIC time series for the New Colpita stream. The modelled DIC data agreed well with the measurements; the concordance correlation coefficients between predicted and measured data were 0.91 and 0.87 for mM-DIC and δ13C-DIC, respectively. The predictions of δ13C-DIC were improved when calendar month was included in the model, which indicates seasonal differences in the δ13C-DIC conductivity relationship. At present, continuous DIC sampling still requires expensive instrumentation. Therefore, modelling DIC from a proxy variable which can be monitored continuously with ease and at relatively low cost, such as conductivity, provides a powerful alternative method of DIC determination.

  14. Lake transparency: a window into decadal variations in dissolved organic carbon concentrations in Lakes of Acadia National Park, Maine

    USGS Publications Warehouse

    Roesler, Collin S.; Culbertson, Charles W.

    2016-01-01

    A forty year time series of Secchi depth observations from approximately 25 lakes in Acadia National Park, Maine, USA, evidences large variations in transparency between lakes but relatively little seasonal cycle within lakes. However, there are coherent patterns over the time series, suggesting large scale processes are responsible. It has been suggested that variations in colored dissolved organic matter (CDOM) are primarily responsible for the variations in transparency, both between lakes and over time and further that CDOM is a robust optical proxy for dissolved organic carbon (DOC). Here we present a forward model of Secchi depth as a function of DOC based upon first principles and bio-optical relationships. Inverting the model to estimate DOC concentration from Secchi depth observations compared well with the measured DOC concentrations collected since 1995 (RMS error < 1.3 mg C l-1). This inverse model allows the time series of DOC to be extended back to the mid 1970s when only Secchi depth observations were collected, and thus provides a means for investigating lake response to climate forcing, changing atmospheric chemistry and watershed characteristics, including land cover and land use.

  15. Cationic complexation with dissolved organic matter: Insights from molecular dynamics computer simulations and NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kalinichev, A. G.; Xu, X.; Kirkpatrick, R.

    2006-12-01

    Dissolved organic matter (DOM) is ubiquitous in soil and surface water and plays many important geochemical and environmental roles acting as a proton donor/acceptor and pH buffer and interacting with metal ions, minerals and organic species to form water-soluble and water-insoluble complexes of widely differing chemical and biological stabilities. There are strong correlations among the concentration of DOM and the speciation, solubility and toxicity of many trace metals in soil and water due to metal-DOM interaction. DOM can also significantly negatively affect the performance of nanofiltration and reverse osmosis membranes used industrially for water purification and desalination, being one of the major causes of a so-called `membrane bio- fouling'. The molecular scale mechanisms and dynamics of the DOM interactions with metals and membranes are, however, quite poorly understood. Methods of computational molecular modeling, combined with element- specific nuclear magnetic resonance (NMR) spectroscopy, can serve as highly effective tools to probe and quantify on a fundamental molecular level the DOM interactions with metal cations in aqueous solutions, and to develop predictive models of the molecular mechanisms responsible for the metal-DOM complexation in the environment. This paper presents the results of molecular dynamics (MD) computer simulations of the interaction of DOM with dissolved Na+, Cs+, Mg2+, and Ca2+. Na+ forms only very weak outer-sphere complexes with DOM. These results and the results of other recent molecular modeling efforts (e.g., Sutton et al., Environmental Toxicology and Chemistry, 24, 1902-1911, 2005), clearly indicate that both the structural and dynamic aspects of the cation-DOM complexation follow a simple trend in terms of the charge/size ratio for the ions. Due to the competition between ion hydration in bulk aqueous solution and adsorption of these cations by the negatively charged DOM functional groups (primarily carboxylate

  16. Vapor Pressure Isotope Effects in Halogenated Organic Compounds and Alcohols Dissolved in Water.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2016-12-20

    Volatilization causes changes in the isotopic composition of organic compounds as a result of different vapor pressures of molecules containing heavy and light isotopes. Both normal and inverse vapor pressure isotope effects (VPIE) have been observed, depending on molecular interactions in the liquid phase and the investigated element. Previous studies have focused mostly on pure compound volatilization or on compounds dissolved in organic liquids. Environmentally relevant scenarios, such as isotope fractionation during volatilization of organics from open water surfaces, have largely been neglected. In the current study, open-system volatilization experiments (focusing thereby on kinetic/-nonequilibrium effects) were carried out at ambient temperatures for trichloromethane, trichloroethene, trichlorofluoromethane, trichlorotrifluoroethane, methanol, and ethanol dissolved in water and, if not previously reported in the literature for these compounds, for volatilization from pure liquids. Stable carbon isotopic signatures were measured using continuous flow isotope ratio mass spectrometry. The results demonstrate that volatilization of the four halogenated compounds from water does not cause a measurable change in the carbon isotopic composition, whereas for pure-phase evaporation, significant inverse isotope effects are consistently observed (+0.3 ‰< ε < + 1.7 ‰). In contrast, methanol and ethanol showed normal isotope effects for evaporation of pure organic liquids (-3.9 ‰ and -1.9 ‰) and for volatilization of compounds dissolved in water (-4.4 ‰ and -2.9 ‰), respectively. This absence of measurable carbon isotope fractionation considerably facilitates the application of isotopic techniques for extraction of field samples and preconcentration of organohalogens-known to be important pollutants in groundwater and in the atmosphere.

  17. Dissolved Organic Carbon Mobilisation in a Groundwater System Stressed by Pumping

    PubMed Central

    Graham, P. W.; Baker, A.; Andersen, M. S.

    2015-01-01

    The concentration and flux of organic carbon in aquifers is influenced by recharge and abstraction, and surface and subsurface processing. In this study groundwater was abstracted from a shallow fractured rock aquifer and dissolved organic carbon (DOC) was measured in observation bores at different distances from the abstraction bore. Groundwater abstraction at rates exceeding the aquifers yield resulted in increased DOC concentration up to 3,500 percent of initial concentrations. Potential sources of this increased DOC were determined using optical fluorescence and absorbance analysis. Groundwater fluorescent dissolved organic material (FDOM) were found to be a combination of terrestrial-derived humic material and microbial or protein sourced material. Relative molecular weight of FDOM within four metres of the abstraction well increased during the experiment, while the relative molecular weight of FDOM between four and ten metres from the abstraction well decreased. When the aquifer is not being pumped, DOC mobilisation in the aquifer is low. We hypothesise that the physical shear stress on aquifer materials caused by intense abstraction significantly increases the temporary release of DOC from sloughing of biofilms and release of otherwise bound colloidal and sedimentary organic carbon (SOC). PMID:26691238

  18. Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids

    SciTech Connect

    Chiou, C.T.; Malcolm, R.L.; Brinton, T.I.; Kile, D.E.

    1986-05-01

    Water solubility enhancements by dissolved humic and fulvic acids from soil and aquatic origins and by synthetic organic polymers have been determined for selected organic pollutants and pesticides (p,p'-DDT,2,4,5,2',5'-PCB, 2,4,4'-PCB, 1,2,3,-trichlorobenzene, and lindane). Significant solubility enhancements of relatively water-insoluble solutes by dissolved organic matter (DOM) of soil and aquatic origins may be described in terms of a partition-like interaction of the solutes with the microscopic organic environment of the high-molecular-weight DOM species; the apparent solute solubilities increase linearly with DOM concentration and show no competitive effect between solutes. The K/sub dom/ values of solutes with soil-derived humic acid are approximately 4 times greater than with soil fulvic acid and 5-7 times greater than with aquatic humic and fulvic acids. The effectiveness of DOM in enhancing solute solubility appears to be largely controlled by the DOM molecular size and polarity. The relative inability of high-molecular-weight poly(acrylic acids) to enhance solute solubility is attributed to their high polarities and extended chain structures that do not permit the formation of a sizable intramolecular nonpolar environment. 41 references, 6 figures, 3 tables.

  19. Closely related phytoplankton species produce similar suites of dissolved organic matter

    PubMed Central

    Becker, Jamie W.; Berube, Paul M.; Follett, Christopher L.; Waterbury, John B.; Chisholm, Sallie W.; DeLong, Edward F.; Repeta, Daniel J.

    2014-01-01

    Production of dissolved organic matter (DOM) by marine phytoplankton supplies the majority of organic substrate consumed by heterotrophic bacterioplankton in the sea. This production and subsequent consumption converts a vast quantity of carbon, nitrogen, and phosphorus between organic and inorganic forms, directly impacting global cycles of these biologically important elements. Details regarding the chemical composition of DOM produced by marine phytoplankton are sparse, and while often assumed, it is not currently known if phylogenetically distinct groups of marine phytoplankton release characteristic suites of DOM. To investigate the relationship between specific phytoplankton groups and the DOM they release, hydrophobic phytoplankton-derived dissolved organic matter (DOMP) from eight axenic strains was analyzed using high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS). Identification of DOM features derived from Prochlorococcus, Synechococcus, Thalassiosira, and Phaeodactylum revealed DOMP to be complex and highly strain dependent. Connections between DOMP features and the phylogenetic relatedness of these strains were identified on multiple levels of phylogenetic distance, suggesting that marine phytoplankton produce DOM that in part reflects its phylogenetic origin. Chemical information regarding the size and polarity ranges of features from defined biological sources was also obtained. Our findings reveal DOMP composition to be partially conserved among related phytoplankton species, and implicate marine DOM as a potential factor influencing microbial diversity in the sea by acting as a link between autotrophic and heterotrophic microbial community structures. PMID:24748874

  20. Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids

    USGS Publications Warehouse

    Chiou, C.T.; Malcolm, R.L.; Brinton, T.I.; Kile, D.E.

    1986-01-01

    Water solubility enhancements by dissolved humic and fulvic acids from soil and aquatic origins and by synthetic organic polymers have been determined for selected organic pollutants and pesticides (p,p???-DDT, 2,4,5,2???,5???-PCB, 2,4,4???-PCB, 1,2,3-trichlorobenzene, and lindane). Significant solubility enhancements of relatively water-insoluble solutes by dissolved organic matter (DOM) of soil and aquatic origins may be described in terms of a partition-like interaction of the the solutes with the microscopic organic environment of the high-molecular-weight DOM species; the apparent solute solubilities increase linearly with DOM concentration and show no competitive effect between solutes. With a given DOM sample, the solute partition coefficient (Kdom) increases with a decrease of solute solubility (Sw) or with an increase of the solute's octanol-water partition coefficient (Kow). The Kdom values of solutes with soil-derived humic acid are approximately 4 times greater than with soil fulvic acid and 5-7 times greater than with aquatic humic and fulvic acids. The effectiveness of DOM in enhancing solute solubility appears to be largely controlled by the DOM molecular size and polarity. The relative inability of high-molecular-weight poly(acrylic acids) to enhance solute solubility is attributed to their high polarities and extended chain structures that do not permit the formation of a sizable intramolecular nonpolar environment.

  1. The migration and transformation of dissolved organic matter during the freezing processes of water.

    PubMed

    Xue, Shuang; Wen, Yang; Hui, Xiujuan; Zhang, Lina; Zhang, Zhaohong; Wang, Jie; Zhang, Ying

    2015-01-01

    This study investigated the partitioning behavior of dissolved organic matter (DOM) in liquid and ice phases, as well as the changes in the optical properties and chlorine reactivity of DOM during the freezing processes of water. DOM was rejected from the ice phase and accumulated in the remaining liquid phase during water freezing. Moreover, the decrease in freezing temperature, as well as the increase in dissolved organic carbon (DOC) concentration of feed water, caused an increase in DOM captured in the ice phase. The ultraviolet-absorbing compounds, trihalomethane precursors, as well as fulvic acid- and humic acid-like fluorescent materials, were more liable to be to be rejected from the ice phase and were more easily retained in the unfrozen liquid phase during water freezing, as compared with organics (on average) that comprise DOC. In addition, it was also found a higher accumulation of these organics in the unfrozen liquid phase during water freezing at higher temperature. The freeze/thaw processes altered the quantity, optical properties, and chlorine reactivity of DOM. The decrease in ultraviolet light at 254 nm as well as the production of aromatic protein- and soluble microbial byproduct-like fluorescent materials in DOM due to freeze/thaw were consistently observed. On the other hand, the changes in DOC, trihalomethane formation potential, and fulvic acid- and humic acid-like fluorescence caused by freeze/thaw varied significantly between samples.

  2. Inorganic nitrogen supply and dissolved organic nitrogen abundance across the US Great Plains.

    PubMed

    Mobley, Megan L; Cleary, Matthew J; Burke, Ingrid C

    2014-01-01

    Across US Great Plains grasslands, a gradient of increasing mean annual precipitation from west to east corresponds to increasing aboveground net primary productivity (ANPP) and increasing N-limitation. Previous work has shown that there is no increase in net N mineralization rates across this gradient, leading to the question of where eastern prairie grasses obtain the nitrogen to support production. One as-yet unexamined source is soil organic N, despite abundant literature from other ecosystems showing that plants take up dissolved soil organic N. This study measured KCl-extractable dissolved organic N (DON) in surface soils across the grassland productivity gradient. We found that KCl-extractable DON pools increased from west to east. If available to and used by plants, this DON may help explain the high ANPP in the eastern Great Plains. These results suggest a need for future research to determine whether, in what quantities, and in what forms prairie grasses use organic N to support primary production.

  3. Performance of experimental horizontal subsurface flow constructed wetlands fed with dissolved or particulate organic matter.

    PubMed

    Caselles-Osorio, Aracelly; García, Joan

    2006-11-01

    In this study, the effect of the influent type of organic matter (dissolved or particulate) on the efficiency of two experimental horizontal subsurface flow constructed wetlands (SSF CWs) was investigated. The SSF CWs' surface area was 0.54 m(2) and the water depth was 0.3m. They were monitored for a period of 9 months. One of the SSF CWs was fed with dissolved organic matter (glucose, assumed to be readily biodegradable), and the other with particulate organic matter (starch, assumed to be slowly biodegradable). The removal efficiency of the systems was tested at different hydraulic retention times (HRTs) in the presence or absence of sulphate. The removal efficiency of the COD was not different in the two systems, reaching eliminations of around 85% in the presence of sulphates and around 95% in their absence. Ammonia N removal was low in the two SSF CWs; the system fed with glucose generally had statistically significant higher removal (45%) than the one fed with starch (40%). Ammonia N removal was more affected by the HRT than by the presence or absence of sulphates. Hydraulic conductivity measurements showed that it was lower near the inlet of the SFF CW fed with glucose, probably connected to the fact that there was a more substantial development of the biofilm. The results of this study suggest that SSF CWs are not sensitive to the type of organic matter in the influents, whether it is readily (like glucose) or slowly (like starch) biodegradable, for the removal of COD.

  4. From litter decomposition to soil organic matter formation: using leaf traits to predict dissolved organic carbon leaching

    NASA Astrophysics Data System (ADS)

    Soong, Jennifer; Parton, William; Calderon, Francisco; Guilbert, Kathleen; Campbell, Nell; Cotrufo, M. Francesca

    2014-05-01

    New evidence suggests that leaching of dissolved organic carbon (DOC) during litter decomposition is a major process by which decomposing litter forms stabilized soil organic matter (Cotrufo et al. 2013). Understanding this DOC flux based on plant leaf litter traits would strengthen our ability to predict ecosystem carbon (C) cycling across different vegetation types. In this study we aim to quantify the proportional relationship between CO2 and DOC partitioning during decomposition of fresh leaf litter from five different plant species, alfalfa, ash, bluestem grass, oak and pine, ranging in structural and chemical composition. The results from this laboratory incubation show a clear relationship between the lignin to cellulose ratios of litter and DOC to CO2 partitioning during four distinct phases of litter decomposition. For example, bluestem grass litter with a low lignin to cellulose ratio loses almost 50% of its C as DOC whereas pine needles with a high lignin to cellulose ratio loses much less C as DOC, indicating a potential ligno-cellulose complexation effect on carbon use efficiency and CO2 vs. DOC fluxes during litter decomposition. DOC production also decreases with time during decomposition, correlating with increasing lignin to cellulose ratios and decreasing availability of soluble, non-structural, leaf compounds (based on FTIR analysis). Initial DOC leaching can be predicted based on the amount of labile fraction in each litter type. Field data using stable isotope labeled bluestem grass show that while 18% of the surface litter C lost in 18 months of decomposition enters the soil, over 50% of litter derived C in the soil is recovered in mineral associated heavy SOM fractions, not as litter fragments in the light fraction, confirming the relative importance of the DOC flux of C from the litter layer to the soil for soil organic matter formation. These results are being used to parameterize a new litter decomposition sub-model to more accurately

  5. Using Dissolved Organic Carbon Isotopes for Groundwater Age Dating in Southern Nevada, USA

    NASA Astrophysics Data System (ADS)

    Thomas, James; Hershey, Ronald; Fereday, Wyatt

    2016-04-01

    Dissolved organic carbon (DOC) 14C offers a method to calculate groundwater ages that is more straightforward than dissolved inorganic carbon (DIC) 14C. To obtain corrected DIC 14C groundwater ages requires models that account for chemical and physical processes that affect both 13C and 14C. This is especially true in carbonate-rock aquifers where a fair amount of dissolution and precipitation of carbonate minerals can occur. A first important step in calculating 14C DOC groundwater ages is to determine the initial 14C DOC (A0) values of the groundwater recharge. For this study, recharge area groundwater samples of DOC 14C, collected from 14 different sites, were used to determine the recharge DOC 14C values. These values ranged from 96 to 120 percent modern carbon (pmc), with an average value of 106.2 pmc. These 14C A0 values support the use of a 100 pmc 14C A0 pre-bomb value to calculate DOC 14C groundwater ages for southern Nevada. Several conditions to successfully use DOC 14C to date groundwater need to be met. First, soluble organic carbon content of aquifers needs to be low, so that little DOC is added to the groundwater as it flows from recharge areas down gradient in an aquifer. For this study, volcanic and carbonate aquifer outcrop rocks showed that these rocks contained low soluble organic carbon. Second, it is important that the DOC does not change character down a flow path, which could indicate transformation of DOC along a flow path and/or addition of DOC to the groundwater. Although specific DOC compounds could not be identified for samples collected at four sites, all four groundwater sample spectra show the same general shape over the duration of the HPLC run indicating that the DOC compound composition of groundwater does not significantly change from up-gradient to down-gradient. Third, another factor that could greatly affect DOC 14C groundwater age calculations is matrix diffusion/adsorption of DOC 14C. Laboratory experiments showed that

  6. Isotopic investigations of dissolved organic N in soils identifies N mineralization as a major sink process

    NASA Astrophysics Data System (ADS)

    Wanek, Wolfgang; Prommer, Judith; Hofhansl, Florian

    2016-04-01

    Dissolved organic nitrogen (DON) is a major component of transfer processes in the global nitrogen (N) cycle, contributing to atmospheric N deposition, terrestrial N losses and aquatic N inputs. In terrestrial ecosystems several sources and sinks contribute to belowground DON pools but yet are hard to quantify. In soils, DON is released by desorption of soil organic N and by microbial lysis. Major losses from the DON pool occur via sorption, hydrological losses and by soil N mineralization. Sorption/desorption, lysis and hydrological losses are expected to exhibit no 15N fractionation therefore allowing to trace different DON sources. Soil N mineralization of DON has been commonly assumed to have no or only a small isotope effect of between 0-4‰, however isotope fractionation by N mineralization has rarely been measured and might be larger than anticipated. Depending on the degree of 15N fractionation by soil N mineralization, we would expect DON to become 15N-enriched relative to bulk soil N, and dissolved inorganic N (DIN; ammonium and nitrate) to become 15N-depleted relative to both, bulk soil N and DON. Isotopic analyses of soil organic N, DON and DIN might therefore provide insights into the relative contributions of different sources and sink processes. This study therefore aimed at a better understanding of the isotopic signatures of DON and its controls in soils. We investigated the concentration and isotopic composition of bulk soil N, DON and DIN in a wide range of sites, covering arable, grassland and forest ecosystems in Austria across an altitudinal transect. Isotopic composition of ammonium, nitrate and DON were measured in soil extracts after chemical conversion to N2O by purge-and-trap isotope ratio mass spectrometry. We found that delta15N values of DON ranged between -0.4 and 7.6‰, closely tracking the delta15N values of bulk soils. However, DON was 15N-enriched relative to bulk soil N by 1.5±1.3‰ (1 SD), and inorganic N was 15N

  7. PHOTOGENERATION OF SINGLET OXYGEN AND FREE RADICALS IN DISSOLVED ORGANIC MATTER ISOLATED FROM THE MISSISSIPPI AND ATCHAFALAYA RIVER PLUMES

    EPA Science Inventory

    The photoreactivity to UV light of ultrafiltered dissolved organic matter (DOM) collected during cruises along salinity transects in the Mississippi and Atchafalaya River plumes was examined by measuring photogenerated free radicals and singlet molecular oxygen (1O2) photosensiti...

  8. EFFECTS OF PHOTOCHEMICAL, MICROBIAL AND SORPTION PROCESSES ON THE OPTICAL PROPERTIES AND DEGRADATION OF DISSOLVED ORGANIC MATTER FROM COASTAL WETLANDS

    EPA Science Inventory

    The dissolved organic matter (DOM) exported from rivers and intertidal marshes to coastal oceans is rich in light-absorbing, fluorescent constituents, including humic substances and other polyphenolic moieties. Interactions between microbial and photochemical processes have impor...

  9. PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

    EPA Science Inventory

    Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...

  10. Molecular transformation and degradation of refractory dissolved organic matter in the Atlantic and Southern Ocean

    NASA Astrophysics Data System (ADS)

    Lechtenfeld, Oliver J.; Kattner, Gerhard; Flerus, Ruth; McCallister, S. Leigh; Schmitt-Kopplin, Philippe; Koch, Boris P.

    2014-02-01

    More than 90% of the global ocean dissolved organic carbon (DOC) is refractory, has an average age of 4000-6000 years and a lifespan from months to millennia. The fraction of dissolved organic matter (DOM) that is resistant to degradation is a long-term buffer in the global carbon cycle but its chemical composition, structure, and biochemical formation and degradation mechanisms are still unresolved. We have compiled the most comprehensive molecular dataset of 197 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses from solid-phase extracted marine DOM covering two major oceans, the Atlantic sector of the Southern Ocean and the East Atlantic Ocean (ranging from 50° N to 70° S). Molecular trends and radiocarbon dating of 34 DOM samples (comprising Δ14C values from -229‰ to -495‰) were combined to model an integrated degradation rate for bulk DOC resulting in a predicted age of >24 ka for the most persistent DOM fraction. First order kinetic degradation rates for 1557 mass peaks indicate that numerous DOM molecules cycle on timescales much longer than the turnover of the bulk DOC pool (estimated residence times of up to ~100 ka) and the range of validity of radiocarbon dating. Changes in elemental composition were determined by assigning molecular formulae to the detected mass peaks. The combination of residence times with molecular information enabled modelling of the average elemental composition of the slowest degrading fraction of the DOM pool. In our dataset, a group of 361 molecular formulae represented the most stable composition in the oceanic environment (“island of stability”). These most persistent compounds encompass only a narrow range of the molecular elemental ratios H/C (average of 1.17 ± 0.13), and O/C (average of 0.52 ± 0.10) and molecular masses (360 ± 28 and 497 ± 51 Da). In the Weddell Sea DOC concentrations in the surface waters were low (46.3 ± 3.3 μM) while the organic radiocarbon was significantly

  11. Near-surface Heating of Young Rift Sediment Causes Mass Production and Discharge of Reactive Dissolved Organic Matter

    PubMed Central

    Lin, Yu-Shih; Koch, Boris P.; Feseker, Tomas; Ziervogel, Kai; Goldhammer, Tobias; Schmidt, Frauke; Witt, Matthias; Kellermann, Matthias Y.; Zabel, Matthias; Teske, Andreas; Hinrichs, Kai-Uwe

    2017-01-01

    Ocean margin sediments have been considered as important sources of dissolved organic carbon (DOC) to the deep ocean, yet the contribution from advective settings has just started to be acknowledged. Here we present evidence showing that near-surface heating of sediment in the Guaymas Basin, a young extensional depression, causes mass production and discharge of reactive dissolved organic matter (DOM). In the sediment heated up to ~100 °C, we found unexpectedly low DOC concentrations in the pore waters, reflecting the combined effect of thermal desorption and advective fluid flow. Heating experiments suggested DOC production to be a rapid, abiotic process with the DOC concentration increasing exponentially with temperature. The high proportions of total hydrolyzable amino acids and presence of chemical species affiliated with activated hydrocarbons, carbohydrates and peptides indicate high reactivity of the DOM. Model simulation suggests that at the local scale, near-surface heating of sediment creates short and massive DOC discharge events that elevate the bottom-water DOC concentration. Because of the heterogeneous distribution of high heat flow areas, the expulsion of reactive DOM is spotty at any given time. We conclude that hydrothermal heating of young rift sediments alter deep-ocean budgets of bioavailable DOM, creating organic-rich habitats for benthic life. PMID:28327661

  12. Near-surface Heating of Young Rift Sediment Causes Mass Production and Discharge of Reactive Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Shih; Koch, Boris P.; Feseker, Tomas; Ziervogel, Kai; Goldhammer, Tobias; Schmidt, Frauke; Witt, Matthias; Kellermann, Matthias Y.; Zabel, Matthias; Teske, Andreas; Hinrichs, Kai-Uwe

    2017-03-01

    Ocean margin sediments have been considered as important sources of dissolved organic carbon (DOC) to the deep ocean, yet the contribution from advective settings has just started to be acknowledged. Here we present evidence showing that near-surface heating of sediment in the Guaymas Basin, a young extensional depression, causes mass production and discharge of reactive dissolved organic matter (DOM). In the sediment heated up to ~100 °C, we found unexpectedly low DOC concentrations in the pore waters, reflecting the combined effect of thermal desorption and advective fluid flow. Heating experiments suggested DOC production to be a rapid, abiotic process with the DOC concentration increasing exponentially with temperature. The high proportions of total hydrolyzable amino acids and presence of chemical species affiliated with activated hydrocarbons, carbohydrates and peptides indicate high reactivity of the DOM. Model simulation suggests that at the local scale, near-surface heating of sediment creates short and massive DOC discharge events that elevate the bottom-water DOC concentration. Because of the heterogeneous distribution of high heat flow areas, the expulsion of reactive DOM is spotty at any given time. We conclude that hydrothermal heating of young rift sediments alter deep-ocean budgets of bioavailable DOM, creating organic-rich habitats for benthic life.

  13. Interactions Between Dissolved Organic Matter and Mercury in the Florida Everglades

    NASA Astrophysics Data System (ADS)

    Aiken, G.; Haitzer, M.; Ryan, J.; Nagy, K.

    2002-12-01

    Interactions of mercury (Hg) with dissolved organic matter (DOM) play important roles in controlling reactivity, bioavailability and transport of Hg in aquatic systems. To better define the nature and magnitude of these interactions, experiments were designed using organic matter isolated from various surface waters in the Florida Everglades to determine Hg-DOM binding constants and to study the interactions between DOM and cinnabar (HgS). The isolates, obtained using XAD resins, exhibited a wide range of elemental compositions, aromatic carbon contents, reduced sulfur contents, and molecular weights. Chemical composition of the DOM, especially aromatic carbon and reduced sulfur functional group content, was found to be important in controlling DOM interactions with Hg(II). Conditional distribution coefficients (KDOM'), measured using an equilibrium dialysis ligand exchange method, were strongly affected by the Hg/DOM concentration ratio. Very strong interactions (KDOM' = 1023.2 L kg-1 at pH = 7.0 and I = 0.1), indicative of Hg-thiol bonds, were observed at Hg/DOM ratios below approximately 1 μg Hg per mg DOM. Hg/DOM ratios above approximately 10 μg Hg per mg DOM gave much lower KDOM' values (10{10.7 }L kg-1 at pH 4.9 to 5.6 and I = 0.1), consistent with Hg binding mainly to oxygen functional groups. These results suggest that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios) is controlled by a small fraction of DOM molecules containing reactive thiol functional groups. DOM-Hg interactions were also studied by HgS (log Ksp = -52.4) dissolution and precipitation experiments. In the dissolution experiments, a significant amount of Hg was released from cinnabar in the presence of DOM, suggesting strong interactions. Conversely, precipitation of metacinnabar (black HgS) was strongly inhibited in the presence of low concentrations (<3 mg C/L) of DOM. In both the dissolution and precipitation experiments, organic matter rich in aromatic

  14. Dissolved Organic Carbon Cycling and Transformation Dynamics in A Northern Forested Peatland

    NASA Astrophysics Data System (ADS)

    Tfaily, M. M.; Lin, X.; Chanton, P. R.; Steinweg, J.; Esson, K.; Kostka, J. E.; Cooper, W. T.; Schadt, C. W.; Hanson, P. J.; Chanton, J.

    2013-12-01

    Peatlands sequester one-third of all soil carbon and currently act as major sinks of atmospheric carbon dioxide. The ability to predict or simulate the fate of stored carbon in response to climatic disruption remains hampered by our limited understanding of the controls of carbon turnover and the composition and functioning of peatland microbial communities. A combination of advanced analytical chemistry and microbiology approaches revealed that organic matter reactivity and microbial community dynamics were closely coupled in an extensive field dataset compiled at the S1 bog site established for the SPRUCE program, Marcell Experimental Forest (MEF). The molecular composition and decomposition pathways of dissolved organic carbon (DOC) were contrasted using parallel factor (PARAFAC)-modeled excitation emission fluorescence spectroscopy (EEMS) and FT-ICR MS. The specific UV absorbance (SUVA) at 254 nm was calculated as an indicator of aromaticity. Fluorescence intensity ratios (BIX and FI) were used to infer the relative contributions from solid phase decomposition and microbial production. Distributions of bulk DOC, its stable (δ13C) and radioactive (Δ14C) isotopic composition were also utilized to infer information on its dynamics and transformation processes. Strong vertical stratification was observed in organic matter composition, the distribution of mineralization products (CO2, CH4), respiration rates, and decomposition pathways, whereas smaller variations were observed between sites. A decline in the aromaticity of pore water DOC was accompanied by an increase in microbially-produced DOC. Solid phase peat, on the other hand, became more humified and highly aromatic with depth. These observations were consistent with radiocarbon data that showed that the radiocarbon signatures of microbial respiration products in peat porewaters more closely resemble those of DOC rather than solid peat, indicating that carbon from recent photosynthesis is fueling the

  15. Cu Binding to Iron Oxide-Organic Matter Coprecipitates in Solid and Dissolved Phases

    NASA Astrophysics Data System (ADS)

    Vadas, T. M.; Koenigsmark, F.

    2015-12-01

    Recent studies indicate that Cu is released from wetlands following storm events. Assymetrical field flow field fractionation (AF4) analyses as well as total and dissolved metal concentration measurements suggest iron oxide-organic matter complexes control Cu retention and release. Coprecipitation products of Fe oxide and organic matter were prepared under conditions similar to the wetland to assess Cu partitioning to and availability from solid phases that settle from solution as well as phases remaining suspended. Cu coprecipitation and sorption to organomineral precipitation solids formed at different Fe:organic carbon (OC) ratios were compared for net Cu removal and extractability. As more humic acid was present during precipitation of Fe, TEM images indicated smaller Fe oxide particles formed within an organic matrix as expected. In coprecipitation reactions, as the ratio of Fe:OC decreased, more Cu was removed from solution at pH 5.5 and below. However, in sorption reactions, there was an inhibition of Cu removal at low OC concentrations. As the pH increased from 5.5 to 7 and as solution phase OC concentration increased, more Cu remained dissolved in both coprecipitation and sorption reactions. The addition of Ca2+, glycine, histidine and citric acid or lowering the pH resulted in more extractable Cu from the coprecipitation compared with the sorption reactions. The variations in Cu extraction were likely due to a combination of a more amorphous structure in CPT products, and the relative abundance of available Fe oxide or OC binding sites. Suspended Fe oxide-organic matter coprecipitates were assessed using AF4 coupled to online TOC analysis and ICP-MS. In laboratory prepared samples, Cu was observed in a mixture of small 1-5 nm colloids of Fe oxide-organic matter precipitates, but the majority was observed in larger organic matter colloids and were not UV absorbing, suggesting more aliphatic carbon materials. In field samples, up to 60% of the dissolved Cu

  16. Watershed dissolved organic carbon export patterns exhibit significant transport-limitations

    NASA Astrophysics Data System (ADS)

    Zarnetske, J. P.; Bouda, M.; Saiers, J. E.; Raymond, P. A.

    2013-12-01

    Dissolved organic carbon (DOC) is a master variable in aquatic ecosystems and drinking water quality. However, it is difficult to reveal how DOC travels from terrestrial environments to streams and is eventually exported from watersheds. Fundamentally, we need to reveal when and where DOC export is controlled by the sources of watershed DOC or the ability to hydrologically transport it. Therefore, we evaluate the importance of DOC source versus hydrologic transport limitations on watershed DOC export patterns across the United States. To do this, we analyzed empirical DOC flux (F_DOC) patterns across many watersheds (n= 655), which span a wide range of watershed sizes, flow regimes, climates, and biomes. They also represent 66% of the areal extent of the conterminous United States. We fit a power law model of F_DOC for each watershed, where F_DOC=aQ^b. This power-law model had a robust goodness of fit for the watersheds in this data set (mean NSE=0.88). We used the calibrated b value for each watershed to characterize DOC export as either transport-limited (b>1; concurrent increase in DOC concentration with flow), chemostatic (b=1; constant DOC concentration with increasing flow), or source-limited (b<1; decreasing DOC concentration with increasing flow). This synthesis of watersheds demonstrates that DOC export is limited by transport processes in a large majority (69%) of the watersheds in the data set. Further, we used an ensemble method to fit statistical models (i.e., boosted regression trees) that predict the transport- vs source-limitation behavior of watersheds. The observed limitation behavior is largely associated with two land cover variables (evergreen forest and developed land extent) and climatic variables (annual precipitation and temperature seasonality). This synthesis indicates that the coupling of terrestrial and aquatic systems in terms of DOC is predominantly controlled by hydrologic transport processes. Overall, these DOC export findings

  17. Transport and Transformation of Dissolved Organic Matter in Soil Interstitial Water Across Forested, Montane Hillslopes

    NASA Astrophysics Data System (ADS)

    Burns, M. A.; McKnight, D. M.; Gabor, R. S.; Brooks, P. D.; Barnard, H. R.

    2013-12-01

    Dissolved organic matter (DOM) is a ubiquitous mixture of compounds formed from the degradation of both terrestrial and microbial material. The abundance and composition of the DOM present in stream water is important to stream processes such as UV light attenuation, nutrient supply and metal sorption. However, an excess of DOM can cause reactions with chlorination compounds at drinking water treatment plants, creating potentially harmful disinfection byproducts. Currently, little is known regarding the influence of soil interstitial water on stream DOM composition. In this study, we explore the role of interstitial water on DOM transport and transformation from the hillslope to the stream in a montane catchment within the Boulder Creek Critical Zone Observatory in Colorado. We installed a suite of tension lysimeters located within the rooting zone across representative north- and south-facing slopes. Interstitial water and stream samples were collected daily for approximately seven weeks during the 2013 spring snow melt period and analyzed for DOM composition using fluorescence spectroscopy. To date, we have used fluorescence index (FI) to evaluate differences between microbial and terrestrial DOM inputs and humification index (HIX) to assess degree of humification undergone by the DOM. Preliminary results indicate that FI was significantly correlated with hillslope aspect (p<.01), with higher FI on north-facing slopes, suggesting more microbial precursor material. Stream samples reveal greater humification throughout the snowmelt period (p<.01). This increase could suggest a transition from deeper groundwater sources to shallow soil interstitial water inputs into the stream during snowmelt. These preliminary results suggest that changes in DOM composition through the catchment during snowmelt can be linked to hydrologic transport. Further site specific model development will reveal explicit changes in the DOM chemistry and will increase our understanding of

  18. Influence of light, temperature and salinity on dissolved organic carbon exudation rates in Zostera marina L.

    PubMed Central

    2012-01-01

    Background Marine angiosperms, seagrasses, are sentinel species of marine ecosystem health and function. Seagrass carbon budgets provide insight on the minimum requirements needed to maintain this valuable resource. Carbon budgets are a balance between C fixation, growth, storage and loss rates, most of which are well characterized. However, relatively few measurements of dissolved organic carbon (DOC) leaf exudation or rhizodeposition rates exist for most seagrass species. Here I evaluate how eelgrass (Zostera marina L.) DOC exudation is affected by a single factor manipulation (light, temperature or salinity). Eelgrass plants were hydroponically exposed to treatments in experimental chambers (separate leaf and rhizome/root compartments) with artificial seawater medium. Regression analysis of changes in the DOC concentration through time was used to calculate DOC exudation rates. Results Exudation rates were similar across all treatments in all experiments. For all experiments, pooled leaf DOC exudation ranged between 0.032 and 0.069 mg C gdw-1 h-1, while rhizodeposition ranged between 0.024 and 0.045 mg C gdw-1 h-1. These rates are consistent with previously published values and provide first-order estimates for mechanistic models. Conclusions Zostera marina carbon losses from either leaf exudation or rhizodeposition account for a small proportion of gross primary production (1.2-4.6%) and appear to be insensitive to short-term (e.g., hours to days) environmental variations in chamber experiments. Based on these preliminary experiments, I suggest that Z. marina DOC exudation may be a passive process and not an active transport process. PMID:22938529

  19. Dissolved organic carbon export and internal cycling in small, headwater lakes

    USGS Publications Warehouse

    Stets, Edward G.; Striegl, Robert G.; Aiken, George R.

    2010-01-01

    Carbon (C) cycling in freshwater lakes is intense but poorly integrated into our current understanding of overall C transport from the land to the oceans. We quantified dissolved organic carbon export (DOCX) and compared it with modeled gross DOC mineralization (DOCR) to determine whether hydrologic or within-lake processes dominated DOC cycling in a small headwaters watershed in Minnesota, USA. We also used DOC optical properties to gather information about DOC sources. We then compared our results to a data set of approximately 1500 lakes in the Eastern USA (Eastern Lake Survey, ELS, data set) to place our results in context of lakes more broadly. In the open-basin lakes in our watershed (n = 5), DOCX ranged from 60 to 183 g C m−2 lake area yr−1, whereas DOCR ranged from 15 to 21 g C m−2 lake area yr−1, emphasizing that lateral DOC fluxes dominated. DOCX calculated in our study watershed clustered near the 75th percentile of open-basin lakes in the ELS data set, suggesting that these results were not unusual. In contrast, DOCX in closed-basin lakes (n = 2) was approximately 5 g C m−2 lake area yr−1, whereas DOCR was 37 to 42 g C m−2 lake area yr−1, suggesting that internal C cycling dominated. In the ELS data set, median DOCX was 32 and 12 g C m−2 yr−1 in open-basin and closed-basin lakes, respectively. Although not as high as what was observed in our study watershed, DOCX is an important component of lake C flux more generally, particularly in open-basin lakes.

  20. Effects of charging on the chromophores of dissolved organic matter from the Rio Negro basin.

    PubMed

    Yan, Mingquan; Korshin, Gregory V; Claret, Francis; Croué, Jean-Philippe; Fabbricino, Massimiliano; Gallard, Hervé; Schäfer, Thorsten; Benedetti, Marc F

    2014-08-01

    This study demonstrates that the deprotonation of dissolved organic matter (DOM) originating from a small creek characteristic for DOM-rich waters located in the Rio Negro basin can be quantified based on measurements of pH effects on its absorbance spectra. The method was ascertained by the data of Near-Edge X-Ray Absorbance Spectroscopy (NEXAFS), potentiometric titration to quantify the structural and compositional differences between the colloidal and hydrophobic fractions that contribute 91% of black-water creek DOM. Changes in the absorbance spectra of the DOM fractions caused by deprotonation quantified via numeric deconvolution which indicated the presence of six well-resolved Gaussian bands in the differential spectra. The emergence of these bands was determined to be associated with the engagement of carboxylic and phenolic functionalities and changes of inter-chromophore interactions in DOM molecules. Interpretation of the data based on the NICA-Donnan approach showed that behavior of DOM chromophores was consistent with results of potentiometric titrations. Similar trends were observed for changes of the spectral slope of the DOM absorbance spectra in the range of wavelengths 325-375 nm (DSlope325-375). The behavior of DSlope325-375 values was modeled based on the NICA-Donnan approach and correlated with potentiometrically-estimated charges attributed to the carboxylic and phenolic groups. The correlations between DSlope325-375 and charges of low- and high-affinity protonation-active groups in DOM were monotonic but not linear and had important differences between the colloidal and hydrophobic fractions.

  1. Dissolved organic carbon reduces uranium toxicity to the unicellular eukaryote Euglena gracilis.

    PubMed

    Trenfield, Melanie A; Ng, Jack C; Noller, Barry; Markich, Scott J; van Dam, Rick A

    2012-05-01

    The influence of dissolved organic carbon (DOC), in the form of Suwannee River fulvic acid (SRFA), on uranium (U) toxicity to the unicellular eukaryote, Euglena gracilis (Z strain), was investigated at pH 6. In a background medium without SRFA, exposure of E. gracilis to 57 μg L(-1) U resulted in a 50% reduction in growth (IC(50)). The addition of 20 mg L(-1) DOC (as SRFA), reduced U toxicity 4 to 5-fold (IC(50) increased to 254 μg L(-1) U). This reduction in toxicity was also evident at more sensitive effect levels with a 10% reduction in growth (IC(10)) occurring at 5 μg L(-1) U in the background medium and at 17 μg L(-1) U in the SRFA medium, respectively. This amelioration of toxicity with the addition of SRFA was linked to a decrease in the bioavailability of U, with geochemical speciation modelling predicting 84% of U would be complexed by SRFA. The decrease in bioavailability of U in the presence of SRFA was also evident from the 11-14 fold reduction in the cellular concentration of U compared to that of E. gracilis in the background medium. Stepwise multiple linear regression analyses indicated that UO(2)(2+) alone explained 51% of the variation in measured U toxicity to E. gracilis. Preliminary U exposures to E. gracilis in the presence of a reactive oxygen species probe, suggest exposure to ≥60 μg L(-1) U may induce oxidative stress, but this endpoint was not considered to be a sensitive biological indicator.

  2. [Factors affecting formation of THMs during dissolved organic nitrogen acetamide chlorination in drinking water].

    PubMed

    Chu, Wen-Hai; Gao, Nai-Yun; Zhao, Shi-Jia; Li, Qing-Song

    2009-05-15

    Chlorination disinfection greatly reduced bacteria and virus in drinking water. However, there is an unintended consequence of disinfection, the generation of chemical disinfection by-products (DBPs). Dissolved organic nitrogen (DON) as the important precursor of DBPs is of current concern. As acetamide (AcAm) occur in important bimolecular, we studied formation pathways for THMs during chlorination of model AcAm. The experiments are designed by Plackett-Burman and Box-Behnken methods. Factors affecting formation of THMs such as AcAm initial concentration, chlorine dosage, pH, temperature, Br(-) concentration and contact time were investigated. The results indicate that AcAm initial concentration, pH and temperature have little effects on formation of THMs. On the contrary, three other factors have important effects on formation of THMs, especially Br(-) concentration. The capacity of THMs generation varies very little when Br(-) has a constant concentration. Generation amount of THMs attach maximum under the condition that dosage of active chlorine, Br(-) concentration and contact time is 8.77 mg/L, 0.77 mg/L and 6.20 h respectively. Bromine ion plays a catalysis role on THMs formation. Controlling the concentration of bromine ion can reduce total generation amount of THMs via AcAm. Bromine partition coefficient tends to increasing along with contact time lapse. Controlling chlorination reaction time can lower the cancer risk. At last, the pathway is proposed for THMs formation via AcAm, and the catalysis mechanism of Br(-) was addressed.

  3. Characteristics of dissolved organic matter formed in aerobic and anaerobic digestion of excess activated sludge.

    PubMed

    Du, Haixia; Li, Fusheng

    2017-02-01

    The characteristics of dissolved organic matter (DOM) formed in aerobic and anaerobic digestion of excess activated sludge (EAS) was investigated for three total solid (TS) concentrations (1.2, 2.3 and 5.2%) and three temperatures (5, 20 and 35 °C). The results on the overall concentration of DOM evaluated by TOC showed significantly higher values in anaerobic than aerobic digestion (2.8-6.9 times for TS 1.2-5.2% at 20 °C). Data analysis with a first-order sequential reaction model revealed that higher occurrence of DOM in anaerobic digestion was a result of comparatively faster hydrolysis (1.3-5.5 times for TS 1.2-5.2% at 20 °C; 1.4-49.3 times for temperatures 5-35 °C with TS 1.2%) and slower degradation (0.3-1.0 times for TS 1.2-5.2% at 20 °C; 0.5-8.3 times for temperatures 5-35 °C with TS 1.2%). In aerobic digestion, more humic substances were formed; while, in anaerobic digestion, proteins and aromatic amino acids were the major constituents. For both digestions, except for a few exceptions, proteins and humic substances increased as the TS concentration increased; and increasing the temperature led to a decrease in the content of proteins formed in both aerobic and anaerobic digestion, and an increase in the content of humic substances in the aerobic digestion. The UV-absorbing DOM constituents were highly heterogeneous, and were comparatively larger in anaerobic digestion; and did not change significantly with the TS concentrations and temperatures.

  4. Dissolved Organic Matter Composition and Microbial Diversity In The Lake Tahoe Basin, Sierra Nevada, California.

    NASA Astrophysics Data System (ADS)

    Aluwihare, L.; Goldberg, S. J.; Ball, G. I.; Mendoza, W. G.; Simpson, A.; Kharbush, J.; Nelson, C. E.

    2014-12-01

    Dissolved organic matter (DOM) inputs into high elevation lakes of the Sierra Nevada, California are seasonally segregated, and this enables an examination of the dominant compositional features and microbial responses associated with allochthonous versus autochthonous DOM inputs. Furthermore, because lakes within this watershed have very different hydraulic residence times, extending from days (e.g., Upper Angora Lake) to centuries (Lake Tahoe), the Tahoe Basin represents an ideal experimental system in which to characterize long-lived DOM. We used a variety of analytical tools, including elemental, stable isotope and radiocarbon measurements, nuclear magnetic resonance (NMR) spectroscopy, comprehensive 2D gas chromatography coupled to time of flight (TOF) mass spectrometry and fluorescence measurements, to characterize solid phase extracted (SPE) DOM, and in some cases, whole DOM. Our data show that DOM with typical terrestrial characteristics is quickly removed in lakes with >annual water residence time, leaving behind SPE DOM that is extremely N-rich, with a functional group distribution that is consistent with protein. Furthermore, our radiocarbon measurements estimate a 100-200 year residence time for the N-rich DOM accumulating in Lake Tahoe. All of the analytical techniques distinguish samples based on lake water residence time, which indicates that the lacustrine reactor plays an important role in determining the composition of DOM that accumulates on long timescales. We also examined temporal variations in the microbial community of Lake Tahoe to identify taxa that may be involved in processing DOM from distinct sources. Our results confirm the importance of DOM as a currency for carbon and nitrogen exchange between different compartments of the terrestrial ecosystem and argue for its inclusion in models that examine the response of lake ecosystems to global change.

  5. Spatial and temporal patterns of dissolved organic matter optical properties across large rivers in Africa

    NASA Astrophysics Data System (ADS)

    Lambert, Thibault; Darchambeau, François; Vieira Borges, Alberto; Alhou, Bassirou; Mbega, Jean-Daniel; Teodoru, Cristian; Marwick, Trent Richard; Bouillon, Steven

    2014-05-01

    Tropical rivers have disproportionally high carbon transport and outgassing compared to temperate and Arctic rivers. Yet the cycling of dissolved organic matter (DOM) within these systems is still poorly studied with the exception of the Amazon basin. The chromophoric or colored dissolved organic matter (CDOM) is the fraction of DOM that absorbs ultraviolet and visible light. As the biochemical nature of DOM (and CDOM) defines its optical properties, optical measurements are particularly useful to assess the composition of DOM in freshwater and hence can be applied as proxies for assessments of DOM sources and its biogeochemical role. However, less is known on how specific optical characteristics can be applied as proxies and how these proxies vary from one system to another. In this study we compared concentrations and stable isotopic signature of dissolved organic carbon with optical properties of DOM from diverse tropical river systems across the African continent including the Congo basin, the Zambezi basin, the Ogooué basin and the Niger basin. These major rivers of the African continent were monitored for long period (from 1-3 years) at biweekly frequency. This large dataset allowed us to compare the spatial and temporal patterns of DOM quality along various environmental gradients, including hydrology, river size, terrestrial vegetation and connectivity to terrestrial inputs. The optical proxies presented and discussed in this study include absorption coefficients a(Λ) at different wavelength (254, 300, 350 and 440 nm), spectral slopes (S275-295and S350-400), the spectral slope ratio (SR=S275-295:S350-400) and the a(250):a(365) ratio.

  6. State factor relationships of dissolved organic carbon and nitrogen losses from unpolluted temperate forest watersheds

    USGS Publications Warehouse

    Perakis, S.S.; Hedin, L.O.

    2007-01-01

    We sampled 100 unpolluted, old-growth forested watersheds, divided among 13 separate study areas over 5 years in temperate southern Chile and Argentina, to evaluate relationships among dominant soil-forming state factors and dissolved carbon and nitrogen concentrations in watershed streams. These watersheds provide a unique opportunity to examine broad-scale controls over carbon (C) and nitrogen (N) biogeochemistry in the absence of significant human disturbance from chronic N deposition and land use change. Variations in the ratio dissolved organic carbon (DOC) to nitrogen (DON) in watershed streams differed by underlying soil parent material, with average C:N = 29 for watersheds underlain by volcanic ash and basalt versus C:N = 73 for sedimentary and metamorphic parent materials, consistent with stronger adsorption of low C:N hydrophobic materials by amorphous clays commonly associated with volcanic ash and basalt weathering. Mean annual precipitation was related positively to variations in both DOC (range: 0.2-9.7 mg C/L) and DON (range: 0.008-0.135 mg N/L) across study areas, suggesting that variations in water volume and concentration may act synergistically to influence C and N losses across dry to wet gradients in these forest ecosystems. Dominance of vegetation by broadleaf versus coniferous trees had negligible effects on organic C and N concentrations in comparison to abiotic factors. We conclude that precipitation volume and soil parent material are important controls over chemical losses of dissolved organic C and N from unpolluted temperate forest watersheds. Our results raise the possibility that biotic imprints on watershed C and N losses may be less pronounced in naturally N-poor forests than in areas impacted by land use change and chronic N deposition. Copyright 2007 by the American Geophysical Union.

  7. Effects of Coral Reef Benthic Primary Producers on Dissolved Organic Carbon and Microbial Activity

    PubMed Central

    Haas, Andreas F.; Nelson, Craig E.; Wegley Kelly, Linda; Carlson, Craig A.; Rohwer, Forest; Leichter, James J.; Wyatt, Alex; Smith, Jennifer E.

    2011-01-01

    Benthic primary producers in marine ecosystems may significantly alter biogeochemical cycling and microbial processes in their surrounding environment. To examine these interactions, we studied dissolved organic matter release by dominant benthic taxa and subsequent microbial remineralization in the lagoonal reefs of Moorea, French Polynesia. Rates of photosynthesis, respiration, and dissolved organic carbon (DOC) release were assessed for several common benthic reef organisms from the backreef habitat. We assessed microbial community response to dissolved exudates of each benthic producer by measuring bacterioplankton growth, respiration, and DOC drawdown in two-day dark dilution culture incubations. Experiments were conducted for six benthic producers: three species of macroalgae (each representing a different algal phylum: Turbinaria ornata – Ochrophyta; Amansia rhodantha – Rhodophyta; Halimeda opuntia – Chlorophyta), a mixed assemblage of turf algae, a species of crustose coralline algae (Hydrolithon reinboldii) and a dominant hermatypic coral (Porites lobata). Our results show that all five types of algae, but not the coral, exuded significant amounts of labile DOC into their surrounding environment. In general, primary producers with the highest rates of photosynthesis released the most DOC and yielded the greatest bacterioplankton growth; turf algae produced nearly twice as much DOC per unit surface area than the other benthic producers (14.0±2.8 µmol h−1 dm−2), stimulating rapid bacterioplankton growth (0.044±0.002 log10 cells h−1) and concomitant oxygen drawdown (0.16±0.05 µmol L−1 h−1 dm−2). Our results demonstrate that benthic reef algae can release a significant fraction of their photosynthetically-fixed carbon as DOC, these release rates vary by species, and this DOC is available to and consumed by reef associated microbes. These data provide compelling evidence that benthic primary producers differentially influence reef

  8. [Dynamics of soil microbial biomass and dissolved organic carbon and nitrogen under flooded condition].

    PubMed

    Qiu, Shaojun; Peng, Peiqin; Rong, Xiangmin; Liu, Qiang; Tang, Qi

    2006-11-01

    With reddish yellow soil (RYS) and alluvial purple soil (APS), the two typical paddy soils in the Dongting Lake floodplain of China as test soils, an incubation test was conducted at 25 degrees C to study the dynamic changes of soil microbial biomass and dissolved organic carbon and nitrogen under flooded condition. Three treatments were installed, i.e., control (CK), ammonium sulfate (N), and rice straw powder plus ammonium sulfate (S-N). The results showed that during incubation, soil microbial biomass carbon (SMBC), soil microbial biomass nitrogen (SMBN), soil dissolved organic carbon (SDOC), and soil dissolved organic nitrogen (SDON) reached their maximum initially, decreased thereafter, and tended to be stable. After amending the substrates to the two soils, the averages of SMBC to soil total carbon, SMBN to soil total nitrogen, SDOC to soil total carbon, and SDON to soil total nitrogen were 2% - 3%, 2% - 3%, 1% or so, and 5% - 6%, respectively. In the two soils, the peak values of SMBC in treatment N and those of SMBN, SDOC and SDON in treatment S-N were the highest, while those of SMBC in treatments N and S-N had no significant difference. The peak values of SMBN, SDOC and SDON in RYS were significantly different between treatments N and S-N, while no significant difference was observed between the peak values of SMBN and SDOC in APS, because the fertility of RYS was lower than that of APS. In the first 7 days of incubation, SMBC/SMBN ratio was < 10, while after 14 days of incubation, this ratio was higher in treatment N than in treatment S-N at the same time in the same soil. The SDOC/SDON ratio in all treatments was the highest at the 3rd d, and the lowest at the 28th d of incubation.

  9. Effects of coral reef benthic primary producers on dissolved organic carbon and microbial activity.

    PubMed

    Haas, Andreas F; Nelson, Craig E; Wegley Kelly, Linda; Carlson, Craig A; Rohwer, Forest; Leichter, James J; Wyatt, Alex; Smith, Jennifer E

    2011-01-01

    Benthic primary producers in marine ecosystems may significantly alter biogeochemical cycling and microbial processes in their surrounding environment. To examine these interactions, we studied dissolved organic matter release by dominant benthic taxa and subsequent microbial remineralization in the lagoonal reefs of Moorea, French Polynesia. Rates of photosynthesis, respiration, and dissolved organic carbon (DOC) release were assessed for several common benthic reef organisms from the backreef habitat. We assessed microbial community response to dissolved exudates of each benthic producer by measuring bacterioplankton growth, respiration, and DOC drawdown in two-day dark dilution culture incubations. Experiments were conducted for six benthic producers: three species of macroalgae (each representing a different algal phylum: Turbinaria ornata--Ochrophyta; Amansia rhodantha--Rhodophyta; Halimeda opuntia--Chlorophyta), a mixed assemblage of turf algae, a species of crustose coralline algae (Hydrolithon reinboldii) and a dominant hermatypic coral (Porites lobata). Our results show that all five types of algae, but not the coral, exuded significant amounts of labile DOC into their surrounding environment. In general, primary producers with the highest rates of photosynthesis released the most DOC and yielded the greatest bacterioplankton growth; turf algae produced nearly twice as much DOC per unit surface area than the other benthic producers (14.0±2.8 µmol h⁻¹ dm⁻²), stimulating rapid bacterioplankton growth (0.044±0.002 log10 cells h⁻¹) and concomitant oxygen drawdown (0.16±0.05 µmol L⁻¹ h⁻¹ dm⁻²). Our results demonstrate that benthic reef algae can release a significant fraction of their photosynthetically-fixed carbon as DOC, these release rates vary by species, and this DOC is available to and consumed by reef associated microbes. These data provide compelling evidence that benthic primary producers differentially influence reef microbial

  10. Constraining The Radiocarbon Distribution Within Major Components of Marine Dissolved Organic Carbon

    NASA Astrophysics Data System (ADS)

    Zigah, P.; Repeta, D.; McNichol, A. P.; Beaupre, S. R.; Xu, L.; Aluwihare, L.; Hemingway, J. D.

    2015-12-01

    Dissolved organic carbon (DOC) is one of the largest active carbon pools on Earth with a carbon inventory similar to that of the atmosphere. The sources and cycling of DOC in the ocean is not well-constrained. However, knowledge of the cycling and annual flux of carbon through DOC is critical to understanding the global carbon cycle and feedback mechanisms in the global climate system. Natural-abundance radiocarbon and stable carbon isotopic values can be used to infer the sources and cycling of DOC in the oceans. Past measurements for the most part have been made on bulk DOC, which represents an average of all DOC components. There is, however, good evidence that the actual range of values within the average is quite large, and recent serial oxidation measurements of the surface and deep ocean total DOC [1, 2, 3] reveal isotopic heterogeneity in the DOC pool with a radiocarbon-enriched modern component and a radiocarbon-depleted older component co-cycling in the surface ocean. Also, modeled data from the serial oxidation of the total DOC suggest the presence of a significant amount of modern DOC in the deep ocean [3]. In this study, we used a detailed size and chemical fractionation approach to examine the isotopic distribution within different size and molecular constituents of DOC. We also used a novel thermal serial oxidation approach to link the isotopic diversity of DOC to its concurrent major structural composition in order to build upon and refine the insights from the total DOC isotopic work. Our data show that, in the deep ocean, a major component of the heteropolysaccharide (HPS)-rich DOC isolated by ultrafiltration has radiocarbon value similar to co-occurring DIC indicating either a chemosynthetic source or conservative transport. In contrast, the fraction of DOC rich in the carboxylic -rich compounds isolated by solid phase extraction was much older than the DIC and also exhibit remarkable isotopic diversity in its constituent organic compounds. Our

  11. Development of gas chromatographic system for dissolved organic carbon analysis in seawater

    SciTech Connect

    Chipman, D.W.; Takahashi, T.

    1992-12-01

    During the first six months of this two-year grant, we have completed the construction of the analytical portion of a prototype gas chromatograph-based system for the analysis of dissolved organic carbon in seawater. We also have begun testing the procedures to be used to cryogenically concentrate and transfer carbon dioxide from the oxidizing atmosphere of the high-temperature furnace into the reducing hydrogen carrier gas of the gas chromatograph. During the second half of the first year, we will construct the high-temperature catalytic oxidation furnace and test the entire system on laboratory-prepared aqueous solutions of various organic compounds. Also during this period, we will take part in an initial scoping study within the Cape Hatteras field area on board the R/V Gyre. This study will involve both the collection of samples of seawater for organic and inorganic carbon analysis and the measurement of surface-water pCO[sub 2].

  12. Development of gas chromatographic system for dissolved organic carbon analysis in seawater. Annual progress report

    SciTech Connect

    Chipman, D.W.; Takahashi, T.

    1992-12-01

    During the first six months of this two-year grant, we have completed the construction of the analytical portion of a prototype gas chromatograph-based system for the analysis of dissolved organic carbon in seawater. We also have begun testing the procedures to be used to cryogenically concentrate and transfer carbon dioxide from the oxidizing atmosphere of the high-temperature furnace into the reducing hydrogen carrier gas of the gas chromatograph. During the second half of the first year, we will construct the high-temperature catalytic oxidation furnace and test the entire system on laboratory-prepared aqueous solutions of various organic compounds. Also during this period, we will take part in an initial scoping study within the Cape Hatteras field area on board the R/V Gyre. This study will involve both the collection of samples of seawater for organic and inorganic carbon analysis and the measurement of surface-water pCO{sub 2}.

  13. Comparison of treatment options for removal of recalcitrant dissolved organic matter from paper mill effluent.

    PubMed

    Ciputra, Sandra; Antony, Alice; Phillips, Ross; Richardson, Des; Leslie, Greg

    2010-09-01

    Recycling paper mill effluent by conventional water treatment is difficult due to the persistence of salt and recalcitrant organics. Elimination of dissolved organic matter (DOM) from paper mill effluent was studied using three treatment options, ion exchange resin (IER), granular activated carbon (GAC) and nanofiltration (NF). The removal efficiency was analysed based on hydrophobicity, molecular weight and fluorogenic origin of the DOM fractions. For IER, GAC and NF treatments, overall removal of dissolved organic carbon was 72%, 76% and 91%, respectively. Based on the hydrophobicity, all the three treatment methods majorly removed hydrophobic acid fractions (HPhoA). Further, IER acted on all fractions, 57% of HPhoA, 44% of transphilic acid and 18% of hydrophilics, substantiating that the removal is by both ion exchange and adsorption. Based on the molecular weight, IER and GAC treatments acted majorly on the high molecular weight fractions, whereas NF eliminated all molecular weight fractions. After GAC adsorption, some amount of humic hydrolysates and low molecular weight neutrals persisted in the effluent. After IER treatment, amount of low molecular weight compounds increased due to resin leaching. Qualitative analysis of fluorescence excitation emission matrices showed that the fulvic acid-like fluorophores were more recalcitrant among the various DOM fractions, considerable amount persisted after all the three treatment methods. Three treatment methods considerably differed in terms of removing different DOM fractions; however, a broad-spectrum process like NF would be needed to achieve the maximum elimination.

  14. Water extraction kinetics of metals, arsenic and dissolved organic carbon from industrial contaminated poplar leaves.

    PubMed

    Shahid, Muhammad; Xiong, Tiantian; Castrec-Rouelle, Maryse; Leveque, Tibo; Dumat, Camille

    2013-12-01

    In industrial areas, tree leaves contaminated by metals and metalloids could constitute a secondary source of pollutants. In the present study, water extraction kinetics of inorganic elements (IE: Pb, Zn, Cd, As, Fe and Mn), dissolved organic carbon, pH and biological activity were studied for industrial contaminated poplar leaves. Moreover, the distribution of the IE through the size fractions of the associated top soil was measured. High quantities of Mn, Zn and As and polysaccharides were released in the solution from the strongly contaminated leaves. The kinetic of release varied with time and metal type. The solution pH decreased while dissolved organic contents increased with time after 30 days. Therefore, these contaminated leaves could constitute a source of more available organic metals and metalloids than the initial inorganic process particles. However, the distribution of the IE through the size fractions of the top soil suggested that a great part of the released IE was adsorbed, reducing in consequence their transfers and bioavailability. It's concluded that mobility/bioavailability and speciation of metals and metalloids released from the decomposition of polluted tree leaves depends on soil characteristics, pollutant type and litter composition, with consequences for environmental risk assessment.

  15. Black Carbon in Estuarine (Coastal) High-molecular-weight Dissolved Organic Matter

    NASA Technical Reports Server (NTRS)

    Mannino, Antonio; Harvey, H. Rodger

    2003-01-01

    Dissolved organic matter (DOM) in the ocean constitutes one of the largest pools of organic carbon in the biosphere, yet much of its composition is uncharacterized. Observations of black carbon (BC) particles (by-products of fossil fuel combustion and biomass burning) in the atmosphere, ice, rivers, soils and marine sediments suggest that this material is ubiquitous, yet the contribution of BC to the ocean s DOM pool remains unknown. Analysis of high-molecular-weight DOM isolated from surface waters of two estuaries in the northwest Atlantic Ocean finds that BC is a significant component of DOM, suggesting that river-estuary systems are important exporters of BC to the ocean through DOM. We show that BC comprises 4-7% of the dissolved organic carbon (DOC) at coastal ocean sites, which supports the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition. Flux calculations suggest that BC could be as important as vascular plant-derived lignin in terms of carbon inputs to the ocean. Production of BC sequesters fossil fuel- and biomass-derived carbon into a refractory carbon pool. Hence, BC may represent a significant sink for carbon to the ocean.

  16. Uptake of uranium(VI) by pyrite under boom clay conditions: influence of dissolved organic carbon.

    PubMed

    Bruggeman, C; Maes, N

    2010-06-01

    The uptake of uranium(VI) by natural pyrite, FeS(2), was studied under conditions relevant for geological disposal of radioactive waste (anoxic atmosphere, approximately 0.014 mol.L(-1) NaHCO(3) electrolyte) with special emphasis on the role of dissolved organic matter. Solution analysis of batch experiments with different initial concentrations of uranium(VI) (10(-8)-10(-4) mol.L(-1)) was combined with X-ray absorption spectroscopy on the solid phase to elucidate the speciation of uranium in these systems and to gain insight into the major reaction mechanisms between uranium and pyrite. The results showed that, under the conditions of the experiments, uranium(VI) was at least partly reduced to a UO(2)(s)-like precipitate, although the predominant valence state of uranium in solution was likely uranium(VI). All observations indicate that the uranium solid-liquid distribution is governed by both reduction and adsorption processes. No significant amounts of uranium colloids (either intrinsic UO(2) colloids or complexes with natural organic matter) were found in any of the samples. The presence of dissolved organic matter did, however, increase the final uranium solution concentration and decrease the fraction of uranium(IV) found in the solid phase.

  17. Compost impacts on dissolved organic carbon and available nitrogen and phosphorus in turfgrass soil.

    PubMed

    Wright, Alan L; Provin, Tony L; Hons, Frank M; Zuberer, David A; White, Richard H

    2008-01-01

    Compost application to turfgrass soils may increase dissolved organic C (DOC) levels which affects nutrient dynamics in soil. The objectives of this study were to investigate the influence of compost source and application rate on soil organic C (SOC), DOC, NO(3), and available P during 29 months after a one-time application to St. Augustinegrass [Stenotaphrum secundatum (Walt.) Kuntze] turf. Compost sources had variable composition, yet resulted in few differences in SOC, DOC, and NO(3) after applied to soil. Available NO(3) rapidly decreased after compost application and was unaffected by compost source and application rate. Available P increased after compost application and exhibited cyclical seasonal patterns related to DOC. Compost application decreased soil pH relative to unamended soil, but pH increased during the course of the study due to irrigation with sodic water. Increasing the compost application rate increased SOC by 3 months, and levels remained fairly stable to 29 months. In contrast, DOC continued to increase from 3 to 29 months after application, suggesting that compost mineralization and growth of St. Augustinegrass contributed to seasonal dynamics. Dissolved organic C was 75%, 78%, and 101% greater 29 months after application of 0, 80, and 160 Mg compostha(-1), respectively, than before application. Impacts of composts on soil properties indicated that most significant effects occurred within a few months of application. Seasonal variability of SOC, DOC, and available P was likely related to St. Augustinegrass growth stages as well as precipitation, as declines occurred after precipitation events.

  18. Dissolved organic matter quality and bioavailability changes across an urbanization gradient in headwater streams.

    PubMed

    Hosen, Jacob D; McDonough, Owen T; Febria, Catherine M; Palmer, Margaret A

    2014-07-15

    Landscape urbanization broadly alters watersheds and stream ecosystems, yet the impact of nonpoint source urban inputs on the quantity, quality, and ultimate fate of dissolved organic matter (DOM) is poorly understood. We assessed DOM quality and microbial bioavailability in eight first-order Coastal Plain headwater streams along a gradient of urbanization (i.e., percent watershed impervious cover); none of the streams had point source discharges. DOM quality was measured using fluorescence excitation-emission matrices (EEMs) coupled with parallel factor analysis (PARAFAC). Bioavailability was assessed using biodegradable dissolved organic carbon (BDOC) incubations. Results showed that watershed impervious cover was significantly related to stream DOM composition: increasing impervious cover was associated with decreased amounts of natural humic-like DOM and enriched amounts of anthropogenic fulvic acid-like and protein-like DOM. Microbial bioavailability of DOM was greater in urbanized streams during spring and summer, and was related to decreasing proportions of humic-like DOM and increasing proportions of protein-like DOM. Increased bioavailability was associated with elevated extracellular enzyme activity of the initial microbial community supplied to samples during BDOC incubations. These findings indicate that changes in stream DOM quality due to watershed urbanization may impact stream ecosystem metabolism and ultimately the fate of organic carbon transported through fluvial systems.

  19. Associations of free-living bacteria and dissolved organic compounds in a plume of contaminated groundwater

    USGS Publications Warehouse

    Harvey, R.W.; Barber, L.B.; ,

    1992-01-01

    Associations of free-living bacteria (FLB) and dissolved organic contaminants in a 4-km-long plume of sewage-contaminated groundwater were investigated. Abundance of FLB in the core of the plume (as delineated by maximum specific conductance) steadily decreased in the direction of flow from a point 0.25 km downgradient from the source to the toe of the plume. At 0.25 km downgradient, FLB comprised up to 31% of the total bacterial population, but constituted < 7% of the population at 2 km downgradient. Abundance of FLB correlated strongly (r = 0.80 n = 23) with total dissolved organic carbon (DOC) in contaminated groundwater between 0.64 and 2.1 km downgradient, although distributions of individual contaminants such as di-, tri- and tetrachloroethene were highly variable, and their association with FLB less clear. Numbers of FLB in the downgradient portion of the plume which is contaminated with branched-chain alkylbenzenesulfonate (ABS) surfactants were low (< 5??108/L) in spite of relatively high levels of DOC (up to 4 mg/L). However, abundance of FLB correlated strongly with non-surfactant DOC along vertical transects through the plume. The ratio of FLB to DOC and the ratio of FLB to attached bacteria generally decreased in the direction of flow and, consequently, with the age of the organic contaminants.

  20. Differences in dissolved organic matter between reclaimed water source and drinking water source.

    PubMed

    Hu, Hong-Ying; Du, Ye; Wu, Qian-Yuan; Zhao, Xin; Tang, Xin; Chen, Zhuo

    2016-05-01

    Dissolved organic matter (DOM) significantly affects the quality of reclaimed water and drinking water. Reclaimed water potable reuse is an effective way to augment drinking water source and de facto reuse exists worldwide. Hence, when reclaimed water source (namely secondary effluent) is blended with drinking water source, understanding the difference in DOM between drinking water source (dDOM) and reclaimed water source (rDOM) is essential. In this study, composition, transformation, and potential risk of dDOM from drinking water source and rDOM from secondary effluent were compared. Generally, the DOC concentration of rDOM and dissolved organic nitrogen (DON) content in reclaimed water source were higher but rDOM exhibited a lower aromaticity. Besides, rDOM comprises a higher proportion of hydrophilic fractions and more low-molecular weight compounds, which are difficult to be removed during coagulation. Although dDOM exhibited higher specific disinfection byproducts formation potential (SDBPFP), rDOM formed more total disinfection byproducts (DBPs) during chlorination including halomethanes (THMs) and haloacetic acids (HAAs) due to high DOC concentration. Likewise, in consideration of DOC basis, rDOM contained more absolute assimilable organic carbon (AOC) despite showing a lower specific AOC (normalized AOC per unit of DOC). Besides, rDOM exhibited higher biotoxicity including genotoxicity and endocrine disruption. Therefore, rDOM presents a greater potential risk than dDOM does. Reclaimed water source needs to be treated carefully when it is blended with drinking water source.

  1. Relevance of dissolved organic nutrients for the Arctic Ocean nutrient budget

    NASA Astrophysics Data System (ADS)

    Torres-Valdés, Sinhué; Tsubouchi, Takamasa; Davey, Emily; Yashayaev, Igor; Bacon, Sheldon

    2016-06-01

    We ask whether dissolved organic nitrogen (DON) and phosphorus (DOP) could account for previously identified Arctic Ocean (AO) inorganic nutrient budget imbalances. We assess transports to/from the AO by calculating indicative budgets. Marked DON:DOP ratio differences between the Amerasian and Eurasian AO reflect different physical and biogeochemical pathways. DON and DOP are exported to the North Atlantic via Davis Strait potentially being enhanced in transit from Bering Strait. Fram Strait transports are balanced. Barents Sea Opening transports may provide an additional nutrient source to the Barents Sea or may be locked within the wider AO Atlantic Water circulation. Gaps in our knowledge are identified and discussed.

  2. BOREAS TGB-5 Dissolved Organic Carbon Data from NSA Beaver Ponds

    NASA Technical Reports Server (NTRS)

    Bourbonniere, Rick; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

    2000-01-01

    The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB-5) team collected several data sets related to carbon and trace gas fluxes and concentrations in the Northern Study Area (NSA). This data set contains concentrations of dissolved organic and inorganic carbon species from water samples collected at various NSA sites. In particular, this set covers the NSA Tower Beaver Pond Site and the NSA Gillam Road Beaver Pond Site, including data from all visits to open water sampling locations during the BOREAS field campaigns from April to September 1994. The data are provided in tabular ASCII files.

  3. Comparison of absorption properties of colored dissolved organic matter in six different case 2 water bodies

    NASA Astrophysics Data System (ADS)

    Nima, Ciren; Frette, Øyvind; Hamre, Børge; Erga, Svein Rune; Chen, Yi-Chun; Zhao, Lu; Muyimbwa, Dennis; Ssenyonga, Taddeo; Ssebiyonga, Nicolausi; Okullo, Willy; Stamnes, Knut; Stamnes, Jakob J.

    2017-02-01

    Colored Dissolved Organic Matter (CDOM) is one of the main factors controlling the penetration of solar radiation in Case 2 water and affecting satellite-based estimation of ocean color. We present absorption properties of CDOM sampled in 6 water bodies including three in Norway (Røst coastal water, Samnangerfjord, Lysefjord), two in China (Bohai Sea, Lake Namtso), and one in Africa (Lake Victoria). These locations, which range from near the equator to subarctic regions, include water types from oligotrophic to eutrophic, and altitudes from sea level to 4,700 m above sea level.

  4. Characteristics of dissolved organic matter following 20years of peatland restoration.

    PubMed

    Höll, Bettina S; Fiedler, Sabine; Jungkunst, Hermann F; Kalbitz, Karsten; Freibauer, Annette; Drösler, Matthias; Stahr, Karl

    2009-12-15

    The changes in the amounts and composition of dissolved organic matter (DOM) following long-term peat restoration are unknown, although this fraction of soil organic matter affects many processes in such ecosystems. We addressed this lack of knowledge by investigating a peatland in south-west Germany that was partly rewetted 20 years ago. A successfully restored site and a moderately drained site were compared, where the mean groundwater levels were close to the soil surface and around 30 cm below surface, respectively. The concentrations of dissolved organic carbon (DOC) at 4 depths were measured over one year. The specific absorbance was measured at 280 nm and the fluorescence spectra were used to describe the aromaticity and complexity of DOM. The investigations showed that 20 years of peatland restoration was able to create typical peatland conditions. The rewetted site had significantly lower DOC concentrations at different depths compared to the drained site. The specific UV absorbance showed that the rewetted site had a lower level of aromatic DOM structures. The decreasing specific UV absorbance might indicate an increasing contribution of small organic molecules to DOM. It was hypothesized that the decreasing DOC concentrations and the relative enrichment of small, readily degradable organic molecules, reflect the slower decomposition of organic matter after the re-establishment of the water table. Seasonal trends provided substantial evidence for our hypothesis that reduced DOC concentrations were caused by reduced peat decomposition. During summer, the elevated DOC values were accompanied by an increase in DOM aromaticity and complexity. Our results demonstrated a close link between C mineralization and DOC production. We concluded that long-term peatland restoration in the form of the successful re-establishment of the water table might result in reduced peat decomposition and lower DOC concentrations. The restoration of peatlands seems to have a

  5. Dissolved Organic Carbon and Disinfection By-Product Precursor Release from Managed Peat Soils

    USGS Publications Warehouse

    Fleck, J.A.; Bossio, D.A.; Fujii, R.

    2004-01-01

    A wetland restoration demonstration project examined the effects of a permanently flooded wetland on subsidence of peat soils. The project, started in 1997, was done on Twitchell Island, in the Sacramento-San Joaquin Delta of California. Conversion of agricultural land to a wetland has changed many of the biogeochemical processes controlling dissolved organic carbon (DOC) release from the peat soils, relative to the previous land use. Dissolved organic C in delta waters is a concern because it reacts with chlorine, added as a disinfectant in municipal drinking waters, to form carcinogenic disinfection byproducts (DBPs), including trihalomethanes (THMs) and haloacetic acids (HAAs). This study explores the effects of peat soil biogeochemistry on DOC and DBP release under agricultural and wetland management. Results indicate that organic matter source, extent of soil organic matter decomposition, and decomposition pathways all are factors in THM formation. The results show that historical management practices dominate the release of DOC and THM precursors. However, within-site differences indicate that recent management decisions can contribute to changes in DOC quality and THM precursor formation. Not all aromatic forms of carbon are highly reactive and certain environmental conditions produce the specific carbon structures that form THMs. Both HAA and THM precursors are elevated in the DOC released under wetland conditions. The findings of this study emphasize the need to further investigate the roles of organic matter sources, microbial decomposition pathways, and decomposition status of soil organic matter in the release of DOC and DBP precursors from delta soils under varying land-use practices.

  6. Dissolved organic matter influences Fe-binding ligand availability for cyanobacteria in oligotrophic Ontario lakes

    NASA Astrophysics Data System (ADS)

    Sorichetti, Ryan; Creed, Irena; Trick, Charles

    2013-04-01

    Natural iron (Fe) binding ligands, such as dissolved organic matter (DOM) and microbial-produced siderophores, are ubiquitously found in terrestrial and aquatic environments. Siderophores are a group of Fe-binding ligands primarily secreted by bacteria and fungi during Fe-limited conditions as a Fe-scavenging strategy. DOM can have high Fe-binding capacity if it is relatively refractory (i.e., high humic acid concentration with high affinity for metal ions). Cyanobacteria have been shown to utilize Fe bound to hydroxamate and catecholate siderophores when cells are Fe-limited. We assessed if the concentrations of DOM or the presence of siderophores, that increase when concentrations of ferric are low, in the water were correlated with the proportion of cyanobacteria in 25 oligotrophic lakes in Canada. We hypothesized that the highest siderophore concentration will be in lakes with modeled free ferric concentrations < 1x10-19 M; a level where cyanobacteria have shown to be competitive for Fe in laboratory experiments. Proportion of cyanobacteria was measured with flow cytometry and DOM quality was assessed using excitation-emission matrices (EEMs) and PARAFAC modeling. Siderophore concentrations were measured using two traditional chemical analyses (Czaky and Arnow tests). Cyanobacteria appeared to be regulated by the availability of ferric concentrations but the relationship was non-linear. The oligotrophic lakes had ferric concentrations that ranged from 1x10-25 M to 1x10-14 M. The highest % cyanobacteria occurred between ferric concentrations 1x10-23 M to 1x10-19 M. Hydroxamate siderophore concentrations showed the same pattern as % cyanobacteria across the modeled ferric gradient. In contrast, catecholate siderophore concentrations showed no relationship with % cyanobacteria or the modeled ferric gradient. A positive relationship was found between DOM quantity and catecholate siderophore concentration (R² = 0.65, p<0.001). It was also found that as the protein

  7. Dissolved oxygen analysis, TMDL model comparison, and particulate matter shunting—Preliminary results from three model scenarios for the Klamath River upstream of Keno Dam, Oregon

    USGS Publications Warehouse

    Sullivan, Annett B.; Rounds, Stewart A.; Deas, Michael L.; Sogutlugil, I. Ertugrul

    2012-01-01

    standards do not specify whether the numeric criteria are based on depth-averaged dissolved oxygen concentration; this was an interpretation of the standards rule by the Oregon Department of Environmental Quality (ODEQ). In this study, both depth-averaged and volume-averaged dissolved oxygen concentrations were calculated from model output. Results showed that modeled depth-averaged concentrations typically were lower than volume-averaged dissolved oxygen concentrations because depth-averaging gives a higher weight to small volume areas near the channel bottom that often have lower dissolved oxygen concentrations. Results from model scenarios in this study are reported using volume-averaged dissolved oxygen concentrations. * Under all scenarios analyzed, violations of the dissolved oxygen standard occurred most often in summer. Of the three dissolved oxygen criteria that must be met, the 30-day standard was violated most frequently. Under the base case (current conditions), fewer violations occurred in the upstream part of the reach. More violations occurred in the down-stream direction, due in part to oxygen demand from the decay of algae and organic matter from Link River and other inflows. * A condition in which Upper Klamath Lake and its Link River outflow achieved Upper Klamath Lake TMDL water-quality targets was most effective in reducing the number of violations of the dissolved oxygen standard in the Link River to Keno Dam reach of the Klamath River. The condition in which point and nonpoint sources within the Link River to Keno Dam reach met Klamath River TMDL allocations had no effect on dissolved oxygen compliance in some locations and a small effect in others under current conditions. On the other hand, meeting TMDL allocations for nonpoint and point sources was predicted to be important in meeting dissolved oxygen criteria when Upper Klamath Lake and Link River also met Upper Klamath TMDL water-quality targets. * The location of greatest dissolved oxygen

  8. Characterization of dissolved organic matter from surface waters with low to high dissolved organic carbon and the related disinfection byproduct formation potential.

    PubMed

    Li, Angzhen; Zhao, Xu; Mao, Ran; Liu, Huijuan; Qu, Jiuhui

    2014-04-30

    In this study, the disinfection byproduct formation potential (DBPFP) of three surface waters with the dissolved organic carbon (DOC) content of 2.5, 5.2, and 7.9mg/L was investigated. The formation and distribution of trihalomethanes and haloacetic acids were evaluated. Samples collected from three surface waters in China were fractionated based on molecular weight and hydrophobicity. The raw water containing more hydrophobic (Ho) fraction exhibited higher formation potentials of haloacetic acid and trihalomethane. The DBPFP of the surface waters did not correlate with the DOC value. The values of DBPFP per DOC were correlated with the specific ultraviolet absorbance (SUVA) for Ho and Hi fractions. The obtained results suggested that SUVA cannot reveal the ability of reactive sites to form disinfection byproducts for waters with few aromatic structures. Combined with the analysis of FTIR and nuclear magnetic resonance spectra of the raw waters and the corresponding fractions, it was concluded that the Ho fraction with phenolic hydroxyl and conjugated double bonds was responsible for the production of trichloromethanes and trichloroacetic acids. The Hi fraction with amino and carboxyl groups had the potential to form dichloroacetic acids and chlorinated trihalomethanes.

  9. Distribution and biological turnover of dissolved organic compounds in the water column of the Black Sea

    NASA Astrophysics Data System (ADS)

    Mopper, Kenneth; Kieber, David J.

    Water column concentrations and turnover rates were determined for a suite of low molecular weight organic compounds in the Black Sea. The classes of compounds studied included amino acids, simple sugars, α-keto acids, aldehydes, ketones, carboxylic acids, flavins and thiols. Our study yielded some new insights, as well as a few surprising discoveries, regarding the composition and cycling of organic matter in the Black Sea. (1) Uptake rates of organic compounds were from 2 to 4640 times faster in oxic surface waters than in anoxic waters. (2) Sharp maxima or minima in concentrations of organic compounds coincided with zones of enhanced microbial activities, especially in the vicinity of the oxic-suboxic and suboxic-anoxic interfaces. (3) The benthic boundary layer, 300-400 m thick, had a markedly different organic composition and substantially higher concentrations of organic acids, and to a lesser extent sugars and thiols, than the overlying water. (4) A dramatic change in the composition and concentration of dissolved free amino acids occurred in the water column during the cruise and appeared to be related to biological patchiness. (5) Organic thiols constituted a significant portion (e.g. 10-20%) of the total reduced sulfur near the top of the sulfidic zone, and may contribute to the origin of hydrogen sulfide in this zone. (6) Major unknown amine and carbonyl compounds were discovered in the anoxic zone, providing evidence that the Black Sea contains unique anaerobic bacteria with possibly new biochemical pathways.

  10. Characterization of Dissolved Organic Carbon in Deep Groundwater from the Witwatersrand Basin

    NASA Astrophysics Data System (ADS)

    Pullin, M. J.; Hendrickson, S.; Simon, P.; Sherwood Lollar, B.; Wilkie, K.; Onstott, T. C.; Washton, N.; Clewett, C.

    2013-12-01

    This work describes the isolation, fractionation, and chemical analysis of dissolved organic carbon (DOC) in deep groundwater in the Witwatersrand Basin, South Africa. The groundwater was accessed through mining boreholes in gold and diamond mine shafts. Filtered water samples were collected and preserved for later analysis. In some cases, the organic carbon was also collected on DAX-8 and XAD-4 adsorption resins in situ and then transported to the surface for removal, clean-up, and lyophilization. Solid state C-13 NMR analysis of that organic carbon was conducted. Organic compounds were also isolated from the water using solid phase extraction cartridges for later analysis by GC-MS. Absorbance, fluorescence, and HPLC analyses was were used to analyze the DOC in the filtered water samples. C-14 and C-13 isotopic analysis of the organic carbon was also conducted. Identifiable components of the DOC include both organic acids and amino acids. However, initial results indicate that the majority of the subsurface DOC is a complex heterogeneous mixture with an average molecular weight of approximately 1000 Da, although this DOC is less complex than that found in soils or surface water. Finally, we will discuss possible sources of the organic carbon and its biogeochemical cycling in the subsurface.

  11. Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

    USGS Publications Warehouse

    Leenheer, Jerry A.; Reddy, Michael M.

    2008-01-01

    Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

  12. Dissolved organic matter composition and bioavailability reflect ecosystem productivity in the Western Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Shen, Y.; Fichot, C. G.; Benner, R.

    2012-12-01

    Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High concentrations and yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting DOM was of limited bioavailability. Concentrations and yields of TDAA in the upper halocline of slope and basin waters were also low, suggesting the Beaufort is not a major source of bioavailable DOM to slope and basin waters. In shelf waters of both systems, elevated concentrations and yields of TDAA were often observed in waters with higher chlorophyll concentrations and productivity. Surface concentrations of DOC were similar (p > 0.05) in the two systems despite the contrasting productivity, but concentrations and yields of TDAA were significantly higher (p < 0.0001) in the Chukchi than in the Beaufort. Unlike bulk DOC, TDAA concentrations and yields reflect ecosystem productivity in the western Arctic. The occurrence of elevated bioavailable DOM concentrations in the Chukchi Sea implies an uncoupling between the biological production and utilization of DOM and has important implications for sustaining heterotrophic microbial growth and diversity in oligotrophic waters of the central Arctic basins.

  13. Photochemical Flocculation of Terrestrial Dissolved Organic Matter (tDOM) and Iron: Mechanisms and Geochemical Implications

    NASA Astrophysics Data System (ADS)

    Mopper, K.; Helms, J. R.; Mao, J.; Abdulla, H. A.; Schmidt-Rohr, K.

    2013-12-01

    Photoflocculation of DOM has received relatively little attention. No previous studies have examined the chemical composition of the flocs nor investigated the coagulation mechanisms. We observed that, after 30 days of simulated solar UV irradiation of 0.1-um filtered Great Dismal Swamp (Virginia) water, 7.1% of the DOC was converted to POC while 75% was remineralized. Approximately 87% of the iron was removed from the dissolved phase after 30 days, but iron did not flocculate until a major fraction of DOM was removed by photochemical degradation and flocculation (>10 days); thus, during the initial 10 days, there were sufficient organic ligands present and/or the pH was low enough to keep iron in solution. Although photoflocculation of iron did eventually occur, it is not clear if iron is required for the initial flocculation of DOM. Using NMR and FT-IR techniques, we found that photochemically flocculated POM was enriched in aliphatics and amide functionality relative to the residual non-flocculated DOM, while carbohydrate-like material was neither photochemical degraded nor flocculated. Based on this spectroscopic evidence, we propose several mechanisms for the formation of the flocs during irradiation. We also speculate that abiotic photochemical flocculation may remove a significant fraction of tDOM and iron from the upper water column between headwaters and the ocean, including estuaries. Fig. 1. Concentrations of dissolved (gray), particulate (black), and adsorbed (white) material as a function of irradiation time: (a) organic carbon, (b) absorption at 300 nm, (c) total iron by atomic absorption, and (d) total nitrogen. Error bars represent the combined standard deviations of the 'total,' 'dissolved,' and 'adsorbed' terms from which the 'particulate' term was calculated. Total nitrogen was not determined for the 'adsorbed' material

  14. Dissolved organic phosphorus speciation in the waters of the Tamar estuary (SW England)

    NASA Astrophysics Data System (ADS)

    Monbet, Phil; McKelvie, Ian D.; Worsfold, Paul J.

    2009-02-01

    The speciation of dissolved organic phosphorus (DOP) in the temperate Tamar estuary of SW England is described. Eight stations from the riverine to marine end-members were sampled during four seasonal campaigns in 2007 and the DOP pool in the water column and sediment porewater was characterized and quantified using a flow injection manifold after sequential enzymatic hydrolysis. This enabled the enzymatically hydrolysable phosphorus (EHP) fraction and its component labile monoester phosphates, diester phosphates and a phytase-hydrolysable fraction that includes myo-inositol hexakisphosphate (phytic acid), to be determined and compared with the total DOP, dissolved reactive phosphorus (DRP) and total dissolved phosphorus (TDP) pools. The results showed that the DOP pool in the water column varied temporally and spatially within the estuary (1.1-22 μg L -1) and constituted 6-40% of TDP. The EHP fraction of DOP ranged from 1.1-15 μg L -1 and represented a significant and potentially bioavailable phosphorus fraction. Furthermore the spatial profiles of the three components of the EHP pool generally showed non-conservative behavior along the salinity gradient, with apparent internal estuarine sources. Porewater profiles followed broadly similar trends but were notably higher at the marine station throughout the year. In contrast to soil organic phosphorus profiles, the labile monoester phosphate fraction was the largest component, with diester phosphates also prevalent. Phytic acid concentrations were higher in the lower estuary, possibly due to salinity induced desorption processes. The EHP fraction is not commonly determined in aquatic systems due to the lack of a suitable measurement technique and the Tamar results reported here have important implications for phosphorus biogeochemistry, estuarine ecology and the development of efficient strategies for limiting the effects of phosphorus on water quality.

  15. Enhancement of the water solubility of organic pollutants such as pyrene and atrazine by dissolved humic and fulvic acids

    SciTech Connect

    Patterson, H.H.; MacDonald, B.; Fang, F.

    1995-12-31

    Many factors determine the fate and transport of an organic pollutant in the environment but water solubility is certainly one of the most important. Among the environmental factors that alter the solubility of a molecule are naturally occurring humic and fulvic acids. We have hypothesized that the humic/fulvic acids from different sources within a watershed have different binding affinities for pollutants such as pyrene and atrazine. This could lead to different rates of transport or bioavailability within the watershed. Humic/fulvic acids were isolated from a stream, adjacent wetland and nearby wooded upland sites. A fluorescence quenching method was developed to quantify the binding coefficient of the pollutants with the dissolved organic carbon. From these results a model was constructed to determine the sites with the greatest potential to modify pollutant contamination in the environment.

  16. Formation of trihalomethanes of dissolved organic matter fractions in reservoir and canal waters.

    PubMed

    Musikavong, Charongpun; Srimuang, Kanjanee; Tachapattaworakul Suksaroj, Thunwadee; Suksaroj, Chaisri

    2016-07-28

    The formation of trihalomethanes (THMs) of hydrophobic organic fraction (HPO), transphilic organic fraction (TPI), and hydrophilic organic fraction (HPI) of reservoir and canal waters from the U-Tapao River Basin, Songkhla, Thailand was investigated. Water samples were collected three times from two reservoirs, upstream, midstream, and downstream of the U-Tapao canal. The HPO was the major dissolved organic matter (DOM) fraction in reservoir and canal waters. On average, the HPO accounted for 53 and 45% of the DOM in reservoir and canal waters, respectively. The TPI of 19 and 23% in reservoir and canal waters were determined, respectively. The HPI of 29% of the reservoir water and HPI of 32% of the canal water were detected. For the reservoir water, the highest trihalomethane formation potential (THMFP)/dissolved organic carbon (DOC) was determined for the HPI, followed by the TPI and HPO, respectively. The average values of the THMFP/DOC of the HPI, TPI, and HPO of the reservoir water were 78, 52, and 49 µg THMs/mg C, respectively. The highest THMFP/DOC of the canal water was detected for the HPI, followed by HPO and TPI, respectively. Average values of the THMFP/DOC of HPI of water at upstream and midstream locations of 58 µg THMs/mg C and downstream location of 113 µg THMs/mg C were determined. Average values of THMFP/DOC of HPO of water at upstream and midstream and downstream locations were 48 and 93 µg THMs/mg C, respectively. For the lowest THMFP/DOC fraction, the average values of THMFP/DOC of TPI of water at upstream and midstream and downstream locations were 35 and 73 µg THMs/mg C, respectively.

  17. Bioavailability of dissolved organic carbon linked with the regional carbon cycle in the East China Sea

    NASA Astrophysics Data System (ADS)

    Gan, Shuchai; Wu, Ying; Zhang, Jing

    2016-02-01

    The regional carbon cycle on continental shelves has created great interest recently due to the enigma of whether these areas are a carbon sink or a source. It is vital for a precise carbon cycle model to take the bioavailability of dissolved organic carbon (DOC) into account, as it impacts the sink and source capacity, especially on dynamic shelves such as the East China Sea. Nine bio-decomposition experiments were carried out to assess differences in the bioavailability of DOC. Samples were collected from different water masses in the East China Sea, such as the Coastal Current, the Taiwan Current, and the Kuroshio Current, as well as from the Changjiang (Yangtze River), the main contributor of terrestrial DOC in the East China Sea. This study aimed to quantify and qualify bioavailable DOC (BDOC) in the East China Sea. Both the degradation constant of BDOC and the carbon output from microorganisms have been quantitatively evaluated. Qualitatively, excitation-emission matrix fluorescence spectra (EEMs) were used to evaluate the intrinsic reasons for BDOC variation. By using EEMs in conjunction with parallel factor analysis (PARAFAC), five individual fluorescent components were identified in this study: three humic-like and two protein-like components (P1, P2). The highest P1 and P2 fluorescence intensities were recorded in the coastal water during a phytoplankton algal bloom, while the lowest intensities were recorded in the Changjiang estuary. Quantitatively, BDOC observed during the incubation ranged from 0 to 26.1 μM. The DOC degradation rate constant varied from 0 to 0.027 (d-1), and was lowest in the Changjiang and highest in algal bloom water and warm shelf water (the Taiwan current). The Taiwan Current and mixed shelf water were the major contributors of BDOC flux to the open ocean, and the East China Sea was a net source of BDOC to the ocean. The results verified the importance of BDOC in regional carbon cycle modeling. Combining the data of BDOC and EEMs

  18. Experimental evidence of dust-induced shaping of surface dissolved organic matter in the oligotrophic ocean

    NASA Astrophysics Data System (ADS)

    Pulido-Villena, Elvira; Djaoudi, Kahina; Barani, Aude; Charrière, Bruno; Delmont, Anne; Hélias-Nunige, Sandra; Marc, Tedetti; Wambeke France, Van

    2016-04-01

    Recent research has shown that dust deposition may impact the functioning of the microbial loop. On one hand, it enhances bacterial mineralization of dissolved organic matter (DOM), and so may limit the carbon export. On the other hand, the interaction between heterotrophic bacteria and DOM in the surface ocean can increase the residence time of DOM, promoting its export and sequestration in the deep ocean. The main goal of this study was to experimentally assess whether the bacterial response to dust deposition is prone to have an effect on the residence time of the DOM pool by modifying its bioavailability. The bacterial degradation of DOM was followed on dust-amended and control treatments during long-term incubations. Dissolved organic carbon concentration decreased by 9 μmol L-1 over the course of the experiment in both control and dust-enriched conditions, with no significant differences between treatments. However, significant differences in DOM optical properties appeared at the latest stage of the incubations suggesting an accumulation of DOM of high molecular weight in the dust-amended treatment. At the end of the incubations, the remaining water was filtered and re-used as a new culture medium for a bacterial natural assemblage. Bacterial abundance and production was lower in the treatment previously submitted to dust enrichment, suggesting a decrease in DOM lability after a dust deposition event. These preliminary results point to a new link between dust and ocean carbon cycle through the modification of the residence time of the DOM pool.

  19. New nutrients exert fundamental control on dissolved organic carbon accumulation in the surface Atlantic Ocean.

    PubMed

    Romera-Castillo, Cristina; Letscher, Robert T; Hansell, Dennis A

    2016-09-20

    The inventories of carbon residing in organic matter dissolved in the ocean [dissolved organic carbon (DOC)] and in the atmosphere as CO2 are of the same order of magnitude, such that small changes in the DOC pool could have important consequences in atmospheric carbon and thus climate. DOC in the global ocean is largely formed in the sunlit euphotic zone, but identifying predictable controls on that production is an important yet unrealized goal. Here, we use a testable and causative correlation between the net production of DOC and the consumption of new nutrients in the euphotic zone of the Atlantic Ocean. We demonstrate that new nutrients introduced to the euphotic zone by upwelling in divergence zones and by winter convective overturn of the water column, and the primary production associated with those nutrients, are the ultimate driver of DOC distributions across the Atlantic basins. As new nutrient input will change with a changing climate, the role of DOC in the ocean's biological pump should likewise be impacted.

  20. Removal of fluorescence and ultraviolet absorbance of dissolved organic matter in reclaimed water by solar light.

    PubMed

    Wu, Qianyuan; Li, Chao; Wang, Wenlong; He, Tao; Hu, Hongying; Du, Ye; Wang, Ting

    2016-05-01

    Storing reclaimed water in lakes is a widely used method of accommodating changes in the consumption of reclaimed water during wastewater reclamation and reuse. Solar light serves as an important function in degrading pollutants during storage, and its effect on dissolved organic matter (DOM) was investigated in this study. Solar light significantly decreased the UV254 absorbance and fluorescence (FLU) intensity of reclaimed water. However, its effect on the dissolved organic carbon (DOC) value of reclaimed water was very limited. The decrease in the UV254 absorbance intensity and FLU excitation-emission matrix regional integration volume (FLU volume) of reclaimed water during solar light irradiation was fit with pseudo-first order reaction kinetics. The decrease of UV254 absorbance was much slower than that of the FLU volume. Ultraviolet light in solar light had a key role in decreasing the UV254 absorbance and FLU intensity during solar light irradiation. The light fluence-based removal kinetic constants of the UV254 and FLU intensity were independent of light intensity. The peaks of the UV254 absorbance and FLU intensity with an apparent molecular weight (AMW) of 100Da to 2000Da decreased after solar irradiation, whereas the DOC value of the major peaks did not significantly change.

  1. Effects of compositional changes on reactivity continuum and decomposition kinetics of lake dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Mostovaya, Alina; Koehler, Birgit; Guillemette, François; Brunberg, Anna-Kristina; Tranvik, Lars J.

    2016-07-01

    To address the link between the composition and decomposition of freshwater dissolved organic matter (DOM), we manipulated the DOM from three boreal lakes using preincubations with UV light to cleave large aromatic molecules and polyvinylpyrrolidone (PVP) to remove colored phenolic compounds. Subsequently, we monitored the dissolved organic carbon (DOC) loss over 4 months of microbial degradation in the dark to assess how compositional changes in DOM affected different aspects of the reactivity continuum, including the distribution of the apparent decay coefficients. We observed profound effects on decomposition kinetics, with pronounced shifts in the relative share of rapidly and more slowly decomposing fractions of the DOM. In the UV-exposed treatment initial apparent decay coefficient k0 was almost threefold higher than in the control. Significantly higher relative DOC loss in the UV-exposed treatment was sustained for 2 months of incubation, after which decay coefficients converged with those in the control. The PVP removed compounds with absorbance and fluorescence characteristics representative of aromatic compounds, which led to slower decomposition, compared to that in the control. Our results demonstrate the reactivity continuum underlying the decomposition of DOM in freshwaters and highlight the importance of intrinsic properties of DOM in determining its decomposition kinetics.

  2. Dissolved organic matter in the Florida everglades: Implications for ecosystem restoration

    USGS Publications Warehouse

    Aiken, G.R.; Gilmour, C.C.; Krabbenhoft, D.P.; Orem, W.

    2011-01-01

    Dissolved organic matter (DOM) in the Florida Everglades controls a number of environmental processes important for ecosystem function including the absorption of light, mineral dissolution/precipitation, transport of hydrophobic compounds (e.g., pesticides), and the transport and reactivity of metals, such as mercury. Proposed attempts to return the Everglades to more natural flow conditions will result in changes to the present transport of DOM from the Everglades Agricultural Area and the northern conservation areas to Florida Bay. In part, the restoration plan calls for increasing water flow throughout the Everglades by removing some of the manmade barriers to flow in place today. The land- and water-use practices associated with the plan will likely result in changes in the quality, quantity, and reactivity of DOM throughout the greater Everglades ecosystem. The authors discuss the factors controlling DOM concentrations and chemistry, present distribution of DOM throughout the Everglades, the potential effects of DOM on key water-quality issues, and the potential utility of dissolved organic matter as an indicator of success of restoration efforts. Copyright ?? 2011 Taylor & Francis Group, LLC.

  3. New nutrients exert fundamental control on dissolved organic carbon accumulation in the surface Atlantic Ocean

    PubMed Central

    Romera-Castillo, Cristina; Letscher, Robert T.; Hansell, Dennis A.

    2016-01-01

    The inventories of carbon residing in organic matter dissolved in the ocean [dissolved organic carbon (DOC)] and in the atmosphere as CO2 are of the same order of magnitude, such that small changes in the DOC pool could have important consequences in atmospheric carbon and thus climate. DOC in the global ocean is largely formed in the sunlit euphotic zone, but identifying predictable controls on that production is an important yet unrealized goal. Here, we use a testable and causative correlation between the net production of DOC and the consumption of new nutrients in the euphotic zone of the Atlantic Ocean. We demonstrate that new nutrients introduced to the euphotic zone by upwelling in divergence zones and by winter convective overturn of the water column, and the primary production associated with those nutrients, are the ultimate driver of DOC distributions across the Atlantic basins. As new nutrient input will change with a changing climate, the role of DOC in the ocean’s biological pump should likewise be impacted. PMID:27582464

  4. Estimating dissolved organic carbon concentration in turbid coastal waters using optical remote sensing observations

    NASA Astrophysics Data System (ADS)

    Cherukuru, Nagur; Ford, Phillip W.; Matear, Richard J.; Oubelkheir, Kadija; Clementson, Lesley A.; Suber, Ken; Steven, Andrew D. L.

    2016-10-01

    Dissolved Organic Carbon (DOC) is an important component in the global carbon cycle. It also plays an important role in influencing the coastal ocean biogeochemical (BGC) cycles and light environment. Studies focussing on DOC dynamics in coastal waters are data constrained due to the high costs associated with in situ water sampling campaigns. Satellite optical remote sensing has the potential to provide continuous, cost-effective DOC estimates. In this study we used a bio-optics dataset collected in turbid coastal waters of Moreton Bay (MB), Australia, during 2011 to develop a remote sensing algorithm to estimate DOC. This dataset includes data from flood and non-flood conditions. In MB, DOC concentration varied over a wide range (20-520 μM C) and had a good correlation (R2 = 0.78) with absorption due to coloured dissolved organic matter (CDOM) and remote sensing reflectance. Using this data set we developed an empirical algorithm to derive DOC concentrations from the ratio of Rrs(412)/Rrs(488) and tested it with independent datasets. In this study, we demonstrate the ability to estimate DOC using remotely sensed optical observations in turbid coastal waters.

  5. [Influence of freshwater marsh tillage on microbial biomass and dissolved organic carbon and nitrogen].

    PubMed

    Huang, Jing-Yu; Song, Chang-Chun; Song, Yan-Yu; Liu, De-Yan; Wan, Zhong-Mei; Liao, Yu-Jing

    2008-05-01

    The changes in microbial biomass carbon (MBC), microbial biomass nitrogen (MBN), dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) were examined in order to assess the effect of surface layer soil (0 - 10 cm) under different land-use types after freshwater marshes tillage in the Sanjiang Plain Northeast China. Land uses were Deyeuxia angustifolia freshwater marshes ((DAM), cultivated land (CL), recovery freshwater marsh (RFM), constructed woodland (CW). After DAM soil tillage, MBC, MBN, DOC and DON declined strongly in agricultural surface soil layer, decreased 63.8%-80.5% (MBC), 56.3%-67.1% (MBN), 43.1%-44.3% (DOC) and 25.2%-56.1% (DON) respectively. In contrast, these C, N fraction had significant recovered in RFM and CW surface soil, increased 36.1%-59.9% (MBC), 46.7%-65.9% (MBN), 67.0%-69.3% (DOC)and 81.2%-88.3% (DON) respectively. Cultivation and land-use affected soil MBC, MBN, DOC and DON intensely. Therefore these labile C, N fractions have the significant relative under different land-use types. However DOC was more obvious controlled than DON by the land-use types. The relative between DOC and MBC, MBN have much difference than DON, the main reason of this distinction is the diverse source in available carbon and nitrogen that taken by microbial property under different land uses.

  6. Hydrologic Controls on Dissolved Organic Matter Mobilization and Transport within Undisturbed Soils

    NASA Astrophysics Data System (ADS)

    Xu, N.; Saiers, J.

    2007-12-01

    Dissolved organic matter (DOM) in soils plays an important role in the transport of nutrients and contaminants through the terrestrial environment. Subsurface pathways deliver a significant portion of carbon to streams that drain forested and agricultural watersheds. Although the importance of rainfall events to the DOM soil-water flux is well known, the hydrologic factors that govern this flux have not been fully examined. The primary purpose of this study is to investigate the soil and rainfall characteristics controlling the mobilization and transport of DOM in undisturbed soils. Intact soil columns including topsoil and subsoil layers were taken from the Harvard forest in Petersham, MA. Unsaturated flow conditions were maintained by applying suction to the bottom of the soil columns. The columns were irrigated by series of interrupted rainfall events using the same total volume of artificial rain water. Preliminary experiments showed continuous leaching of DOM (measured by dissolved organic carbon) with an initial peak in concentration that coincided with the passage of the wetting front. The leached DOM was also characterized by UV absorbance, fluorescence spectroscopy in the emission mode, and additional spectroscopic derived indexes such as the humification index. Ongoing column experiments are focusing on the effects of rainfall intensity, frequency, and rainfall history on DOM mobilization and transport through natural, structured soils. These investigations can elucidate the influence of factors that are associated with climate change on DOC dynamics. Results of our analyses should also provide insight into the mechanisms that govern DOM mobilization in soils.

  7. The origin and function of dissolved organic matter in agro-urban coastal streams

    NASA Astrophysics Data System (ADS)

    Petrone, Kevin C.; Fellman, Jason B.; Hood, Eran; Donn, Michael J.; Grierson, Pauline F.

    2011-03-01

    Streams draining urban and agriculture catchments are often a source of inorganic nutrients to downstream aquatic ecosystems, but little is known about how changes in land use influence the quality and biodegradability of dissolved organic matter (DOM). We used parallel factor analysis of excitation-emission fluorescence spectroscopy and biodegradation incubations to examine how DOM composition influences bioavailable dissolved organic carbon (DOC) in surface waters of urban and agricultural catchments during summer (low flow), winter (high flow) and spring (flow recession). Percent bioavailable DOC was variable for all catchments (2-57%) and negatively related to percent humic-like fluorescence, but positively related to percent protein-like fluorescence and simple fluorescence metrics of DOM precursor material (fluorescence index and β:α values). Conversely, highly variable DOC concentrations (2-140 mg L-1) were negatively related to protein-like fluorescence and positively related to humic-like fluorescence. Elevated concentrations of DOC (>30 mg L-1) in agro-urban streams revealed fluorescence indices (<1.3) typical of wetland and forest-dominated ecosystems, suggesting that enriched stream DOM is either derived from the destabilization of legacy soil carbon or currently produced from remnant wetlands and patches of native vegetation. Overall, we demonstrate that fluorescence characteristics can be used to predict bioavailable DOC in human-dominated catchments to better understand the flow of carbon and nutrients in aquatic food webs for improved monitoring and management of coastal ecosystems.

  8. The river as a chemostat: fresh perspectives on dissolved organic matter flowing down the river continuum

    USGS Publications Warehouse

    Creed, Irena F.; McKnight, Diane M.; Pellerin, Brian; Green, Mark B.; Bergamaschi, Brian; Aiken, George R.; Burns, Douglas A.; Findlay, Stuart E G; Shanley, James B.; Striegl, Robert G.; Aulenbach, Brent T.; Clow, David W.; Laudon, Hjalmar; McGlynn, Brian L.; McGuire, Kevin J.; Smith, Richard A.; Stackpoole, Sarah M.

    2015-01-01

    A better understanding is needed of how hydrological and biogeochemical processes control dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) composition from headwaters downstream to large rivers. We examined a large DOM dataset from the National Water Information System of the US Geological Survey, which represents approximately 100 000 measurements of DOC concentration and DOM composition at many sites along rivers across the United States. Application of quantile regression revealed a tendency towards downstream spatial and temporal homogenization of DOC concentrations and a shift from dominance of aromatic DOM in headwaters to more aliphatic DOM downstream. The DOC concentration–discharge (C-Q) relationships at each site revealed a downstream tendency towards a slope of zero. We propose that despite complexities in river networks that have driven many revisions to the River Continuum Concept, rivers show a tendency towards chemostasis (C-Q slope of zero) because of a downstream shift from a dominance of hydrologic drivers that connect terrestrial DOM sources to streams in the headwaters towards a dominance of instream and near-stream biogeochemical processes that result in preferential losses of aromatic DOM and preferential gains of aliphatic DOM.

  9. Investigating extent of dissolved organic carbon stabilization by metal based coagulant in a wetland environment

    NASA Astrophysics Data System (ADS)

    Henneberry, Y.; Mourad, D.; Kraus, T.; Bachand, P.; Fujii, R.; Horwath, W.

    2008-12-01

    This study is part of a larger project designed to investigate the feasibility of using metal-based coagulants to remove dissolved organic carbon (DOC) from island drainage water in the San Joaquin Delta and subsequently retaining the metal-DOC precipitate (floc) in wetlands constructed at the foot of levees to promote levee stability. Dissolved organic carbon is a constituent of concern as some forms of DOC can be converted to carcinogenic compounds during drinking water treatment. The focus of this work is to assess floc stability over time and to determine whether floc can be permanently sequestered as part of wetland sediment. Drainage water collected seasonally from Twitchell Island was coagulated with ferric sulfate and polyaluminum chloride at optimal and 50%-optimal dosage levels. Floc was incubated in the laboratory under anaerobic conditions for six weeks under various conditions including different DOC concentrations, microbial inoculants, and addition of nutrients. Preliminary results indicate the floc is a stable system; little to no DOC was released from the floc into the water column under incubations with native microbial inoculate. In addition, floc incubated with previously coagulated water appeared to remove additional DOC from the water column. Future work will involve field and laboratory studies using 13C labeled plant material to examine the effects of fresh plant matter and the effects of peat soil DOC on floc stability, in order to elucidate mechanisms behind carbon stabilization by metal-based floc.

  10. Dissolved Organic Matter in Arctic and Boreal Streams: Rates and Fates of Decomposition

    NASA Astrophysics Data System (ADS)

    Mutschlecner, A.; Harms, T.

    2015-12-01

    As high-latitude regions warm, new inputs of carbon from thawing permafrost may influence the carbon cycle. Some of this newly released carbon, bound up in molecules of dissolved organic matter (DOM), will be exported into streams and rivers where it may be incorporated into microbial biomass, released to the atmosphere as carbon dioxide, or exported downstream. The factors that control the fate of dissolved organic carbon (DOC) are not fully understood, nor are the seasonal and spatial dynamics of these relationships. We sampled six streams along an arctic-boreal gradient in interior Alaska, collecting water from under ice in April, during snowmelt (May), and in early summer (June). These samples were incubated in the laboratory to determine the fraction of DOC that is susceptible to microbial decomposition and the fraction released as carbon dioxide. Nitrogen and phosphorous additions were used to determine the effect of nutrient limitation on DOC processing. Percent DOC loss across sites ranged from 37-71% in April before snowmelt, 0-9% during snowmelt, and 0-53% in June. We observed no effect of nutrient addition on lability of DOC. Seasonal data are critical to predicting how the processing of DOC in streams will respond to changes in permafrost extent, as well as to changes in the timing of snowmelt and ice-off.

  11. Seasonal and temporal characterization of dissolved organic matter in rainwater by proton nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Seaton, Pamela J.; Kieber, Robert J.; Willey, Joan D.; Avery, G. Brooks; Dixon, Joshua L.

    2013-02-01

    Dissolved organic carbon in rainwater was concentrated by two separate techniques and characterized by 1H-NMR. The total 1H-NMR integral of lyophilized rainwater was higher in every rain sample than that of C18 solid phase extracted samples and always contained a higher percentage integral in the region of protons bound to carbon atoms singly bound to oxygen (H-C-O), such as alcohols, polyols and carbohydrate-like compounds. C18 extracted samples had higher % integral in the alkyl region, consistent with reverse phase extraction of more hydrophobic components in rainwater. Differences in both the 1H-NMR integration and spectral pattern of lyophilized rainwater samples were especially apparent between spring and winter rains, with spring samples having higher percent carbohydrate (H-C-O) signal and winter rains having higher percent alkyl protons and a spectral pattern consistent with the presence of saturated fatty acids. Spring rains are characterized by lower % Alkyl signal coupled with higher % H-C-O than all other events while marine winter events appear in regions characterized by relatively high % Alkyl and average % H-C-O, consistent with increased abundance of fatty acids or fatty acid oxidation products. The 1H-NMR data presented in this manuscript are important because they provide spectral data relating to the source and chemical characteristics of dissolved organic carbon in rainwater as a function of season and air mass back trajectory.

  12. The Photodegradation of Ibuprofen and Dissolved Organic Matter in Lake Superior and St. Louis River Water

    PubMed Central

    Moynan, Angela B.

    2012-01-01

    Abstract Ibuprofen can enter bodies of water via waste water treatment. The question was what effect does photodegradation have on ibuprofen and dissolved organic matter (DOM) in Lake Superior (oligiotrophic) and St. Louis (tannic stained) River water? Ibuprofen concentrations of 15,000, 30,000, and 60,000 μg/L were made from lake, river, and distilled water, as well as additional distilled concentrations of 7,500 and 120,000 μg/L. Half of the eighty-four trial cups were placed in an ultraviolet light cabinet and half of the set were placed in a dark cabinet for three days. After the exposure period, a UV-Vis was performed to measure change in molar mass and the summed absorbance of colored dissolved organic matter (CDOM). It appears that ibuprofen decreases in molar mass after exposure to light in distilled and lake water with 15,000 μg/L of ibuprofen. Surprisingly, the molar mass of DOM in river water increases after UV exposure. Possibly, this occurred because the river water has such a high molar mass of DOM and was not filtered. Microbial biomass could also have contributed to this increase. Ibuprofen entering bodies of water via the waste water treatment system appears to be affected by UV light exposure, but in different ways. PMID:23244688

  13. Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

    DOE PAGES

    Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.; ...

    2016-12-22

    The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10–4. Heteroatomic molecules, especially those containing multiple S and N atoms, were foundmore » to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C10H21N2S4Hg+ and C8H17N2S4Hg+ were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

  14. Optical characterization of dissolved organic matter in tropical rivers of the Guayana Shield, Venezuela

    NASA Astrophysics Data System (ADS)

    Yamashita, Youhei; Maie, Nagamitsu; BriceñO, Henry; Jaffé, Rudolf

    2010-03-01

    Tropical rivers are an important source of dissolved organic matter (DOM) to coastal oceans. However, temporal and spatial variability of DOM composition and thus its quality in such rivers, on landscape and basin scales, have not been well documented. In this study, we present data on the spatial distribution of DOM quantity and quality based on source, molecular weight, and composition using optical properties including excitation emission matrix fluorescence with parallel factor analysis. We compared such DOM quantity and quality determinations in main river channels and their tributaries for three river systems of the Guayana Shield, Venezuela. Spatial variabilities of DOM parameters were strongly related to differences in the geological settings of the drainage basins and presumably their associated vegetation cover. Linear relationships between quantitative and qualitative DOM parameters were also evident, suggesting that high DOC concentration correlated with chromophoric dissolved organic matter (CDOM) characteristics of higher molecular weight associated with terrestrial sources, while low DOC concentrations correlated with CDOM characteristics of lower molecular weight associated primarily with microbial sources. Such relationships seem to imply that DOM concentrations and their sources/characteristics may be coupled in the studied fluvial systems. In addition, shifts in DOM compositions between terrestrial and microbial signals were observed with changes in water discharge and in watersheds disturbed by gold mining activities. The observed linkages between, and the changes among DOM quantity and quality, suggest that the biogeochemistry of DOM in tropical rivers may be quite sensitive to climatic and land use change.

  15. New nutrients exert fundamental control on dissolved organic carbon accumulation in the surface Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Romera-Castillo, Cristina; Letscher, Robert T.; Hansell, Dennis A.

    2016-09-01

    The inventories of carbon residing in organic matter dissolved in the ocean [dissolved organic carbon (DOC)] and in the atmosphere as CO2 are of the same order of magnitude, such that small changes in the DOC pool could have important consequences in atmospheric carbon and thus climate. DOC in the global ocean is largely formed in the sunlit euphotic zone, but identifying predictable controls on that production is an important yet unrealized goal. Here, we use a testable and causative correlation between the net production of DOC and the consumption of new nutrients in the euphotic zone of the Atlantic Ocean. We demonstrate that new nutrients introduced to the euphotic zone by upwelling in divergence zones and by winter convective overturn of the water column, and the primary production associated with those nutrients, are the ultimate driver of DOC distributions across the Atlantic basins. As new nutrient input will change with a changing climate, the role of DOC in the ocean’s biological pump should likewise be impacted.

  16. Seasonal Variation in the Quality of Dissolved and Particulate Organic Matter Exchanged Between a Salt Marsh and Its Adjacent Estuary

    NASA Astrophysics Data System (ADS)

    Osburn, C. L.; Mikan, M.; Etheridge, J. R.; Burchell, M. R.; Birgand, F.

    2015-12-01

    Salt marshes are transitional ecosystems between terrestrial and marine environments. Along with mangroves and other vegetated coastal habitats, salt marshes rank among the most productive ecosystems on Earth, with critical global importance for the planet's carbon cycle. Fluorescence was used to examine the quality of dissolved and particulate organic matter (DOM and POM) exchanging between a tidal creek in a created salt marsh and its adjacent estuary in eastern North Carolina, USA. Samples from the creek were collected hourly over four tidal cycles in May, July, August, and October of 2011. Absorbance and fluorescence of chromophoric DOM (CDOM) and of base-extracted POM (BEPOM) served as the tracers for organic matter quality while dissolved organic carbon (DOC) and base-extracted particulate organic carbon (BEPOC) were used to compute fluxes. Fluorescence was modeled using parallel factor analysis (PARAFAC) and principle components analysis (PCA) of the PARAFAC results. Of nine PARAFAC components modeled, we used multiple linear regression to identify tracers for recalcitrant DOM; labile soil-derived source DOM; detrital POM; and planktonic POM. Based on mass balance, recalcitrant DOC export was 86 g C m-2 yr-1 and labile DOC export was 49 g C m-2 yr-1. The marsh also exported 41 g C m-2 yr-1 of detrital terrestrial POC, which likely originated from lands adjacent to the North River estuary. Planktonic POC export from the marsh was 6 g C m-2 yr-1. Using the DOM and POM quality results obtained via fluorescence measurements and scaling up to global salt marsh area, we estimated that the potential release of CO2 from the respiration of salt marsh DOC and POC transported to estuaries could be 11 Tg C yr-1, roughly 4% of the recently estimated CO2 release for marshes and estuaries globally.

  17. Ultraviolet-visible absorption spectra of chromophoric dissolved