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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. PMID:27019968

  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. Modeling the removal of dissolved organic carbon by ion exchange in a completely mixed flow reactor.

    PubMed

    Boyer, Treavor H; Miller, Cass T; Singer, Philip C

    2008-04-01

    A mathematical model was developed to describe removal of dissolved organic carbon (DOC) by a macroporous, strong-base anion exchange resin in a completely mixed flow reactor with resin recycle and partial resin regeneration. The two-scale model consisted of a microscale model describing the uptake of DOC by the resin coupled with a macroscale model describing the continuous-flow process. Equilibrium and kinetic parameters were estimated from batch laboratory experiments. The model was validated using continuous-flow data from two pilot plant studies. Model predictions were found to be in good agreement with the observed pilot plant data.

  4. Modeling dissolved organic carbon in temperate forest soils: TRIPLEX-DOC model development and validation

    NASA Astrophysics Data System (ADS)

    Wu, H.; Peng, C.; Moore, T. R.; Hua, D.; Li, C.; Zhu, Q.; Peichl, M.; Arain, M. A.; Guo, Z.

    2014-05-01

    Even though dissolved organic carbon (DOC) is the most active carbon (C) cycling in soil organic carbon (SOC) pools, it receives little attention from the global C budget. DOC fluxes are critical to aquatic ecosystem inputs and contribute to the C balance of terrestrial ecosystems, but few ecosystem models have attempted to integrate DOC dynamics into terrestrial C cycling. This study introduces a new process-based model, TRIPLEX-DOC, that is capable of estimating DOC dynamics in forest soils by incorporating both ecological drivers and biogeochemical processes. TRIPLEX-DOC was developed from Forest-DNDC, a biogeochemical model simulating C and nitrogen (N) dynamics, coupled with a new DOC process module that predicts metabolic transformations, sorption/desorption, and DOC leaching in forest soils. The model was validated against field observations of DOC concentrations and fluxes at white pine forest stands located in southern Ontario, Canada. The model was able to simulate seasonal dynamics of DOC concentrations and the magnitudes observed within different soil layers, as well as DOC leaching in the age sequence of these forests. Additionally, TRIPLEX-DOC estimated the effect of forest harvesting on DOC leaching, with a significant increase following harvesting, illustrating that land use change is of critical importance in regulating DOC leaching in temperate forests as an important source of C input to aquatic ecosystems.

  5. 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.; Primeau, F.

    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

  6. 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.

  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.; Primeau, F.

    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. Agent-based modeling of hyporheic dissolved organic carbon transport and transformation

    NASA Astrophysics Data System (ADS)

    Gabrielsen, P. J.; Wilson, J. L.; Pullin, M.

    2011-12-01

    Dissolved organic carbon (DOC) is a complex suite of organic compounds present in natural ecosystems, and is particularly studied in river and stream systems. The hyporheic zone (HZ), a region of surface water-shallow groundwater exchange, has been identified as a hotspot of DOC processing and is generally regarded as a net sink of organic matter. More recent studies into stream DOC have shifted to examining DOC quality rather than bulk quantity. DOC quality variability has been linked to hydrologic and climatic variability, both focuses of current climate change research. A new agent-based model in the NetLogo modeling environment couples hydrologic transport with chemical and biological transformation of DOC to simulate changing DOC quality in hyporheic flow. A pore-scale model implements a Lattice Boltzmann fluid dynamic model and surficial interactions to simulate sorption and microbial uptake. Upscaled to a stream meander scale, this model displays spatial variation and evolution of DOC quality. Model output metrics are correlated to field sample analytical results from a hyporheic meander of the East Fork Jemez River, Sandoval Co., NM.

  9. Hydrochemical Modeling of Dissolved Organic Carbon in a Small, Undisturbed, Forested Watershed in Southern Chile

    NASA Astrophysics Data System (ADS)

    Valdivia, M. V.; Walter, M. T.; Salmon, C. D.; Hedin, L. O.; Walter, M. F.

    2004-12-01

    The objective of the present study is to model Dissolved Organic Carbon (DOC) concentrations in a stream draining a small, undisturbed, old-growth forested watershed in Southern Chile and test model results against measured data. DOC plays an important role in several processes in terrestrial and aquatic ecosystems. For example, through the formation of organic complexes, DOC can influence nutrient availability, affect the solubility, mobility, and toxicity of metals, and control the absorption of pesticides to soils. DOC also influences biological activity by absorbing UV-B radiation and can contribute significantly to freshwater acidity. Additionally, DOC is linked to the formation of trihalomethanes as by-products of the disinfection of drinking water with chlorine, which constitutes a potentially serious threat to human health. Despite plentiful research on biogeochemical processes controlling DOC production and consumption, there is little information from minimally impacted environments, which can provide valuable baseline information from which to evaluate the more impacted ecosystems. Our study focused on a virtually unpolluted old-growth forested watershed in Southern Chile. We developed a conceptual model that assumes DOC production in forest soils is a function of temperature and DOC transport from soil to stream water is a function of discharge and hydrological flow paths. The hydrological response of the catchment under study was simulated using a simple lumped model, based on two years of meteorological data previously collected. Three different equations were used to simulate DOC concentrations in soil water as a function of temperature, and ultimately to derive DOC concentrations in streamflow. Model results were tested against two years of measured DOC concentrations in streamflow, and all three models provided a reasonably good representation of the DOC response of the small studied watershed and a better agreement to the observed DOC than

  10. 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. PMID:27328766

  11. Molecular Simulation of Copper Complexation by a Model of Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Newton, A. G.; Sposito, G.

    2008-12-01

    The coadsorption of cations and organic matter to mineral surfaces has been proposed as a mechanism to stabilize soil organic carbon and explain enhanced cation adsorption in soils. Spectroscopic investigations of coadsorption in copper (Cu)-organic ligand-mineral systems have provided conclusive evidence that ternary surface complexes do occur in instances where the simple organic ligand possesses a minimal number of homogeneous binding sites. Although the results of many experimental and spectroscopic investigations of ternary systems with dissolved organic matter (DOM) suggest that ternary surface complexes may be present, unambiguous conclusions cannot be drawn due to the nature of DOM and the heterogeneity of DOM binding sites. Molecular simulations of ternary surface complexes are powerful tools that can be used in the interpretation of spectroscopic data from these experimental systems. Molecular simulations of Cu-DOM coadsorption at mineral surfaces require a model of Cu-DOM that adequately reproduces the physical-chemical behavior of natural Cu-DOM. The Cu-saturated Schulten DOM molecule, whose charge from deprotonated carboxyl groups was balanced by Cu2+ ions, was modeled using the COMPASS forcefield and energy minimization and molecular dynamics algorithms. Compared to previous simulations of Na- and Ca-saturated Schulten DOM, the Cu-DOM was more compact and spherical, as demonstrated by the decreases in the surface area, surface area: volume ratio, porosity, and radius of gyration and by an increase in the volume. The Cu-DOM complex is more polar than Ca-DOM and less polar than Na-DOM, as indicated by the dipole moment and extent of hydrogen bonding. The Cu2+ ion coordination environment contains an average of four oxygen atoms at 2.04 Å from the metal center. These first shell atoms are primarily water and carboxylate oxygen, although oxygen atoms from carbonyl, phenolic, and esters functionalities as well as nitrogen groups are also present. The DOM

  12. 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.

  13. 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.

  14. Dissolved organic matter adsorption to model surfaces: adlayer formation, properties, and dynamics at the nanoscale.

    PubMed

    Armanious, Antonius; Aeppli, Meret; Sander, Michael

    2014-08-19

    Adlayers of dissolved organic matter (DOM) form on many surfaces in natural and engineered systems and affect a number of important processes in these systems. Yet, the nanoscalar properties and dynamics of DOM adlayers remain poorly investigated. This work provides a systematic analysis of the properties and dynamics of adlayers formed from a diverse set of eight humic and fulvic acids, used as DOM models, on surfaces of self-assembled monolayers (SAMs) of different alkylthiols covalently bound to gold supports. DOM adsorption to positively charged amine-terminated SAMs resulted in the formation of water-rich adlayers with nanometer thicknesses that were relatively rigid, irreversibly adsorbed, and collapsed upon air drying, as demonstrated by combined quartz crystal microbalance and ellipsometry measurements. DOM adlayer thicknesses varied only slightly with solution pH from 5 to 8 but increased markedly with increasing ionic strength. Contact angle measurements revealed that the DOM adlayers were relatively polar, likely due to the high water contents of the adlayers. Comparing DOM adsorption to SAM-coated sensors that systematically differed in surface charge and polarity characteristics showed that electrostatics dominated DOM-surface interactions. Laccase adsorption to DOM adlayers on amine-terminated SAMs served to demonstrate the applicability of the presented experimental approach to study the interactions of (bio)macromolecules and (nano)particles with DOM.

  15. Modeling priming effects on microbial consumption of dissolved organic carbon in rivers

    NASA Astrophysics Data System (ADS)

    Hotchkiss, E. R.; Hall, R. O.; Baker, M. A.; Rosi-Marshall, E. J.; Tank, J. L.

    2014-05-01

    Rivers receive and process large quantities of terrestrial dissolved organic carbon (DOC). Biologically available (unstable) DOC leached from primary producers may stimulate (i.e., prime) the consumption of more stable terrestrially derived DOC by heterotrophic microbes. We measured microbial DOC consumption (i.e., decay rates) from contrasting C sources in 10 rivers in the western and Midwestern United States using short-term bioassays of river water, soil and algal leachates, glucose, and commercial humate. We added inorganic nutrients (ammonium and phosphorus) to a subset of bioassays. We also amended a subset of river, soil, and commercial humate bioassays with glucose or algal leachates to test the hypothesis that unstable DOC primes consumption of more stable DOC. We used prior measurements of source-specific DOC bioavailability, linked with a Bayesian process model, to estimate means and posterior probability distributions for source-specific DOC decay rates in multisource bioassays. Modeled priming effects ranged from a -130 to +370% change in more stable DOC decay when incubated with unstable DOC. Glucose increased modeled river DOC decay by an average of 87% among all rivers. Glucose and algal leachates increased soil leachate and commercial humate decay by an average of 25% above background rates. Inorganic nutrient additions did not have consistent effects on DOC decay, likely because most of the study rivers had high ambient background nutrients. Our results demonstrate that the priming effect can augment DOC decay in rivers. In addition, Bayesian models can be used to estimate mechanisms driving aquatic ecosystem processes that are difficult to measure directly.

  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

    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.

  1. 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, Rob

    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.

  2. 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

  3. 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...

  4. 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

    2014-12-01

    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. PMID:25371136

  5. 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.

  6. 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.

  7. 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.

  8. 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. PMID:27017138

  9. 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.

  10. Dissolved organic carbon fluxes in the Middle Atlantic Bight: An integrated approach based on satellite data and ocean model products

    NASA Astrophysics Data System (ADS)

    Mannino, Antonio; Signorini, Sergio R.; Novak, Michael G.; Wilkin, John; Friedrichs, Marjorie A. M.; Najjar, Raymond G.

    2016-02-01

    Continental margins play an important role in global carbon cycle, accounting for 15-21% of the global marine primary production. Since carbon fluxes across continental margins from land to the open ocean are not well constrained, we undertook a study to develop satellite algorithms to retrieve dissolved organic carbon (DOC) and combined these satellite data with physical circulation model products to quantify the shelf boundary fluxes of DOC for the U.S. Middle Atlantic Bight (MAB). Satellite DOC was computed through seasonal relationships of DOC with colored dissolved organic matter absorption coefficients, which were derived from an extensive set of in situ measurements. The multiyear time series of satellite-derived DOC stocks (4.9 Teragrams C; Tg) shows that freshwater discharge influences the magnitude and seasonal variability of DOC on the continental shelf. For the 2010-2012 period studied, the average total estuarine export of DOC into the MAB shelf is 0.77 Tg C yr-1 (year). The integrated DOC tracer fluxes across the shelf boundaries are 12.1 Tg C yr-1 entering the MAB from the southwest alongshore boundary, 18.5 Tg C yr-1 entering the MAB from the northeast alongshore boundary, and 29.0 Tg C yr-1 flowing out of the MAB across the entire length of the 100 m isobath. The magnitude of the cross-shelf DOC flux is quite variable in time (monthly) and space (north to south). The highly dynamic exchange of water along the shelf boundaries regulates the DOC budget of the MAB at subseasonal time scales.

  11. Influence of pH, hardness, dissolved organic carbon concentration, and dissolved organic matter source on the acute toxicity of copper to Daphnia magna in soft waters: implications for the biotic ligand model.

    PubMed

    Ryan, Adam C; Tomasso, Joseph R; Klaine, Stephen J

    2009-08-01

    The influence of pH, dissolved organic carbon (DOC) concentration, water hardness, and dissolved organic matter (DOM) source on the acute toxicity of copper were investigated with standardized 48-h Daphnia magna toxicity tests. Toxicity tests were conducted according to a four-factor complete factorial design. Nominal factor levels were as follows: pH 6 and 8; DOC, 2.5 and 10 mg/L; hardness, 10, 20, and 40 mg/L as CaCO3; and two DOM sources (collected from the Black River and Edisto River, SC, USA). The experimental design resulted in 24 different factor level combinations. Results indicated that all factors had significant effects on copper toxicity. Furthermore, a strong interactive effect of DOC concentration and pH was detected. Because the biotic ligand model (BLM) has become a widely used tool for predicting toxicity and interpreting toxicity test results, its performance with these data was evaluated. Seventy percent of BLM predictions were within twofold of the observed median lethal concentrations. However, BLM parameters could be adjusted to improve model performance with this data set. This analysis suggested that in soft waters, the CuOH+ complex binds more strongly with the biotic ligand and that the competitive effect of hardness cations should be increased. The results of the present study may have implications for application of the BLM to some types of surface waters. Furthermore, a comprehensive analysis of BLM performance with all available data should be performed, and necessary updates to model parameters should be made to produce the most robust and widely applicable model.

  12. Cryptic wetlands: integrating hidden wetlands in regression models of the export of dissolved organic carbon from forested landscapes

    NASA Astrophysics Data System (ADS)

    Creed, I. F.; Sanford, S. E.; Beall, F. D.; Molot, L. A.; Dillon, P. J.

    2003-12-01

    This study examines the relationship between wetlands hidden beneath the forest canopy (cryptic wetlands) and dissolved organic carbon (DOC) export to streams and lakes in forested ecosystems. In the Turkey Lakes Watershed (TLW), located in the Algoma Highlands of central Ontario, Canada, there is substantial natural variation in average annual DOC export (kgC ha-1 year-1), ranging from 11·4 to 31·5 kgC ha-1 year-1 in catchments with no apparent wetlands. We hypothesized that the natural variation in DOC export was related to cryptic wetlands. Cryptic wetlands were derived manually from geographic coordinates that were surveyed with a differential global positioning system, and automatically from identification of topographic depressions and flat slopes (<1·5° ) within a digital elevation model (DEM) in a geographic information system. For the TLW catchments, which are characterized by shallow soils over bedrock, a significant correlation (r2 ≥ 0·9, p < 0·001) between manual and automated methods was observed for scales up to 50 m when a light detection and ranging DEM was used for the topographic analysis. Regression models indicated that cryptic wetlands (%) explained the majority of the natural variation in DOC export (kgC ha-1 year-1), with r2 = 0·88 (p < 0·001) for the model based on the manually derived wetlands and r2 = 0·85 (p < 0·001) for the model based on the automatically derived wetlands. The strength and significance of the automatically derived wetlands (%) versus DOC export (kgC ha-1 year-1) regression model diminished when other sources of DEMs were used. This study emphasizes the importance of including cryptic wetlands in predictive models of DOC export, particularly in catchments where the topography includes depressions and flat areas but no apparent wetlands. Copyright

  13. An optical model for the remote sensing of coloured dissolved organic matter in coastal/ocean waters

    NASA Astrophysics Data System (ADS)

    Tiwari, S. P.; Shanmugam, P.

    2011-07-01

    An optical model is developed for the remote sensing of coloured dissolved organic matter (CDOM) in a wide range of waters within coastal and open ocean environments. The absorption of CDOM (denoted as a g) is generally considered as an exponential form model, which has two important parameters - the slope S and absorption of CDOM at a reference wavelength a g( λ0). The empirical relationships for deriving these two parameters are established using in-situ bio-optical datasets. These relationships use the spectral remote sensing reflectance (R rs) ratio at two wavelengths R rs(670)/R rs(490), which avoids the known atmospheric correction problems and is sensitive to CDOM absorption and chlorophyll in coastal/ocean waters. This ratio has tight relationships with a g(412) and a g(443) yielding correlation coefficients between 0.77 and 0.78. The new model, with the above parameterization applied to independent datasets (NOMAD SeaWiFS match-ups and Carder datasets), shows good retrievals of the a g( λ) with regression slopes close to unity, little bias and low mean relative and root mean square errors. These statistical estimates improve significantly over other inversion models (e.g., Linear Matrix-LM and Garver-Siegel-Maritorena-GSM semi-analytical models) when applied to the same datasets. These results demonstrate a good performance of the proposed model in both coastal and open ocean waters, which has the potential to improve our knowledge of the biogeochemical cycles and processes in these domains.

  14. 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

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

    PubMed

    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

  16. 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.

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

    PubMed

    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.

  18. 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

  19. Diagnosis of Processes Controlling Dissolved Organic Carbon (DOC) Export in a Subarctic Region by a Dynamic Ecosystem Model

    NASA Astrophysics Data System (ADS)

    Tang, J.

    2015-12-01

    Permafrost thawing in high latitudes allows more soil organic carbon (SOC) to become hydrologically accessible. This can increase dissolved organic carbon (DOC) exports and carbon release to the atmosphere as CO2 and CH4, with a positive feedback to regional and global climate warming. However, this portion of carbon loss through DOC export is often neglected in ecosystem models. In this paper, we incorporate a set of DOC-related processes (DOC production, mineralization, diffusion, sorption-desorption and leaching) into an Arctic-enabled version of the dynamic ecosystem model LPJ-GUESS (LPJ-GUESS WHyMe) to mechanistically model the DOC export, and to link this flux to other ecosystem processes. The extended LPJ-GUESS WHyMe with these DOC processes is applied to the Stordalen catchment in northern Sweden. The relative importance of different DOC-related processes for mineral and peatland soils for this region have been explored at both monthly and annual scales based on a detailed variance-based Sobol sensitivity analysis. For mineral soils, the annual DOC export is dominated by DOC fluxes in snowmelt seasons and the peak in spring is related to the runoff passing through top organic rich layers. Two processes, DOC sorption-desorption and production, are found to contribute most to the annual variance in DOC export. For peatland soils, the DOC export during snowmelt seasons is constrained by frozen soils and the processes of DOC production and mineralization, determining the magnitudes of DOC desorption in snowmelt seasons as well as DOC sorption in the rest of months, play the most important role in annual variances of DOC export. Generally, the seasonality of DOC fluxes is closely correlated with runoff seasonality in this region. The current implementation has demonstrated that DOC-related processes in the framework of LPJ-GUESS WHyMe are at an appropriate level of complexity to represent the main mechanism of DOC dynamics in soils. The quantified contributions

  20. Transient Dissolved Organic Carbon Through Soils

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    Dissolved organic carbon (DOC) is an important constituent of soil solution that plays a role in many chemical and biological processes in soils; it is also an important energy source for bacteria in the soil ecosystem. Hydrology has a significant control on the transport and fate of dissolved organic carbon in the soil but mechanisms that affect said transport are not well understood. In particular, dynamic information on DOC transport through forest soils on short time scales (one or two precipitation event) is lacking at present. DOC is a very complex mix of organic compounds. A key to quantifying DOC dynamics is to establish useful approximations for behavior of this complex mixture. Biodegradable dissolved organic carbon (BDOC) is an important part of DOC. It is reported that between 12 and 44% of DOC released from the forest floor can be decomposed in solutions by indigenous microbes. In our study, we considered how DOC, BDOC, and flow interact in soil columns. In-situ soil cores with two different lengths were installed under a mixed deciduous canopy. The effects of artificial rain on DOC and BDOC transport were examined by dripping nano pure water amended with bromide on the top of soil cores and sampling the water collected at the bottom of the cores for DOC and BDOC. We used plug-flow biofilm reactors to measure the BDOC concentration. It is likely that reduced rates of decomposition in dry soils will cause microbial products of DOC to accumulate; hence DOC concentration should be high at the first flush of rain and decline as the event proceeds. The experimental results show the expected pattern, that is, the first samples we collected always had the highest DOC and BDOC concentrations. The concentrations tend to decline through the simulated precipitation event. Application of a second “storm” forty minutes after the cessation of the first application of water resulted in effluent DOC concentration increasing a small amount initially and then

  1. Effect of model dissolved organic matter coating on sorption of phenanthrene by TiO2 nanoparticles.

    PubMed

    Wang, Xilong; Ma, Enxing; Shen, Xiaofang; Guo, Xiaoying; Zhang, Meng; Zhang, Haiyun; Liu, Ye; Cai, Fei; Tao, Shu; Xing, Baoshan

    2014-11-01

    Dissolved organic matter (DOM) may alter the sorption of hydrophobic organic contaminants (HOC) to metal oxide nanoparticles (NPs), but the role of DOM and NP types is poorly understood. Here, phenanthrene sorption was quantified on four types of nano-TiO2 (three rutile, one anatase), and a bulk, raw TiO2 powder. Prior to the sorption experiments, these nanoparticles were coated using four different organic materials: Lignin (LIG), tannic acid (TAN), Congo red (CON), and capsorubin (CAP). Lignin, tannic acid, congo red and capsorubin coating substantially enhanced phenanthrene sorption to various TiO2 particles. After coating with a specific DOM, Kd values by the DOM-coated TiO2 particles on percent organic carbon content and surface area (SA) basis (Koc/SA) generally followed the order: TiO2 NPs with hydrophobic surfaces > bulk TiO2 particles > other TiO2 NPs. Different Koc/SA values of various DOM-TiO2 complexes resulted from distinct conformation of the coated DOM and aggregation.

  2. 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.

  3. Temporal evolution of hyporheic dissolved organic carbon

    NASA Astrophysics Data System (ADS)

    Gabrielsen, P. J.

    2010-12-01

    Dissolved organic carbon (DOC) is a complex suite of organic compounds present in natural ecosystems, and is particularly studied in river systems. The hyporheic zone (HZ), a region of surface water-shallow groundwater exchange, has been identified as a hotspot of DOC processing and is generally regarded as a net sink of organic matter. More recent studies into riverine DOC have shifted to examining DOC quality rather than bulk quantity. DOC quality variability has been linked to hydrologic and climatic variability, both focuses of current climate change research. This presentation examines the effect of organic and inorganic HZ DOC processes, i.e. microbial uptake and sorption, respectively, on DOC quality as measured through molecular weight distributions (MWDs). Sediment and water samples from East Fork Jemez River in northern New Mexico are used to experimentally simulate DOC processes and observe the subsequent effect on MWD evolution. Parallel factor analysis (PARAFAC) of excitation-emission matrices (EEMs) is also used to examine fluorescent properties throughout DOC process experimentation, providing a second characterizing metric. Results from this study will be applied to a field sampling campaign in the summer of 2011 along the East Fork Jemez River to study temporal and spatial variability in organic and inorganic DOC processes.

  4. 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

  5. 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.

  6. Coupling GIS-based and Steady State Dissolved Organic Carbon Models for Export and Lake Retention in a Large Watershed on the Precambrian Shield

    NASA Astrophysics Data System (ADS)

    Molot, L. A.; Dillon, P. J.; Creed, I.; Beall, F.; Clair, T.

    2001-12-01

    A GIS-based regional model was coupled to steady state dissolved organic carbon (DOC) catchment export and lake retention models developed on small, calibrated headwater lakes in order to predict the fate of exported organic carbon from a large watershed. The coupled DOC export-retention model is driven by runoff and the extent of wetlands and is therefore hydrologically controlled. Lake, wetland, and catchment areas for 859 lakes in the Lake Muskoka watershed, situated on the Precambrian Shield in central Ontario, were estimated from a hydrologically conditioned, digital elevation model derived from Ontario Base Map elevation data (1:10,000). The 4770 km2 watershed has an average wetland cover of 4.9% with lakes covering 16.9%. The model predicted that almost half of DOC exported downstream from wetlands was stored in lake sediments or evaded to the atmosphere with the remainder discharged from Lake Muskoka to Georgian Bay in the Great Lakes. Predicted and observed DOC discharges from Lake Muskoka were similar as were predicted and observed lake concentrations of DOC. Predicted DOC discharge was also similar to predicted discharge from a same-sized watershed with 4.9% wetland but only one lake whose area was equal to the total area of the 859 lakes. Therefore, it appears that for the purpose of modeling DOC export, large regions of the Precambrian Shield with significant DOC inputs from wetlands (i.e., > 4.9% wetlands) can be treated as single-lake catchments.

  7. Spectrophotometric discrimination of river dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Baker, Andy

    2002-11-01

    There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic-like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic-like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

    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.

  10. 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.

  11. Developing and improving a simple runoff model of dissolved organic carbon considering soil infiltration and river runoff processes in a forested watershed

    NASA Astrophysics Data System (ADS)

    Ebata, K.; Ichikawa, Y.; Matsumoto, Y.; Nishida, K.

    2015-12-01

    Estimation of dissolved organic carbon (DOC) runoff from forested watershed is important for carbon cycle researches and water quality control. Recently, a few process-based models have been proposed to estimate DOC loading to water environments, which assume DOC source in topsoil and transport process to the river. However, the models require large number of input data and are not designed for short time scale calculation of intensive rainfall runoff with in Asian monsoon area. We proposed a new DOC runoff model with both soil and river runoff processes enforced by DOC Source Area (DSA) concept. The data were collected at middle stream (98ha) and downstream (1798ha) in the Mizugaki Experimental Watershed, Yamanashi, Japan from 2009 to 2012. Dry-wet cycle and long-term variation in soil were successfully simulated by advection-diffusion and dissolution formulations of the Soil Submodel. Runoff Submodel included hydrological calculation unit, TOPMODEL, to separately quantify base flow (Qb), subsurface flow (Qsf) and overland flow (Qof). Qsf and Qof were assumed to represent for DSA, and the DOC loading was calculated by Qsf, Qof and the estimated DOC concentration from the Soil Submodel. The results showed that the model performed well for 4 among 11 events at the middle stream while the simulated DOC loadings were overestimated for all 8 events downstream. The reason of the low performance of the model was attributed to the error of Qsf and Qof calculated by TOPMODEL.

  12. Dissolved Fe(II) in a river-estuary system rich in dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Hopwood, Mark J.; Statham, Peter J.; Milani, Ambra

    2014-12-01

    Reduced iron, Fe(II), accounts for a significant fraction of dissolved Fe across many natural surface waters despite its rapid oxidation under oxic conditions. Here we investigate the temporal and spatial variation in dissolved Fe redox state in a high dissolved organic matter (DOM) estuarine system, the River Beaulieu. We couple manual sample collection with the deployment of an autonomous in situ analyser, designed to simultaneously measure dissolved Fe(II) and total dissolved Fe, in order to investigate processes operating on the diurnal timescale and to evaluate the performance of the analyser in a high DOM environment. Concentrations of dissolved Fe available to the ligand ferrozine are elevated throughout the estuary (up to 21 μM in freshwater) and notably higher than those previously reported likely due to seasonal variation. Fe(II) is observed to account for a large, varying fraction of the dissolved Fe available to ferrozine (25.5 ± 12.5%) and this fraction decreases with increasing salinity. We demonstrate that the very high DOM concentration in this environment and association of this DOM with dissolved Fe, prevents the accurate measurement of dissolved Fe concentrations in situ using a sensor reliant on rapid competitive ligand exchange.

  13. Precipitates in landfill leachate mediated by dissolved organic matters.

    PubMed

    Li, Zhenze; Xue, Qiang; Liu, Lei; Li, Jiangshan

    2015-04-28

    Clogging of landfill leachate collection system is so ubiquitous that it causes problems to landfills. Although precipitations of calcite and other minerals have been widely observed, the mechanism of precipitation remains obscure. We examined the clog composition, dissolved organic matters, leachate chemical compositions and the correlation of these variables in view of the precipitation process. It is shown that Dissolved Organic Carbon (DOC) inhibits precipitation of landfill leachate. Using the advanced NICA-Donnan model, the analysis of aqueous chemical reactions between Mg-Ca-DOC-CO2 suggests a good agreement with experimental observations. Calcite and dolomite are both found to be oversaturated in most of the landfill leachate samples. DOC is found to preferentially bind with Mg than Ca, leading to more likely precipitation of Calcite than dolomite from landfill leachate. The NICA-Donnan model gives a reasonable estimation of dolomite saturation index in a wide range of DOC. Modeling confirms the major precipitation mechanism in terms of alkaline earth metal carbonate. Uncertainties in model parameters are discussed with particular focus on DOC composition, functional group types and density concentration and the influential factors. PMID:25661175

  14. Precipitates in landfill leachate mediated by dissolved organic matters.

    PubMed

    Li, Zhenze; Xue, Qiang; Liu, Lei; Li, Jiangshan

    2015-04-28

    Clogging of landfill leachate collection system is so ubiquitous that it causes problems to landfills. Although precipitations of calcite and other minerals have been widely observed, the mechanism of precipitation remains obscure. We examined the clog composition, dissolved organic matters, leachate chemical compositions and the correlation of these variables in view of the precipitation process. It is shown that Dissolved Organic Carbon (DOC) inhibits precipitation of landfill leachate. Using the advanced NICA-Donnan model, the analysis of aqueous chemical reactions between Mg-Ca-DOC-CO2 suggests a good agreement with experimental observations. Calcite and dolomite are both found to be oversaturated in most of the landfill leachate samples. DOC is found to preferentially bind with Mg than Ca, leading to more likely precipitation of Calcite than dolomite from landfill leachate. The NICA-Donnan model gives a reasonable estimation of dolomite saturation index in a wide range of DOC. Modeling confirms the major precipitation mechanism in terms of alkaline earth metal carbonate. Uncertainties in model parameters are discussed with particular focus on DOC composition, functional group types and density concentration and the influential factors.

  15. Method of dissolving organic filter cake

    SciTech Connect

    Hollenbeck, K.H.; Norman, L.R.

    1989-03-07

    A method of dissolving a polysaccharide-containing filter cake present in a subterranean formation is described, comprising: injecting an effective amount of a treatment fluid comprising a water soluble source of fluoride ions present in an amount sufficient to provide a molar concentration of from about 0.01 to about 0.5 and a source of hydrogen ions present in an amount sufficient to produce a pH in the treatment fluid in the range of from about 2 to about 4 into a subterranean formation wherein a filter cake is present; and maintaining the treatment fluid within the subterranean formation and in contact with the filter cake for a sufficient time to dissolve at least a portion of the filter cake.

  16. 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

  17. Seasonal Changes in Arctic Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Boot, C. M.; Wallenstein, M. D.; Schimel, J.

    2011-12-01

    The Arctic is a landscape in flux. Temperatures are shifting upward and plant communities are transitioning from tussock to shrub tundra in some regions. Decomposition processes sensitive to temperature, moisture, and plant inputs are controls on the source/sink dynamics of the Arctic C pool. The response of decomposition to warming will, in part, determine if the Arctic C pool feeds back positively or negatively to climate change. The portion of the C pool immediately available to decomposers is dissolved organic matter (DOM). The aim of this is study is to examine the molecular composition of DOM to determine which components vary seasonally in soil pore water among three vegetation types at Toolik Field Station in Alaska. Vegetation types include wet sedge (Carex aquatilis and Eriophorum angustifolium), moist acidic tussock (E. vaginatum) and shrub tundra (Betula nana and Salix sp.). These sites were sampled during winter/summer transitions in 2010 in order to capture both growing season and winter dynamics. We expected the chemical composition of DOM in pore water to be distinct among plant communities due to differences in root exudates, litter chemistry and microbial community; and vary seasonally due to shifting temperature and water availability and their impacts on decomposition of DOM. Soil pore water was isolated through centrifugation and is being characterized with ultra high performance liquid chromatography (UPLC) in line with a quadrupole time of flight mass spectrometer (QTOF-MS) as well as with specific UV absorbance at 254 nm (SUVA), and excitation emission matrices (EEMs) generated by fluorescence spectroscopy. The DOM concentrations across vegetation types show consistent seasonal patterns, spiking at thaw, and declining through late summer. As soils freeze these patterns diverge-in tussock soils DOM concentration decreases slightly, while in shrub and wet sedge sites it increases. SUVA values (indicator of aromaticity) were consistent among

  18. Spatio-temporal variation in the characteristics of dissolved organic matter in the streams of boreal forests: impacts on modelled copper speciation.

    PubMed

    Cuss, C W; Guéguen, C; Hill, E; Dillon, P J

    2010-08-01

    Dissolved organic matter (DOM) is an important constituent of natural waters that controls numerous biogeochemical processes such as the toxicity and mobility of metals. In order to predict how metals behave in the presence of DOM, it is necessary to understand its acidic properties. In this study, we report the variations in the acid character of aquatic organic acids using 30 years of sampling data collected from three boreal streams. Based on a charge balance model, significant spatial and temporal variation in carboxylic acid site density was observed. The seasonal average carboxylic group density ranged from 8.01 +/- 1.47 to 12.0 +/- 1.90 microeq mg C(-1) and the overall (multi-site) average site density (winter excluded) was 9.66 +/- 0.125 microeq mg C(-1) (n = 3193). Both different sources of DOM and seasonal differences in source availability were found to contribute to variations in site density. In the deciduous catchment where wetland contributions to DOM were negligible, the seasonal variability in site density was highly marked with increases of up to 50% observed between spring and fall. Less seasonal variation was noted at the coniferous sites, which had relatively high wetland source contributions. The geochemical equilibrium speciation model MINTEQA2 showed that the increase in site density observed from winter to fall coincided with a decrease in free copper concentration. We conclude that some source-based differences in DOM that may result from variation in both catchment characteristics and seasonal DOC loadings necessitate the determination of location-specific and/or seasonal site density values due to the resulting variability in metal speciation that has been predicted through modelling.

  19. Recent advances in structure and reactivity of dissolved organic matter: radiation chemistry of non-isolated natural organic matter and selected model compounds.

    PubMed

    Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Cottrell, Barbara A; Gonsior, Michael; Cooper, William J

    2012-01-01

    The importance of natural organic matter (NOM) as a source of carbon in natural waters, as the source of reactive oxygen species, or for the complications its presence causes in treatment of natural waters, is undeniable. Recent studies have also pointed to the major photochemical role of triplet excited state of natural organic matter in the environmental fate of pharmaceutical and personal care products (PPCPs) in waters. However, the characterization of NOM is problematic due to its complex molecular structure. One approach to better understand NOM chemistry is the use of model compounds. As the condensation of a plant's phenolic compounds leads to humification and the formation of NOM, a structurally broad group of nine phenolic compounds were selected as model compounds for this study. With methods used in the discipline of radiation chemistry, the oxidative chemistry and transient spectra of these phenols were studied. In addition, the oxidative chemistry and transient spectra of a sample of NOM from the Black River, North Carolina, USA, was characterized. This natural water sample was used as received and represents the first studies of non-isolated NOM by pulsed radiolysis. The results of the transient spectra of the NOM revealed that the radical intermediates were very long lived. This phenomenon was not captured using the nine model compounds suggesting that more complex compounds are needed to further our understanding of the oxidation chemistry of NOM.

  20. Dissolved Organic Matter in the Hudson River Plume

    NASA Astrophysics Data System (ADS)

    Chen, R. F.; Gardner, G. B.

    2004-12-01

    As part of the LATTE (Lagrangian Transport and Transformation Experiment) program, dissolved organic carbon (DOC), total nitrogen (TN), and chromophoric dissolved organic matter (CDOM) were measured in the Hudson River Estuary and Plume. As revealed by high resolution measurements from the Integrated Coastal Observation System (ICOS), dissolved organic matter has several sources within the estuary including the Hudson and Raritan Rivers, and a yet unidentified anthropogenic source off Manhattan. The quantity of dissolved organic matter that is exported from the Hudson River Estuary is significantly greater than that which the Hudson River can supply by simply conservative mixing with coastal seawater. In May, 2004, rhodamine dye was injected at the surface as the plume flowed out onto the New York/New Jersey shelf, once as the plume turned north towards Long Island, and once as the plume flowed south along the New Jersey coast. The ECOShuttle (a towed-undulating vehicle) carrying a rhodamine fluorometer was able to track these dye patches. An examination of dissolved organic matter transformations that occurred over these two to two and one-half day Lagrangian experiments will be discussed. In addition seasonal distributions of dissolved organic matter distributions will be presented from cruises in June 2003, June 2004 and September 2004 under different river flow and wind conditions.

  1. 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.

  2. 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.

  3. Influence of dissolved organic materials on turbid water optical properties and remote-sensing reflectance

    NASA Technical Reports Server (NTRS)

    Witte, W. G.; Whitlock, C. H.; Harriss, R. C.; Usry, J. W.; Poole, L. R.; Houghton, W. M.; Morris, W. D.; Gurganus, E. A.

    1982-01-01

    The effects of dissolved organic materials on turbid-water optical properties are assessed, by means of field measurements and laboratory simulations in which upwelled reflectance, attenuation, absorption, and backscatter spectral properties at wavelengths from 450 to 800 nm are examined in relation to water chemistry. The data show that dissolved organic materials decrease upwelled reflectance from turbid waters, and that the decrease in reflectance is a nonlinear function of concentration with the largest gradients at low carbon concentrations, depending on wavelength. Upwelled reflectance is found to be highly correlated with two backscatter-absorption parameters used in some optical models, which are nonlinear with dissolved organic material concentration change.

  4. 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

  5. Dissolved organic carbon and dissolved organic nitrogen export from forested watersheds in Nova Scotia: Identifying controlling factors

    NASA Astrophysics Data System (ADS)

    Aitkenhead-Peterson, J. A.; Alexander, J. E.; Clair, T. A.

    2005-12-01

    Riverine nutrient export represents a transfer of terrestrial nutrients to lakes, estuaries and the near-coastal zone. In this study, we constructed regional predictive models for riverine dissolved organic carbon (DOC) and organic nitrogen (DON) exports. We used a subset of 10 watersheds to construct regional empirical models of DOC and DON export, reserving two watersheds for testing the predictive ability of each model. For the subset of 10 watersheds, mean watershed soil column C:N ratio explained 75% of the variance in DOC export and 73% of the variance in DON export (p < 0.01). Organic C:N explained 63% and 71% of the variance in DOC and DON exports, respectively. There was a stronger relationship between riverine DOC:DON ratio and mineral soil C:N (R2 = 0.77 p < 0.001) than with organic C:N (R2 = 0.49 p < 0.05), suggesting that de-coupling of DOC and DON dynamics in rivers may occur when hydrologic flow paths favor organic layers. We suggest that mean watershed soil C:N ratio is likely to be an integrator of several controls on riverine DOC export including temperature and precipitation (climatic control), soil texture and nutrient status (edaphic control), vegetative species and their associated micro-flora (biological control) and watershed topography (topographical control). Soil C:N appears to be a useful tool for predicting variability in both DOC and DON flux at a regional scale.

  6. Utilizing Colored Dissolved Organic Matter to Derive Dissolved Black Carbon Export by Arctic Rivers

    NASA Astrophysics Data System (ADS)

    Stubbins, Aron; Spencer, Robert; Mann, Paul; Holmes, R.; McClelland, James; Niggemann, Jutta; Dittmar, Thorsten

    2015-10-01

    Wildfires have produced black carbon (BC) since land plants emerged. Condensed aromatic compounds, a form of BC, have accumulated to become a major component of the soil carbon pool. Condensed aromatics leach from soils into rivers, where they are termed dissolved black carbon (DBC). The transport of DBC by rivers to the sea is a major term in the global carbon and BC cycles. To estimate Arctic river DBC export, 25 samples collected from the six largest Arctic rivers (Kolyma, Lena, Mackenzie, Ob’, Yenisey and Yukon) were analyzed for dissolved organic carbon (DOC), colored dissolved organic matter (CDOM), and DBC. A simple, linear regression between DOC and DBC indicated that DBC accounted for 8.9 ± 0.3% DOC exported by Arctic rivers. To improve upon this estimate, an optical proxy for DBC was developed based upon the linear correlation between DBC concentrations and CDOM light absorption coefficients at 254 nm (a254). Relatively easy to measure a254 values were determined for 410 Arctic river samples between 2004 and 2010. Each of these a254 values was converted to a DBC concentration based upon the linear correlation, providing an extended record of DBC concentration. The extended DBC record was coupled with daily discharge data from the six rivers to estimate riverine DBC loads using the LOADEST modeling program. The six rivers studied cover 53% of the pan-Arctic watershed and exported 1.5 ± 0.1 million tons of DBC per year. Scaling up to the full area of the pan-Arctic watershed, we estimate that Arctic rivers carry 2.8 ± 0.3 million tons of DBC from land to the Arctic Ocean each year. This equates to ~8% of Arctic river DOC export, slightly less than indicated by the simpler DBC vs DOC correlation-based estimate. Riverine discharge is predicted to increase in a warmer Arctic. DBC export was positively correlated with river runoff, suggesting that the export of soil BC to the Arctic Ocean is likely to increase as the Arctic warms.

  7. Estimating the Age Distribution of Oceanic Dissolved Organic Carbon

    NASA Astrophysics Data System (ADS)

    Follett, C. L.; Forney, D. C.; Repeta, D.; Rothman, D.

    2010-12-01

    Dissolved organic carbon (DOC) is a large, ubiquitous component of open ocean water at all depths and impacts atmospheric carbon dioxide levels at both short and long timescales. It is currently believed that oceanic DOC contains a multi-thousand-year-old refractory deep-water component which is mixed with a young labile component in surface waters. Unfortunately, the only evidence for this comes from a few isolated depth profiles of both DOC concentration and bulk radiocarbon. Although the profile data is consistent with a two-component mixing model, directly separating the two components has proven to be a challenge. We explore the validity of the two component mixing model by directly estimating the age distribution of oceanic DOC. The two-component model suggests that the age distribution is composed of two distinct peaks. In order to obtain an estimate of the age distribution we first record changes in both concentration and percent radiocarbon as a sample is oxidized under ultra-violet radiation [1]. We formulate a mathematical model relating the age distribution to these changes, assuming that they result from components of different radiocarbon age and UV-reactivity. This allows us to numerically invert the data and estimate the age distribution. We apply our procedure to DOC samples collected from three distinct depths (50, 500, and 2000 meters) in the north-central Pacific Ocean. [1] S.R. Beaupre, E.R.M. Druffel, and S. Griffin. A low-blank photochemical extraction system for concentration and isotopic analyses of marine dissolved organic carbon. Limnol. Oceanogr. Methods, 5:174-184, 2007.

  8. 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

  9. Latitudinal Gradients in Degradation of Marine Dissolved Organic Carbon

    PubMed Central

    Arnosti, Carol; Steen, Andrew D.; Ziervogel, Kai; Ghobrial, Sherif; Jeffrey, Wade H.

    2011-01-01

    Heterotrophic microbial communities cycle nearly half of net primary productivity in the ocean, and play a particularly important role in transformations of dissolved organic carbon (DOC). The specific means by which these communities mediate the transformations of organic carbon are largely unknown, since the vast majority of marine bacteria have not been isolated in culture, and most measurements of DOC degradation rates have focused on uptake and metabolism of either bulk DOC or of simple model compounds (e.g. specific amino acids or sugars). Genomic investigations provide information about the potential capabilities of organisms and communities but not the extent to which such potential is expressed. We tested directly the capabilities of heterotrophic microbial communities in surface ocean waters at 32 stations spanning latitudes from 76°S to 79°N to hydrolyze a range of high molecular weight organic substrates and thereby initiate organic matter degradation. These data demonstrate the existence of a latitudinal gradient in the range of complex substrates available to heterotrophic microbial communities, paralleling the global gradient in bacterial species richness. As changing climate increasingly affects the marine environment, changes in the spectrum of substrates accessible by microbial communities may lead to shifts in the location and rate at which marine DOC is respired. Since the inventory of DOC in the ocean is comparable in magnitude to the atmospheric CO2 reservoir, such a change could profoundly affect the global carbon cycle. PMID:22216139

  10. 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.

  11. 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...

  12. 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…

  13. [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.

  14. 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.

  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. Photoinactivation of Staphylococcus aureus and Vibrio parahaemolyticus in the model aquatic microcosm: effect of light intensity and dissolved biodegradable organic compound.

    PubMed

    Nola, Moïse; Matchim, Armelle G Simo; Mobili, Olga Blanche; Nougang, Mireille; Krier, François; Chihib, Nour-Eddine; Hornez, Jean-Pierre; Njiné, Thomas

    2010-01-01

    The impact of light (1,000 × 100,000 lx) on the inactivation of S. aureus and V. parahaemolyticus has been assessed under different concentrations of dissolved biodegradable organic compound (BOC) at pH 7.0. First, a gradual decrease in the number of cultivable cells was observed. Secondly, a cell reactivation was observed and it was marked in the absence of BOC. In the absence of BOC, the lowest value of cell inhibition rate (CIR) during the first 3 h was 0.138 h(-1) for S. aureus and 0.218 h(-1) for V. parahaemolyticus. In the presence of 10,100 and 1,000 mg/l of BOC, it was 0.196 h(-1), 0.243 h(-1) and 0.257 h(-1) for S. aureus respectively, and 0.285 h(-1), 0.306 h(-1) and 0.409 h(-1) for V. parahaemolyticus respectively. The CIRs values of each bacterial species significantly varied (P<0.001) with the changes in BOC concentration. In most cases, no significant difference was noted in the CIRs of both species when they were under the same light intensity and BOC. Nevertheless, it seems important to consider the impact of dissolved BOC during the treatment of bacterial polluted water. PMID:20962392

  17. Unimodal response of fish yield to dissolved organic carbon.

    PubMed

    Finstad, Anders G; Helland, Ingeborg P; Ugedal, Ola; Hesthagen, Trygve; Hessen, Dag O

    2014-01-01

    Here, we demonstrate a contrasting effect of terrestrial coloured dissolved organic material on the secondary production of boreal nutrient poor lakes. Using fish yield from standardised brown trout gill-net catches as a proxy, we show a unimodal response of lake secondary productivity to dissolved organic carbon (DOC). This suggests a trade-off between positive and negative effects, where the initial increase may hinge upon several factors such as energy subsidising, screening of UV-radiation or P and N load being associated with organic carbon. The subsequent decline in production with further increase in DOC is likely associated with light limitations of primary production. We also show that shallow lakes switch from positive to negative effects at higher carbon loads than deeper lakes. These results underpin the major role of organic carbon for structuring productivity of boreal lake ecosystems. PMID:24165396

  18. 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

  19. Predicting dissolved organic nitrogen export from a drained loblolly pine plantation

    NASA Astrophysics Data System (ADS)

    Tian, Shiying; Youssef, Mohamed A.; Skaggs, R. Wayne; Chescheir, G. M.; Amatya, Devendra M.

    2013-04-01

    Dissolved organic nitrogen (DON) export from terrestrial ecosystems influences the ecology of receiving surface waters. The soil carbon (C) and nitrogen (N) model, DRAINMOD-N II, was modified to simulate key processes associated with DON transformations and transport in the soil profile. DON production is modeled by tracking dynamic C:N ratios of dissolved organic matter originating from various organic matter pools. The Langmuir isotherm was used to quantify the assumed instantaneous equilibrium between potentially soluble organic N in solid and aqueous phases. DON transport with soil water was simulated using a numerical solution to the advection-dispersion reaction equation. The modified model was used for simulating temporal variations of DON export from three loblolly pine (Pinus taeda L.) plantations located in eastern North Carolina. Results showed that the model can accurately predict DON export dynamics during storm events with Nash-Sutcliffe efficiency (E) of 0.5, seasonal DON losses with E above 0.6, and annual DON losses with E above 0.7. In addition to the well-recognized role of hydrological processes, reasonable quantifications of the seasonal changes in the potentially soluble soil organic matter, the DON sorption to soil particles, and the dynamic C:N ratios of dissolved organic matter were found to be essential for mechanistic representation of DON export dynamics. Specifically, adapting the dynamic C:N ratios enabled the model to reasonably describe the temporal variations of correlations between DON and dissolved organic carbon in drainage water.

  20. Iron traps terrestrially derived dissolved organic matter at redox interfaces.

    PubMed

    Riedel, Thomas; Zak, Dominik; Biester, Harald; Dittmar, Thorsten

    2013-06-18

    Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters. PMID:23733946

  1. Chemical composition of dissolved organic nitrogen in the ocean

    NASA Astrophysics Data System (ADS)

    McCarthy, Matthew; Pratum, Tom; Hedges, John; Benner, Ronald

    1997-11-01

    Fixed nitrogen is one of the main limiting nutrients for primary production in the ocean, where it is biologically available in the form of dissolved inorganic and organic matter. Inorganic nitrogen concentrations are consequently very low in surface waters of temperate ocean gyres, yet fixed nitrogen persists in the form of dissolved organic matter. The small, rapidly cycling organic compounds fundamental to microbial and planktonic growth (such as free amino acids, amines and urea) account for only a minor fraction of total dissolved organic nitrogen (DON). In contrast, the vast majority of DON, especially in the deep ocean, resides in the form of nitrogenous substances that are resistant to biological degradation. These substances, which represent an enormous reservoir of fixed nitrogen, are not readily identified by conventional biochemical techniques, but have been assumed to consist largely of structurally complex macromolecules resulting from the degradation and spontaneous abiotic condensation of biochemical precursors. Here we present 15N NMR measurements that contradict this view. Our results show that most higher-molecular-weight DON in the ocean exists in amide form, rather than as a collection of nitrogen heterocycles that might be indicative of spontaneous condensation products. Because these amides are unlikely to form abiotically, the bulk of the ocean's DON reservoir appears to derive directly from degradation-resistant biomolecules.

  2. 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.

  3. 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

  4. Effect of bacteria and dissolved organics on mineral dissolution kinetics:

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

    2010-05-01

    Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and

  5. The Oxidant Budget of Dissolved Organic Carbon Driven Isotope Excursions

    NASA Astrophysics Data System (ADS)

    Bristow, T. F.; Kennedy, M. J.

    2008-12-01

    Negative carbon isotope values, falling below the mantle average of about -5 per mil, in carbonate phases of Ediacaran age sedimentary rocks are widely regarded as reflecting negative excursions in the carbon isotopic composition of seawater lasting millions of years. These isotopic signals form the basis of chemostratigraphic correlations between Ediacaran aged sections in different parts of the world, and have been used to track the oxidation of the biosphere. However, these isotopic values are difficult to accommodate within limits prescribed by the current understanding of the carbon cycle, and a hypothetical Precambrian ocean dissolved organic carbon (DOC) pool 100 to 1000 times the size of the modern provides a potential source of depleted carbon not considered in Phanerozoic carbon cycle budgets. We present box model results that show the remineralization of such a DOC pool to drive an isotope excursion of the magnitude observed in the geological record exhausts global budgets of free oxygen and sulfate in 800 k.y. These results are incompatible with the estimated duration of late Ediacaran isotope excursions of more than 10 m.y., as well as geochemical and biological indicators that oceanic sulfate and oxygen levels were maintained or even increased at the same time. Therefore the carbon isotope record is probably not a useful tool for monitoring oxygen levels in the atmosphere and ocean. Covariation between the carbon and oxygen isotope records is often observed during negative excursions and is indicative of local processes or diagenetic overprinting.

  6. Monitoring dissolved organic carbon in surface and drinking waters.

    PubMed

    Volk, Christian; Wood, Larry; Johnson, Bruce; Robinson, Jeff; Zhu, Hai Wei; Kaplan, Louis

    2002-02-01

    The presence of natural organic matter (NOM) strongly impacts drinking water treatment, water quality, and water behavior during distribution. Dissolved organic carbon (DOC) concentrations were determined daily over a 22 month period in river water before and after conventional drinking water treatment using an on-line total organic carbon (TOC) analyzer. Quantitative and qualitative variations in organic matter were related to precipitation and runoff, seasons and operating conditions. Following a rainfall event, DOC levels could increase by 3.5 fold over baseflow concentrations, while color, UV absorbance values and turbidity increased by a factor of 8, 12 and 300, respectively. Treated water DOC levels were closely related to the source water quality, with an average organic matter removal of 42% after treatment.

  7. 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.

  8. 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

  9. Why dissolved organic matter (DOM) enhances photodegradation of methylmercury

    SciTech Connect

    Qian, Yun; Yin, Xiangping Lisa; Brooks, Scott C; Liang, Liyuan; Gu, Baohua

    2014-01-01

    Methylmercury (MeHg) is known to degrade photochemically, but it remains unclear what roles naturally dissolved organic matter (DOM) and complexing organic ligands play in MeHg photodegradation. Here we investigate the rates and mechanisms of MeHg photodegradation using DOM samples with varying oxidation states and origins as well as organic ligands with known molecular structures. All DOM and organic ligands increased MeHg photodegradation under solar irradiation, but the first-order rate constants varied depending on the oxidation state of DOM and the type and concentration of the ligands. Compounds containing both thiols and aromatics (e.g., thiosalicylate and reduced DOM) increased MeHg degradation rates far greater than those containing only aromatic or thiol functional groups (e.g., salicylate or glutathione). Our results suggest that, among other factors, the synergistic effects of thiolate and aromatic moieties in DOM greatly enhance MeHg photodegradation.

  10. Cosorption study of organic pollutants and dissolved organic matter in a soil.

    PubMed

    Flores-Céspedes, F; Fernández-Pérez, M; Villafranca-Sánchez, M; González-Pradas, E

    2006-08-01

    In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.

  11. Adsorption of paraquat on soil organic matter: effect of exchangeable cations and dissolved organic carbon.

    PubMed

    Gondar, Dora; López, Rocío; Antelo, Juan; Fiol, Sarah; Arce, Florencio

    2012-10-15

    Herbicides that interact with soil organic matter do so with both the solid and the dissolved fractions, so that the distribution of herbicide between the soil solution and solid phases is determined by competitive effects. In the present study, adsorption experiments were carried out with the cationic herbicide paraquat and untreated and acid-washed samples of a peat soil, at different values of pH and ionic strength. Less herbicide was adsorbed onto the untreated peat than onto the acid-washed peat; the difference was due to the presence of exchangeable cations, as demonstrated in experiments carried out by adding Ca(2+) to suspensions of acid-washed peat. The results were interpreted by an electrostatic model and the fitting parameters indicated that the adsorption constants were the same for both samples of peat, although the number of binding sites available was different. Simultaneous resolution of the adsorption equilibrium of paraquat for the soil organic matter (SOM) and of the binding equilibrium between paraquat and dissolved organic matter (DOM) enabled the distribution of paraquat between the solid and solution phases to be determined. The increased solubility of the SOM with increasing pH led to a decrease in the fraction of paraquat retained on the peat surface above pH 5.5, which favors the mobility of the herbicide in the soil.

  12. Importance of Dissolved Organic Nitrogen to Water Quality in Narragansett Bay

    EPA Science Inventory

    This preliminary analysis of the importance of the dissolved organic nitrogen (DON) pool in Narragansett Bay is being conducted as part of a five-year study of Narragansett Bay and its watershed. This larger study includes water quality and ecological modeling components that foc...

  13. Spectroscopic characterization of dissolved organic matter isolated from rainwater.

    PubMed

    Santos, Patrícia S M; Otero, Marta; Duarte, Regina M B O; Duarte, Armando C

    2009-02-01

    Rainwater is a matrix containing extremely low concentrations (in the range of muM C) of dissolved organic carbon (DOC) and for its characterization, an efficient extraction procedure is essential. A recently developed procedure based on adsorption onto XAD-8 and XAD-4 resins in series was used in this work for the extraction and isolation of rainwater dissolved organic matter (DOM). Prior to the isolation and fractionation of DOM, and to obtain sufficient mass for the spectroscopic analyses, individual rainwater samples were batched together according to similar meteorological conditions on a total of three composed samples. The results of the isolation procedure indicated that the resin tandem procedure is not applicable for rainwater DOM since the XAD-4 resin caused samples contamination. On the other hand, the XAD-8 resin allowed DOM recoveries of 39.9-50.5% of the DOC of the original combined samples. This recovered organic fraction was characterized by UV-visible, molecular fluorescence, FTIR-ATR and 1H NMR spectroscopies. The chemical characterization of the rainwater DOM showed that the three samples consist mostly of hydroxylated and carboxylic acids with a predominantly aliphatic character, containing a minor component of aromatic structures. The obtained results suggest that the DOM in rainwater, and consequently in the precursor atmospheric particles, may have a secondary origin via the oxidation of volatile organic compounds from different origins.

  14. 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.

  15. 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.

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

    PubMed Central

    Jagadamma, Sindhu; Mayes, Melanie A.; Phillips, Jana R.

    2012-01-01

    Background Physico-chemical sorption onto soil minerals is one of the major processes of dissolved organic carbon (OC) stabilization in deeper soils. The interaction of DOC on soil solids is related to the reactivity of soil minerals, the chemistry of sorbate functional groups, and the stability of sorbate to microbial degradation. This study was conducted to examine the sorption of diverse OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols, Ultisols and Alfisols). Methodology Equilibrium batch experiments were conducted using 0–100 mg C L−1 at a solid-solution ratio of 1∶60 for 48 hrs on natural soils and on soils sterilized by γ-irradiation. The maximum sorption capacity, Qmax and binding coefficient, k were calculated by fitting to the Langmuir model. Results Ultisols appeared to sorb more glucose, alanine, and salicylic acid than did Alfisols or Mollisols and the isotherms followed a non-linear pattern (higher k). Sterile experiments revealed that glucose and alanine were both readily degraded and/or incorporated into microbial biomass because the observed Qmax under sterile conditions decreased by 22–46% for glucose and 17–77% for alanine as compared to non-sterile conditions. Mollisols, in contrast, more readily reacted with oxalic acid (Qmax of 886 mg kg−1) and sinapyl alcohol (Qmax of 2031 mg kg−1), and no degradation was observed. The reactivity of Alfisols to DOC was intermediate to that of Ultisols and Mollisols, and degradation followed similar patterns as for Ultisols. Conclusion This study demonstrated that three common temperate soil orders experienced differential sorption and degradation of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC. PMID:23209742

  17. 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.

  18. Qualitative changes of riverine dissolved organic matter at low salinities due to flocculation

    NASA Astrophysics Data System (ADS)

    Asmala, Eero; Bowers, David G.; Autio, Riitta; Kaartokallio, Hermanni; Thomas, David N.

    2014-10-01

    The flocculation of dissolved organic matter (DOM) was studied along transects through three boreal estuaries. Besides the bulk concentration parameters, a suite of DOM quality parameters were investigated, including colored DOM (CDOM), fluorescent DOM, and the molecular weight of DOM as well as associated dissolved iron concentrations. We observed significant deviations from conservative mixing at low salinities (<2) in the estuarine samples of dissolved organic carbon (DOC), UV absorption (a(CDOM254)), and humic-like fluorescence. The maximum deviation from conservative mixing for DOC concentration was -16%, at salinities between 1 and 2. An associated laboratory experiment was conducted where an artificial salinity gradient between 0 and 6 was created. The experiment confirmed the findings from the estuarine transects, since part of the DOC and dissolved iron pools were transformed to particulate fraction (>0.2 µm) and thereby removing them from the dissolved phase. We also measured flocculation of CDOM, especially in the UV region of the absorption spectrum. Protein-like fluorescence of DOM decreased, while humic-like fluorescence increased because of salt-induced flocculation. Additionally, there was a decrease in molecular weight of DOM. Consequently, the quantity and quality of the remaining DOM pool was significantly changed after influenced to flocculation. Based on these results, we constructed a mechanistic, two-component flocculation model. Our findings underline the importance of the coastal filter, where riverine organic matter is flocculated and exported to the sediments.

  19. Dissolved organic matter export from a forested watershed during Hurricane Irene

    NASA Astrophysics Data System (ADS)

    Yoon, Byungman; Raymond, Peter A.

    2012-09-01

    We incorporate high-resolution time-series data to calculate the total amount of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) transported during Hurricane Irene in Esopus Creek in New York (August 2011). During this 200-yr event the Esopus Creek experienced a 330-fold discharge increase and a 4-fold increase in concentration, resulting in the export of roughly 43% and 31% of its average annual DOC and DON fluxes, respectively, in just 5 days. The source of this large dissolved organic matter (DOM) flux also shifted during its course and showed an increased contribution of aromatic organic matter. We conclude that more frequent large events due to climate change will increase the export of terrigenous dissolved organic matter, and potentially impact the water quality and biogeochemistry of lakes and coastal systems. In addition, we show that the use of conventional models for extreme events lead to erroneous flux calculations, unless supported by high resolution data collected during the events.

  20. Molecular-level dynamics of refractory dissolved organic matter

    NASA Astrophysics Data System (ADS)

    Niggemann, J.; Gerdts, G.; Dittmar, T.

    2012-04-01

    Refractory dissolved organic matter (DOM) accounts for most of the global oceanic organic carbon inventory. Processes leading to its formation and factors determining its stability are still largely unknown. We hypothesize that refractory DOM carries a universal molecular signature. Characterizing spatial and temporal variability in this universal signature is a key to understanding dynamics of refractory DOM. We present results from a long-term study of the DOM geo-metabolome in the open North Sea. Geo-metabolomics considers the entity of DOM as a population of compounds, each characterized by a specific function and reactivity in the cycling of energy and elements. Ten-thousands of molecular formulae were identified in DOM by ultrahigh resolution mass spectrometry analysis (FT-ICR-MS, Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry). The DOM pool in the North Sea was influenced by a complex interplay of processes that produced, transformed and degraded dissolved molecules. We identified a stable fraction in North Sea DOM with a molecular composition similar to deep ocean DOM. Molecular-level changes in this stable fraction provide novel information on dynamics and interactions of refractory DOM.

  1. 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. PMID:27172378

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    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.

  3. Chromophoric Dissolved Organic Matter Export from U.S. Rivers

    NASA Astrophysics Data System (ADS)

    Spencer, R. G.; Aiken, G.; Dornblaser, M.; Butler, K. D.; Holmes, R. M.; Fiske, G.; Mann, P. J.; Stubbins, A.

    2012-12-01

    Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. Utilizing CDOM and dissolved organic carbon (DOC) flux data we establish a robust universal relationship between CDOM and DOC loads. The application of this relationship allows future studies to derive DOC loads from CDOM utilizing emerging in-situ or remote sensing technologies and thus refine river-to-ocean DOC fluxes, as well as exploit historic imagery to examine how fluxes may have changed. Calculated CDOM yields from the 15 U.S. rivers highlight the importance of certain regions with respect to CDOM flux to the coastal ocean. This approach indicates that future studies might predict CDOM and DOC yields for different watershed types that could then be readily converted to loads providing for the estimation of CDOM and DOC export from ungauged watersheds. Examination of CDOM yields also highlights important geographical regions for future study with respect to the role of terrigenous CDOM in ocean color budgets and CDOM's role in biogeochemical processes.

  4. Groundwater-transported dissolved organic nitrogen exports from coastal watersheds

    USGS Publications Warehouse

    Kroeger, K.D.; Cole, Marci L.; Valiela, I.

    2006-01-01

    We analyzed groundwater-transported nitrogen (N) exports from 41 watershed segments that comprised 10 Cape Cod, Massachusetts watersheds to test the hypotheses that chemical form of N exports is related to land use and to length of flow paths through watersheds. In the absence of human habitation, these glacial outwash-plain watersheds exported largely dissolved organic N (DON) but at relatively low annual rate. Addition of people to watersheds increased rates of both total dissolved N (TDN) and DON export through groundwater. Percent of TDN as DON in groundwater was negatively related to path length of groundwater through aquifers, but %DON was not significantly related to population density on the watersheds. DON was often the dominant form of N exported from the watersheds, even at high population densities. Our results suggest that natural sources are not entirely responsible for organic N exports from watersheds, but, instead, a substantial portion of anthropogenic N introduced to watersheds is exported as DON. This finding is in disagreement with previous results, which suggest that anthropogenic N is exported from watersheds largely as NO 3- and that DON exported from watersheds is from natural sources. ?? 2006, by the American Society of Limnology and Oceanography, Inc.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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...

  11. 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...

  12. 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.

  13. 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...

  14. 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.

  15. 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

  16. Climate Variability, Dissolved Organic Carbon, UV Exposure, and Amphibian Decline

    NASA Astrophysics Data System (ADS)

    Brooks, P. D.; O'Reilly, C. M.; Diamond, S.; Corn, S.; Muths, E.; Tonnessen, K.; Campbell, D. H.

    2001-12-01

    Increasing levels of UV radiation represent a potential threat to aquatic organisms in a wide range of environments, yet controls on in situ variability on UV exposure are relatively unknown. The primary control on the penetration of UV radiation in surface water environments is the amount of photoreactive dissolved organic carbon (DOC). Consequently, biogeochemical processes that control the cycling of DOC also affect the exposure of aquatic organisms to UV radiation. Three years of monitoring UV extinction and DOC composition in Rocky Mountain, Glacier, Sequoia/ Kings Canyon, and Olympic National Parks demonstrate that the amount of fulvic acid DOC is much more important than the total DOC pool in controlling UV attenuation. This photoreactive component of DOC originates primarily in soil, and is subject both to biogeochemical controls (e.g. temperature, moisture, vegetation, soil type) on production, and hydrologic controls on transport to surface water and consequently UV exposure to aquatic organisms. Both of these controls are positively related to precipitation with greater production and transport associated with higher precipitation amounts. For example, an approximately 20 percent reduction in precipitation from 1999 to 2000 resulted in a 27% - 59% reduction in the amount of photoreactive DOC at three sites in Rocky Mountain National Park. These differences in the amount of hydrophobic DOC result in an increase in UV exposure in the aquatic environment by a factor of 2 or more. Implications of these findings for observed patterns of amphibian decline will be discussed.

  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. 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

    2015-01-01

    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. PMID:25704539

  19. Molecular characterization of dissolved organic matter (DOM): a critical review.

    PubMed

    Nebbioso, Antonio; Piccolo, Alessandro

    2013-01-01

    Advances in water chemistry in the last decade have improved our knowledge about the genesis, composition, and structure of dissolved organic matter, and its effect on the environment. Improvements in analytical technology, for example Fourier-transform ion cyclotron (FT-ICR) mass spectrometry (MS), homo and hetero-correlated multidimensional nuclear magnetic resonance (NMR) spectroscopy, and excitation emission matrix fluorimetry (EEMF) with parallel factor (PARAFAC) analysis for UV-fluorescence spectroscopy have resulted in these advances. Improved purification methods, for example ultrafiltration and reverse osmosis, have enabled facile desalting and concentration of freshly collected DOM samples, thereby complementing the analytical process. Although its molecular weight (MW) remains undefined, DOM is described as a complex mixture of low-MW substances and larger-MW biomolecules, for example proteins, polysaccharides, and exocellular macromolecules. There is a general consensus that marine DOM originates from terrestrial and marine sources. A combination of diagenetic and microbial processes contributes to its origin, resulting in refractory organic matter which acts as carbon sink in the ocean. Ocean DOM is derived partially from humified products of plants decay dissolved in fresh water and transported to the ocean, and partially from proteinaceous and polysaccharide material from phytoplankton metabolism, which undergoes in-situ microbial processes, becoming refractory. Some of the DOM interacts with radiation and is, therefore, defined as chromophoric DOM (CDOM). CDOM is classified as terrestrial, marine, anthropogenic, or mixed, depending on its origin. Terrestrial CDOM reaches the oceans via estuaries, whereas autochthonous CDOM is formed in sea water by microbial activity; anthropogenic CDOM is a result of human activity. CDOM also affects the quality of water, by shielding it from solar radiation, and constitutes a carbon sink pool. Evidence in support

  20. Photodegradation of dissolved organic matter in ice under solar irradiation.

    PubMed

    Xue, Shuang; Wang, Chao; Zhang, Zhaohong; Song, Youtao; Liu, Qiang

    2016-02-01

    The photodegradation behavior of dissolved organic matter (DOM) with different origins in ice under solar irradiation was investigated. Exposure to sunlight at 2.7 × 10(5) J m(-2) resulted in dissolved organic carbon (DOC) reductions of 22.1-36.5% in ice. The naturally occurring DOM had higher photodegradation potentials than the wastewater-derived DOM in ice. Ultraviolet (UV)-absorbing compounds in DOM, regardless of DOM origin, had much higher photodegradation potentials than gross DOC in ice. The susceptibility of UV-absorbing compounds with natural origin to sunlight exposure in ice was higher than those derived from wastewater. Trihalomethane (THM) precursors were more susceptible to photochemical reactions than gross DOC and haloacetic acid (HAA) precursors in ice. THM precursors in naturally occurring DOM were more photoreactive than those in wastewater-derived DOM in ice, while the photoreactivity of HAA precursors in ice was independent of DOM origin. In ice, the photoreactivity of humic-like fluorescent materials, regardless of DOM origin, was higher than that of gross DOC and protein-like fluorescent materials. DOC reductions caused by sunlight irradiation were found to be negatively correlated to DOC levels, and positively correlated to the aromaticity of DOM. The photodegradation of both wastewater-derived and naturally occurring DOM in ice was significantly facilitated at both acid and alkaline pH, as compared to neutral pH. The photodegradation of DOM in ice, regardless of the origin, was facilitated by nitrate ion [Formula: see text] , nitrite ion [Formula: see text] , ferric ion (Fe(3+)) and ferrous ion (Fe(2+)), and on the other hand, was inhibited by chloridion ion (Cl(-)) and copper ion (Cu(2+)).

  1. Dissolved organic carbon and its potential predictors in eutrophic lakes.

    PubMed

    Toming, Kaire; Kutser, Tiit; Tuvikene, Lea; Viik, Malle; Nõges, Tiina

    2016-10-01

    Understanding of the true role of lakes in the global carbon cycle requires reliable estimates of dissolved organic carbon (DOC) and there is a strong need to develop remote sensing methods for mapping lake carbon content at larger regional and global scales. Part of DOC is optically inactive. Therefore, lake DOC content cannot be mapped directly. The objectives of the current study were to estimate the relationships of DOC and other water and environmental variables in order to find the best proxy for remote sensing mapping of lake DOC. The Boosted Regression Trees approach was used to clarify in which relative proportions different water and environmental variables determine DOC. In a studied large and shallow eutrophic lake the concentrations of DOC and coloured dissolved organic matter (CDOM) were rather high while the seasonal and interannual variability of DOC concentrations was small. The relationships between DOC and other water and environmental variables varied seasonally and interannually and it was challenging to find proxies for describing seasonal cycle of DOC. Chlorophyll a (Chl a), total suspended matter and Secchi depth were correlated with DOC and therefore are possible proxies for remote sensing of seasonal changes of DOC in ice free period, while for long term interannual changes transparency-related variables are relevant as DOC proxies. CDOM did not appear to be a good predictor of the seasonality of DOC concentration in Lake Võrtsjärv since the CDOM-DOC coupling varied seasonally. However, combining the data from Võrtsjärv with the published data from six other eutrophic lakes in the world showed that CDOM was the most powerful predictor of DOC and can be used in remote sensing of DOC concentrations in eutrophic lakes. PMID:27318445

  2. Dissolved organic carbon and its potential predictors in eutrophic lakes.

    PubMed

    Toming, Kaire; Kutser, Tiit; Tuvikene, Lea; Viik, Malle; Nõges, Tiina

    2016-10-01

    Understanding of the true role of lakes in the global carbon cycle requires reliable estimates of dissolved organic carbon (DOC) and there is a strong need to develop remote sensing methods for mapping lake carbon content at larger regional and global scales. Part of DOC is optically inactive. Therefore, lake DOC content cannot be mapped directly. The objectives of the current study were to estimate the relationships of DOC and other water and environmental variables in order to find the best proxy for remote sensing mapping of lake DOC. The Boosted Regression Trees approach was used to clarify in which relative proportions different water and environmental variables determine DOC. In a studied large and shallow eutrophic lake the concentrations of DOC and coloured dissolved organic matter (CDOM) were rather high while the seasonal and interannual variability of DOC concentrations was small. The relationships between DOC and other water and environmental variables varied seasonally and interannually and it was challenging to find proxies for describing seasonal cycle of DOC. Chlorophyll a (Chl a), total suspended matter and Secchi depth were correlated with DOC and therefore are possible proxies for remote sensing of seasonal changes of DOC in ice free period, while for long term interannual changes transparency-related variables are relevant as DOC proxies. CDOM did not appear to be a good predictor of the seasonality of DOC concentration in Lake Võrtsjärv since the CDOM-DOC coupling varied seasonally. However, combining the data from Võrtsjärv with the published data from six other eutrophic lakes in the world showed that CDOM was the most powerful predictor of DOC and can be used in remote sensing of DOC concentrations in eutrophic lakes.

  3. Dissolved organic carbon (DOC) in Arctic ground ice

    NASA Astrophysics Data System (ADS)

    Fritz, M.; Opel, T.; Tanski, G.; Herzschuh, U.; Meyer, H.; Eulenburg, A.; Lantuit, H.

    2015-01-01

    Thermal permafrost degradation and coastal erosion in the Arctic remobilize substantial amounts of organic carbon (OC) and nutrients which have been accumulated in late Pleistocene and Holocene unconsolidated deposits. Their vulnerability to thaw subsidence, collapsing coastlines and irreversible landscape change is largely due to the presence of large amounts of massive ground ice such as ice wedges. However, ground ice has not, until now, been considered to be a source of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and other elements, which are important for ecosystems and carbon cycling. Here we show, using geochemical data from a large number of different ice bodies throughout the Arctic, that ice wedges have the greatest potential for DOC storage with a maximum of 28.6 mg L-1 (mean: 9.6 mg L-1). Variation in DOC concentration is positively correlated with and explained by the concentrations and relative amounts of typically terrestrial cations such as Mg2+ and K+. DOC sequestration into ground ice was more effective during the late Pleistocene than during the Holocene, which can be explained by rapid sediment and OC accumulation, the prevalence of more easily degradable vegetation and immediate incorporation into permafrost. We assume that pristine snowmelt is able to leach considerable amounts of well-preserved and highly bioavailable DOC as well as other elements from surface sediments, which are rapidly stored in ground ice, especially in ice wedges, even before further degradation. In the Yedoma region ice wedges represent a significant DOC (45.2 Tg) and DIC (33.6 Tg) pool in permafrost areas and a fresh-water reservoir of 4172 km3. This study underlines the need to discriminate between particulate OC and DOC to assess the availability and vulnerability of the permafrost carbon pool for ecosystems and climate feedback upon mobilization.

  4. Dissolved organic carbon (DOC) in Arctic ground ice

    NASA Astrophysics Data System (ADS)

    Fritz, M.; Opel, T.; Tanski, G.; Herzschuh, U.; Meyer, H.; Eulenburg, A.; Lantuit, H.

    2015-04-01

    Thermal permafrost degradation and coastal erosion in the Arctic remobilize substantial amounts of organic carbon (OC) and nutrients which have accumulated in late Pleistocene and Holocene unconsolidated deposits. Permafrost vulnerability to thaw subsidence, collapsing coastlines and irreversible landscape change are largely due to the presence of large amounts of massive ground ice such as ice wedges. However, ground ice has not, until now, been considered to be a source of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and other elements which are important for ecosystems and carbon cycling. Here we show, using biogeochemical data from a large number of different ice bodies throughout the Arctic, that ice wedges have the greatest potential for DOC storage, with a maximum of 28.6 mg L-1 (mean: 9.6 mg L-1). Variation in DOC concentration is positively correlated with and explained by the concentrations and relative amounts of typically terrestrial cations such as Mg2+ and K+. DOC sequestration into ground ice was more effective during the late Pleistocene than during the Holocene, which can be explained by rapid sediment and OC accumulation, the prevalence of more easily degradable vegetation and immediate incorporation into permafrost. We assume that pristine snowmelt is able to leach considerable amounts of well-preserved and highly bioavailable DOC as well as other elements from surface sediments, which are rapidly frozen and stored in ground ice, especially in ice wedges, even before further degradation. We found that ice wedges in the Yedoma region represent a significant DOC (45.2 Tg) and DIC (33.6 Tg) pool in permafrost areas and a freshwater reservoir of 4200 km2. This study underlines the need to discriminate between particulate OC and DOC to assess the availability and vulnerability of the permafrost carbon pool for ecosystems and climate feedback upon mobilization.

  5. Complexation of Cu with dissolved organic carbon in municipal solid waste incinerator bottom ash leachates

    SciTech Connect

    Meima, J.A.; Van Zomeren, A.; Comans, R.N.J.

    1999-05-01

    The complexation of Cu with dissolved organic carbon (DOC) in leachates from fresh and 1.5-year old municipal solid waste incinerator (MSWI) bottom ash was studied using a competitive ligands-exchange solvent extraction procedure. At least two different ligands appear to be involved in the complexation of copper with DOC. The dissolved Cu appears to be 95--100% organically bound in leachates from both the fresh and the weathered bottom ash, and geochemical modeling indicates that the leaching of Cu from these ashes is primarily controlled by the availability of the organic ligands in the bottom ash. The mechanism that binds Cu to the solid phase is likely to be tenorite in the fresh bottom ash, and sorption to amorphous Fe/Al-(hydr)-oxides in the weathered bottom ash.

  6. Elevated dissolved organic carbon biodegradability from thawing and collapsing permafrost

    NASA Astrophysics Data System (ADS)

    Abbott, Benjamin W.; Larouche, Julia R.; Jones, Jeremy B.; Bowden, William B.; Balser, Andrew W.

    2014-10-01

    As high latitudes warm, a portion of the large organic carbon pool stored in permafrost will become available for transport to aquatic ecosystems as dissolved organic carbon (DOC). If permafrost DOC is biodegradable, much will be mineralized to the atmosphere in freshwater systems before reaching the ocean, accelerating carbon transfer from permafrost to the atmosphere, whereas if recalcitrant, it will reach marine ecosystems where it may persist over long time periods. We measured biodegradable DOC (BDOC) in water flowing from collapsing permafrost (thermokarst) on the North Slope of Alaska and tested the role of DOC chemical composition and nutrient concentration in determining biodegradability. DOC from collapsing permafrost was some of the most biodegradable reported in natural systems. However, elevated BDOC only persisted during active permafrost degradation, with a return to predisturbance levels once thermokarst features stabilized. Biodegradability was correlated with background nutrient concentration, but nutrient addition did not increase overall BDOC, suggesting that chemical composition may be a more important control on DOC processing. Despite its high biodegradability, permafrost DOC showed evidence of substantial previous microbial processing, and we present four hypotheses explaining this incongruity. Because thermokarst features form preferentially on river banks and lake shores and can remain active for decades, thermokarst may be the dominant short-term mechanism delivering sediment, nutrients, and biodegradable organic matter to aquatic systems as the Arctic warms.

  7. 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

  8. 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

  9. Copper-binding ability of dissolved organic matter derived from anaerobically digested biosolids

    SciTech Connect

    Han, N.; Thompson, M.L.

    1999-05-01

    The fate of metals in soils where soluble organic compound are present may be strongly influenced by the degree to which they are complexed by organic ligands. The authors undertook this study to determine the combined effect of molecular weight (MW) and hydrophobicity on the Cu-binding ability of dissolved organic compounds in biosolids (i.e., sewage sludge). Dissolved organic matter (DOM) from anaerobically digested sewage biosolids was fractionated by using a combination of MW fractionation and XAD-8 resin chromatography. The Cu-binding abilities of the DOM fractions were obtained by using a Cu{sup 2+}-ion-selective electrode (Cu-ISE) technique. The Cu-binding ability of fractionated DOM decreased significantly with increasing molecular weight, indicating that low-MW DOM had more metal-binding sites than high-MW DOM. Within each MW fraction, the hydrophilic and the hydrophobic components also exhibited differences in Cu-binding ability. For the DOM with MW 500--3,500 Da, the hydrophilic fraction showed a greater Cu-binding capacity than did the hydrophobic fraction, whereas the hydrophobic acid components were most important in binding Cu for DOM with MW > 3,500 Da. The maximum Cu-binding capacities of different biosolids-derived DOM fractions, estimated by employing a Langmuir model, ranged from 1.85 to 14.3 mmol Cu mol{sup {minus}1} dissolved organic C (DOC), which is the same order of magnitude as similar measurements of DOM from other sources.

  10. 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.

  11. 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. PMID:25157605

  12. 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.

  13. Analysis of spatial distribution characteristics of dissolved organic matter in typical greenhouse soil of northern China using three dimensional fluorescence spectra technique and parallel factor analysis model.

    PubMed

    Pan, Hong-wei; Lei, Hong-jun; Han, Yu-ping; Xi, Bei-dou; He, Xiao-song; Xu, Qi-gong; Li, Dan

    2014-06-01

    The aim of the present work is to study the soil DOM characteristics in the vegetable greenhouse with a long-term of cultivation. Results showed that the soil DOM mainly consisted of three components, fulvic acid-like (C1), humic acid-like (C2) and protein-like (C3), with C1 as the majority one. The distribution of DOM in space was also studied. In vertical direction, C1 and C2 decreased significantly with the increase in soil depth, while C3 component decreased after increased. The humification coefficient decreased fast from 0-20 to 30-40 cm, and then increased from 30-40 to 40-50 cm. In the horizontal direction, the level of C2 component varied greatly in space, while that of C1 component changed little, and that of C3 component fell in between the above two. The change in the humification degree of each soil layer significantly varied spatially. Humification process of soil organic matter mainly occurred in the surface soil layer. In addition, the humification degree in space also changed significantly. The new ideas of this study are: (1) Analyze the composition and spatial heterogeneity of soil DOM in the vegetable greenhouse; (2) Use three dimensional fluorescence spectra technology and parallel factor analysis model successfully to quantify the components of soil DOM, which provides a new method for the soil DOM analysis. PMID:25358168

  14. 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...

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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. PMID:23274796

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. [Effects of dissolved organic matter on copper absorption by ryegrass].

    PubMed

    Tang, Chao; Wang, Bin; Liu, Man-Qiang; Hu, Feng; Li, Hui-Xin; Jiao, Jia-Guo

    2012-08-01

    In this study, dissolved organic matter (DOM) was extracted from earthworm casts and from the cattle manure with which the earthworms were fed, and a water culture experiment was conducted to study the effects of the DOM on the copper (Cu2+) absorption by ryegrass in the presence of different concentration Cu2+ (0, 5 and 10 mg x L(-1)). With the increasing concentration of Cu2+ in the medium, there was a gradual decrease in the dry mass of ryegrass shoots and roots and in the root length, surface area, volume, and tip number. In the presence of medium Cu2+, DOM increased the biomass of shoots and roots and the root length, surface area, volume, and tip number significantly. DOM reduced the Cu2+ concentration in roots, promoted the Cu2+ translocation from roots to shoots, and significantly increased the Cu2+ accumulation in shoots. The DOM from earthworm casts had better effects than that from cattle manure, and high concentration DOM had better effects than low concentration DOM. PMID:23189712

  5. 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. PMID:25385632

  6. 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.

  7. 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.

  8. Influence of dissolved organic carbon on methylmercury bioavailability across Minnesota stream ecosystems.

    PubMed

    Tsui, Martin Tsz Ki; Finlay, Jacques C

    2011-07-15

    Stream ecosystems are widely contaminated by mercury (Hg) via atmospheric transport and deposition in watersheds. Dissolved organic carbon (DOC) is well-known to be the dominant ligand for aqueous methylmercury (MeHg), the bioaccumulative form of Hg in aquatic food webs. However, it is less clear if and how the concentration and character (e.g., aromaticity) of DOC influences the availability of dissolved MeHg to stream food webs. In this work, we analyzed total-Hg and/or MeHg concentrations in water, seston, and macroinvertebrates (filter-feeding hydropsychid caddisflies), and other physiochemical properties in 30 streams along a south-north geographic gradient in eastern Minnesota that corresponds to substantial changes in dominant land cover (i.e., agriculture, urban, wetland, and forest). In general, MeHg concentrations in seston and hydropsychids were higher in watersheds with more forest and wetland coverage, and increased with dissolved MeHg concentration. However, we found that the efficiency of MeHg incorporation into the stream food webs (i.e., bioconcentration factors of MeHg in both seston and hydropsychids, BCF(MeHg) = solid MeHg ÷ dissolved MeHg) decreased significantly with DOC concentration and aromaticity, suggesting that MeHg bioavailability to the base of food webs was attenuated at higher levels of terrestrial DOC. Therefore, our findings suggest that there is a dual role of DOC on MeHg cycling in streams: terrestrial DOC acts as the primary carrier ligand of dissolved MeHg for transport into surface waters, yet this aromatic DOC also attenuates dissolved MeHg uptake by aquatic food webs. Thus, consideration of MeHg bioavailability and its environmental regulation could help improve predictive models of MeHg bioaccumulation in stream ecosystems.

  9. 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.

  10. Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane.

    PubMed

    Thayalakumaran, Thabo; Lenahan, Matthew J; Bristow, Keith L

    2015-01-01

    Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic-rich sugar mill by-products applied as fertilizer and/or sugarcane sap released during harvest. CFC-12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O2 and NO3 (-) ) and both Fe(2+) and Mn(2+) greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture.

  11. Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane.

    PubMed

    Thayalakumaran, Thabo; Lenahan, Matthew J; Bristow, Keith L

    2015-01-01

    Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic-rich sugar mill by-products applied as fertilizer and/or sugarcane sap released during harvest. CFC-12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O2 and NO3 (-) ) and both Fe(2+) and Mn(2+) greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture. PMID:25213667

  12. Fluxes of dissolved organic carbon from Chesapeake Bay sediments

    SciTech Connect

    Burdige, D.J.; Homstead, J. )

    1994-08-01

    Benthic fluxes of dissolved organic carbon (DOC) were measured over an annual cycle at two contrasting sites in Chesapeake Bay. At an organic-rich, sulfidic site in the mesohaline portion of the Bay (site M) DOC fluxes from the sediments ranged from 1.4 to 2.9 mmol/m[sup 2]/d. Measured benthic DOC fluxes at site M corresponded to [approximately]3-13% of the depth-integrated benthic C remineralization rates ([Sigma]OCR), and agreed well with calculated diffusive DOC fluxes based on porewater DOC profiles. This agreement suggests that DOC fluxes from site M sediments were likely controlled by molecular diffusion. The second site that was studied is a heavily bioturbated site in the southern Bay (site S). The activity of macrobenthos did not appear to enhance DOC fluxes from these sediments, since measured benthic DOC fluxes (>0.5 mmol/m[sup 2]/d) were lower than those at site M. The ratios of benthic DOC fluxes to [Sigma]OCR values at site S were also slightly smaller than those observed at site M. Benthic DOC fluxes from Chesapeake Bay sediments do not appear to significantly affect the transport of DOC through this estuary, although uncertainties in the reactivity of DOC in estuaries makes this conclusion somewhat tentative at this time. However, when these results are used to make a lower limit estimate of the globally integrated benthic DOC flux from marine sediments, a value similar to that previously calculated by Burdige et al. is obtained. This observation further supports suggestions in this paper about the importance of benthic DOC fluxes in the oceanic C cycle.

  13. 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.

  14. 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.

  15. 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. PMID:25714090

  16. Dissolved organic carbon and sulfur in southwestern Quebec lakes: Relationships with catchment and lake properties

    SciTech Connect

    Houle, D.; Carignan, R.; Lachance, M.

    1995-06-01

    In 59 southwestern Quebec lakes, dissolved organic S (DOS) concentration averages 185{+-}92 {mu}g liter{sup -1} (9.2% of total S) and ranges from undetectable to 437 {mu}g liter{sup -1} (22% of total S). DOS can be predicted from dissolved organic C (DOC) concentrations: DOS ({mu}g liter{sup -1}) = 2.20 log{sub 10}(DOC) + 7, r{sup 2} = 0.55. When applied to 1,238 lakes from five Quebec regions, this relationship indicates that DOS can account for 8.5% (Ottawa) to 22.2% (North Shore) of total S. These results stress the importance of evaluating DOS concentrations in studies of catchment S budgets. Multiple regression models using lake and catchment properties as independent variables respectively explain 75, 43, 49, and 69% of the variance in DOC, DOS, DOC: DOS, and color. The regressions found for DOC, color, and DOS include a flowpath index, accounting for dissolved organic matter (DOM) leaching from the catchment, and a term for in-lake losses. The DOC:DOS regression includes the flowpath index, lake perimeter, and altitude and suggests that DOM supply and composition also depend on catchment properties. 23 refs., 3 figs., 5 tabs.

  17. 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...

  18. 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...

  19. 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...

  20. 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.

  1. A model for partitioning the light absorption coefficient of natural waters into phytoplankton, nonalgal particulate, and colored dissolved organic components: A case study for the Chesapeake Bay

    NASA Astrophysics Data System (ADS)

    Zheng, Guangming; Stramski, Dariusz; DiGiacomo, Paul M.

    2015-04-01

    We present a model, referred to as Generalized Stacked-Constraints Model (GSCM), for partitioning the total light absorption coefficient of natural water (with pure-water contribution subtracted), anw(λ), into phytoplankton, aph(λ), nonalgal particulate, ad(λ), and CDOM, ag(λ), components. The formulation of the model is based on the so-called stacked-constraints approach, which utilizes a number of inequality constraints that must be satisfied simultaneously by the model outputs of component absorption coefficients. A major advancement is that GSCM provides a capability to separate the ad(λ) and ag(λ) coefficients from each other using only weakly restrictive assumptions about the component absorption coefficients. In contrast to the common assumption of exponential spectral shape of ad(λ) and ag(λ) in previous models, in our model these two coefficients are parameterized in terms of several distinct spectral shapes. These shapes are determined from field data collected in the Chesapeake Bay with an ultimate goal to adequately account for the actual variability in spectral shapes of ad(λ) and ag(λ) in the study area. Another advancement of this model lies in its capability to account for potentially nonnegligible magnitude of ad(λ) in the near-infrared spectral region. Evaluation of model performance demonstrates good agreement with measurements in the Chesapeake Bay. For example, the median ratio of the model-derived to measured ad(λ), ag(λ), and aph(λ) at 443 nm is 0.913, 1.064, and 1.056, respectively. Whereas our model in its present form can be a powerful tool for regional studies in the Chesapeake Bay, the overall approach is readily adaptable to other regions or bio-optical water types.

  2. 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...

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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.

  6. Modeling dissolved and free phase gas dynamics under decompression.

    PubMed

    Wienke, B R

    1990-04-01

    Dissolved and free gases do not behave the same way in tissue under pressure, and their interaction is complex. Differences are highlighted, particularly with respect to time scales, gradients and transport. Impacts of free phases on diving are described, contrasting increased off-gassing pressures, slower ascent rates, safety stops and reduced repetitive exposures as consistent practical measures within Haldane models (limited supersaturation) which can be played off against buildup of dissolved gas. Simple computations illustrate the points.

  7. Linking CDOM spectral absorption to dissolved organic carbon concentrations and loadings in boreal estuaries

    NASA Astrophysics Data System (ADS)

    Asmala, Eero; Stedmon, Colin A.; Thomas, David N.

    2012-10-01

    The quantity of chromophoric dissolved organic matter (CDOM) and dissolved organic carbon (DOC) in three Finnish estuaries (Karjaanjoki, Kyrönjoki and Kiiminkijoki) was investigated, with respect to predicting DOC concentrations and loadings from spectral CDOM absorption measurements. Altogether 87 samples were collected from three estuarine transects which were studied in three seasons, covering a salinity range between 0 and 6.8, and DOC concentrations from 1572 μmol l-1 in freshwater to 222 μmol l-1 in coastal waters. CDOM absorption coefficient, aCDOM(375) values followed the trend in DOC concentrations across the salinity gradient and ranged from 1.67 to 33.4 m-1. The link between DOC and CDOM was studied using a range of wavelengths and algorithms. Wavelengths between 250 and 270 nm gave the best predictions with single linear regression. Total dissolved iron was found to influence the prediction in wavelengths above 520 nm. Despite significant seasonal and spatial differences in DOC-CDOM models, a universal relationship was tested with an independent data set and found to be robust. DOC and CDOM yields (loading/catchment area) from the catchments ranged from 1.98 to 5.44 g C m-2 yr-1, and 1.67 to 11.5 aCDOM(375) yr-1, respectively.

  8. 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.

  9. 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

  10. Composition of dissolved organic nitrogen in rivers associated with wetlands.

    PubMed

    Watanabe, Akira; Tsutsuki, Kiyoshi; Inoue, Yudzuru; Maie, Nagamitsu; Melling, Lulie; Jaffé, Rudolf

    2014-09-15

    As basic information for assessing reactivity and functionality of wetland-associated dissolved organic matter (DOM) based on their composition and structural properties, chemical characteristics of N in ultrafiltered DOM (UDON; >1 kD) isolated from wetland-associated rivers in three climates (cool-temperate, Hokkaido, Japan; sub-tropical, Florida, USA; tropical, Sarawak, Malaysia) were investigated. The UDON was isolated during dry and wet seasons, or during spring, summer, and autumn. The proportion of UDON present as humic substances, which was estimated as the DAX-8 adsorbed fraction, ranged from 47 to 91%, with larger values in the Sarawak than at the other sites. The yield of hydrolyzable amino acid N ranged 1.24 to 7.01 mg g(-1), which correlated positively to the total N content of UDOM and tended to be larger in the order of Florida>Hokkaido>Sarawak samples. X-ray photoelectron N1s spectra of UDON showed a strong negative correlation between the relative abundances of amide/peptide N and primary amine N. The relative abundances of amide/peptide N and primary amine N in the Sarawak samples were smaller (70-76%) and larger (20-23%) respectively compared to those (80-88% and 4-9%) in the Florida and Hokkaido samples. Assuming terminal amino groups and amide N of peptides as major constituents of primary amine N and amide/peptide N, respectively, the average molecular weight of peptides was smaller in the Sarawak samples than that in the Florida and Hokkaido samples. Seasonal variations in UDON composition were scarce in the Sarawak and Florida samples, whereas the distribution of humic substance-N and nonhumic substance-N and compositions of amino acids and N functional groups showed a clear seasonality in the Hokkaido samples. While aromatic N increased from spring to autumn, contributions from fresh proteinaceous materials were also enhanced during autumn, resulting in the highest N content of UDOM for this season. PMID:24946034

  11. 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.

  12. 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. PMID:26837382

  13. Natural versus wastewater derived dissolved organic carbon: implications for the environmental fate of organic micropollutants.

    PubMed

    Neale, Peta A; Antony, Alice; Gernjak, Wolfgang; Leslie, Greg; Escher, Beate I

    2011-08-01

    The interaction of organic micropollutants with dissolved organic carbon (DOC) can influence their transport, degradation and bioavailability. While this has been well established for natural organic carbon, very little is known regarding the influence of DOC on the fate of micropollutants during wastewater treatment and water recycling. Dissolved organic carbon-water partition coefficients (K(DOC)) for wastewater derived and reference DOC were measured for a range of micropollutants using a depletion method with polydimethylsiloxane disks. For micropollutants with an octanol-water partition coefficient (log K(OW)) greater than 4 there was a significant difference in K(DOC) between reference and wastewater derived DOC, with partitioning to wastewater derived DOC over 1000 times lower for the most hydrophobic micropollutants. The interaction of nonylphenol with wastewater derived DOC from different stages of a wastewater and advanced water treatment train was studied, but little difference in K(DOC) was observed. Organic carbon characterisation revealed that reference and wastewater derived DOC had very different properties due to their different origins. Consequently, the reduced sorption capacity of wastewater derived DOC may be related to their microbial origin which led to reduced aromaticity and lower molecular weight. This study suggests that for hydrophobic micropollutants (log K(OW) > 4) a higher concentration of freely dissolved and thus bioavailable micropollutants is expected in the presence of wastewater derived DOC than predicted using K(DOC) values quantified using reference DOC. The implication is that naturally derived DOC may not be an appropriate surrogate for wastewater derived DOC as a matrix for assessing the fate of micropollutants in engineered systems. PMID:21703657

  14. 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…

  15. Trophic complexity in aqueous systems: bacterial species richness and protistan predation regulate dissolved organic carbon and dissolved total nitrogen removal.

    PubMed

    Saleem, Muhammad; Fetzer, Ingo; Harms, Hauke; Chatzinotas, Antonis

    2016-02-24

    Loading of water bodies with dissolved organic carbon (DOC) and dissolved total nitrogen (DTN) affects their integrity and functioning. Microbial interactions mitigate the negative effects of high nutrient loads in these ecosystems. Despite numerous studies on how biodiversity mediates ecosystem functions, whether and how diversity and complexity of microbial food webs (horizontal, vertical) and the underlying ecological mechanisms influence nutrient removal has barely been investigated. Using microbial microcosms accommodating systematic combinations of prey (bacteria) and predator (protists) species, we showed that increasing bacterial richness improved the extent and reliability of DOC and DTN removal. Bacterial diversity drove nutrient removal either due to species foraging physiology or functional redundancy, whereas protistan diversity affected nutrient removal through bacterial prey resource partitioning and changing nutrient balance in the system. Our results demonstrate that prey-predator diversity and trophic interactions interactively determine nutrient contents, thus implying the vital role of microbial trophic complexity as a biological buffer against DOC and DTN.

  16. Trophic complexity in aqueous systems: bacterial species richness and protistan predation regulate dissolved organic carbon and dissolved total nitrogen removal.

    PubMed

    Saleem, Muhammad; Fetzer, Ingo; Harms, Hauke; Chatzinotas, Antonis

    2016-02-24

    Loading of water bodies with dissolved organic carbon (DOC) and dissolved total nitrogen (DTN) affects their integrity and functioning. Microbial interactions mitigate the negative effects of high nutrient loads in these ecosystems. Despite numerous studies on how biodiversity mediates ecosystem functions, whether and how diversity and complexity of microbial food webs (horizontal, vertical) and the underlying ecological mechanisms influence nutrient removal has barely been investigated. Using microbial microcosms accommodating systematic combinations of prey (bacteria) and predator (protists) species, we showed that increasing bacterial richness improved the extent and reliability of DOC and DTN removal. Bacterial diversity drove nutrient removal either due to species foraging physiology or functional redundancy, whereas protistan diversity affected nutrient removal through bacterial prey resource partitioning and changing nutrient balance in the system. Our results demonstrate that prey-predator diversity and trophic interactions interactively determine nutrient contents, thus implying the vital role of microbial trophic complexity as a biological buffer against DOC and DTN. PMID:26888033

  17. 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...

  18. 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

  19. 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.

  20. 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.

  1. 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 ...

  2. 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...

  3. 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.

  4. 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...

  5. 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)...

  6. PHOTOCHEMICALLY-INDUCED TRANSFORMATIONS OF DISSOLVED ORGANIC MATTER IN RIVERINE WATERS

    EPA Science Inventory

    We demonstrated that exposure of riverine water to natural sunlight initiated degradation and corresponding alteration to the stable carbon isotope ratio and biochemical composition of the associated dissolved organic carbon (DOC). Water samples were collected from two distinct ...

  7. 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...

  8. 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...

  9. CHANGES IN SPECTRAL AND PHOTOCHEMICAL PROPERTIES OF COLORED DISSOLVED ORGANIC MATTER IN A COASTAL ESTUARY

    EPA Science Inventory

    Colored dissolved organic matter (CDOM) is the primary determinant of UV penetration and exposure in freshwater and coastal environments. CDOM is photochemically reactive and its photoreactions can lead to reductions in UV absorbance and increased UV exposure in aquatic ecosystem...

  10. [Evolution of Dissolved Organic Matter Properties in a Constructed Wetland of Xiao River, Hebei].

    PubMed

    Ma, Li-na; Zhang, Hui; Tan, Wen-bing; Yu, Min-da; Huang, Zhi-gang; Gao, Ru-tai; Xi, Bei-dou; He, Xiao-song

    2016-01-01

    The evolution of water DOC and COD, and the source, chemical structure, humification degree and redox of dissolved organic matter (DOM) in a constructed wetland of Xiao River, Hebei, was investigated by 3D excitation--emission matrix fluorescence spectroscopy coupled with ultraviolet spectroscopy and chemical reduction, in order to explore the geochemical processes and environmental effects of DOM. Although DOC contributes at least 60% to COD, its decrease in the constructed wetland is mainly caused by the more extensive degradation of elements N, H, S, and P than C in DOM, and 65% is contributed from the former. DOM is mainly consisted of microbial products based on proxies f470/520 and BIX, indicating that DOM in water is apparently affected by microbial degradation. The result based on PARAFAC model shows that DOM in the constructed wetland contains protein-like and humus-like components, and Fulvic- and humic-like components are relatively easier to degrade than protein-like components. Fulvic- and humic-like components undergo similar decomposition in the constructed wetland. A common source of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) exists; both CDOM and FDOM are mainly composed of a humus-like material and do not exhibit selective degradation in the constructed wetland. The proxies E2 /E3, A240-400, r(A, C) and HIX in water have no changes after flowing into the constructed wetland, implying that the humification degree of DOM in water is hardly affected by wet constructed wetland. However, the constructed wetland environment is not only beneficial in forming the reduced state of DOM, but also facilitates the reduction of ferric. It can also improve the capability of DOM to function as an electron shuttle. This result may be related to the condition that the aromatic carbon of DOM can be stabilized well in the constructed wetland.

  11. Effects of dissolved organic matter on toxicity and bioavailability of copper for lettuce sprouts.

    PubMed

    Inaba, Shoko; Takenaka, Chisato

    2005-05-01

    It is well known that dissolved organic matter in soil solution may affect the toxicity or bioavailability of heavy metals to plants, but existing information on various organic substances is insufficient for treating problems with heavy metal-contaminated soils. To clarify how dissolved organic matter alters the toxicity and bioavailability of metals, we germinated lettuce seeds exposed to solutions containing Cu and several kinds of dissolved organic matters. Low molecular weight organic acids (citric, malic, and oxalic acids) increased the toxicity and bioavailability of Cu, but low concentrations of the synthetic chelators ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine penta-acetic acid (DTPA) decreased the toxicity and bioavailability of Cu. In contrast, humic acid appeared to be the most effective organic substance for detoxifying Cu, even though it did not significantly decrease the bioavailability of Cu. Consequently, the bioavailability and toxic effects of Cu in soil depend on the nature of coexisting organic substances in the soil solution.

  12. 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.

  13. Chromatographic methods for the isolation, separation and characterisation of dissolved organic matter.

    PubMed

    Sandron, Sara; Rojas, Alfonso; Wilson, Richard; Davies, Noel W; Haddad, Paul R; Shellie, Robert A; Nesterenko, Pavel N; Kelleher, Brian P; Paull, Brett

    2015-09-01

    This review presents an overview of the separation techniques applied to the complex challenge of dissolved organic matter characterisation. The review discusses methods for isolation of dissolved organic matter from natural waters, and the range of separation techniques used to further fractionate this complex material. The review covers both liquid and gas chromatographic techniques, in their various modes, and electrophoretic based approaches. For each, the challenges that the separation and fractionation of such an immensely complex sample poses is critically reviewed. PMID:26290053

  14. Chromatographic methods for the isolation, separation and characterisation of dissolved organic matter.

    PubMed

    Sandron, Sara; Rojas, Alfonso; Wilson, Richard; Davies, Noel W; Haddad, Paul R; Shellie, Robert A; Nesterenko, Pavel N; Kelleher, Brian P; Paull, Brett

    2015-09-01

    This review presents an overview of the separation techniques applied to the complex challenge of dissolved organic matter characterisation. The review discusses methods for isolation of dissolved organic matter from natural waters, and the range of separation techniques used to further fractionate this complex material. The review covers both liquid and gas chromatographic techniques, in their various modes, and electrophoretic based approaches. For each, the challenges that the separation and fractionation of such an immensely complex sample poses is critically reviewed.

  15. 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.

  16. [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.

  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. 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.

  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

    2016-04-01

    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

    2012-10-01

    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. PMID:22475414

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

    SciTech Connect

    Walsh, J.J.; Carder, K.L.; Mueller-Karger, F.E.

    1992-10-15

    Using bio-optical estimates of gelbstoff and a few platinum measurements of dissolved organic carbon (DOC{sub pt}), a budget of the meridional flux of DOC and dissolved organic nitrogen (DON) across 36{degrees}25{prime}N in the North Atlantic is constructed from previous inverse models of water and element transport. Distinct southward subsurface fluxes of dissolved organic matter (DOM) within subducted shelf water, cabelled slope water, and overturned basin water are inferred. Within two cases of a positive gradient of DOC{sub pt} between terrestrial/shelf and offshore stocks, the net equatorward exports of O{sub 2} and DOC{sub pt} from the northern North Atlantic yield molar ratios of 2.1 to 9.1, compared to the expected Redfield O{sub 2}/C ratio of 1.3. In the first case, 63% of the apparent oxygen utilization demands of the water column may be met by DOC, instead of only 14% in the second scenario, preserving a role for falling particles in the sea. With a DOC/DON ratio of 10, the larger net southward export of DON across 36{degrees}25{prime}N balances the postulated net northward input of 1.7 x 10{sup 3} kg NO{sub 3} s{sup {minus}1} of unutilized nitrate within the Gulf Stream. Without an enhanced supply of DOM from the shelves, a zero seaward gradient of DOM in the third case suggests that none of the poleward nitrate flux is returned southward as DON, but instead a net poleward flux of DON prevails as well. The authors present estimates are confounded, however, by the seasonal and multiyear variability of sinking processes in the North Atlantic. Future active and passive remote sensors, field programs, and simulation models must now discriminate between particulate and dissolved components of surface color signals to verify the importance of both continental margins and DOM in global biogeochemical cycles. 98 refs., 4 figs., 4 tabs.

  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. PMID:26497563

  5. 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.

  6. 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

  7. 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. PMID:25978545

  8. Environmental photoinactivation of extracellular phosphatases and the effects of dissolved organic matter.

    PubMed

    Janssen, Elisabeth M L; McNeill, Kristopher

    2015-01-20

    Alkaline phosphatases are ubiquitous extracellular enzymes in aquatic systems and play a central role in the biogeochemical cycling of phosphorus. Yet, the photochemical stability of phosphatase and effects of natural organic matter (DOM) are not completely understood. We demonstrate that phosphatase activity in natural biofilm samples decreased during sunlight exposure similar to well-defined bacterial phosphatase solutions. Direct photoinactivation was slowed by more than 50% in the presence of redox-active dissolved organic matter (DOM, 10 mgC L(–1)) or a model antioxidant (esculetin, 50 μM), even after light screening effects had been accounted for. Thus, DOM can not only inhibit enzymes (in the dark) or sensitize photodegradation by producing photochemically produced reactive intermediates but can also significantly quench direct photoinactivation of phosphatase. Our data further suggest that direct photooxidation of tryptophan residues within the protein structure are significantly involved in the photoinactivation of phosphatase because a loss of tryptophan-like fluorescence paralleled photoinactivation kinetics and because DOM acted as an antioxidant toward photoinactivation, a phenomenon recently established for the photooxidation of freely dissolved tryptophan. Thus, photoinactivation of phosphatase can be significantly slowed in the presence of naturally occurring antioxidants like DOM. The mechanistic link between tryptophan photooxidation and inactivation of phosphatase may have applicability to other extracellular enzymes but remains to be established.

  9. 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.

  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. 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

  12. 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.

  13. 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

  14. Technical Note: Dissolved organic matter fluorescence - a finite mixture approach to deconvolve excitation-emission matrices

    NASA Astrophysics Data System (ADS)

    Butturini, A.; Ejarque, E.

    2013-09-01

    The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

  15. Technical Note: Dissolved organic matter fluorescence - a finite mixture approach to deconvolve excitation-emission matrices

    NASA Astrophysics Data System (ADS)

    Butturini, A.; Ejarque, E.

    2013-03-01

    The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves single EEM is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimization algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. A small heterogeneous data set of 21 EEMs from a human-impacted Mediterranean river is used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

  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. 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

  19. 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...

  20. 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 ...

  1. Abiotic effects on effluent dissolved organic nitrogen along an estuarine transect.

    PubMed

    Funkey, Carolina P; Latour, Robert J; Bronk, Deborah A

    2015-03-01

    Biological nutrient removal is a process commonly used in water resource recovery facilities to reduce dissolved inorganic nitrogen (DIN) concentrations in effluent; this process is less effective at removing all of the effluent dissolved organic nitrogen (EDON). The goal of this study was to investigate the fate of EDON after it undergoes the disinfection process and enters receiving waters. The authors quantified the abiotic effects of effluent exposure to sunlight, increased salinity, and a combination of the two factors. Effluent dissolved organic nitrogen showed significant breakdown during the disinfection process (UV and chlorine) and when exposed to sunlight and increasing salinity. Approximately 7% of the EDON was transformed to DIN and dissolved primary amines after exposure to 9 hours of sunlight and a salinity increase from 0 to 33. The production of DIN and primary amines should be taken into account when considering sources of labile nitrogen to aquatic ecosystems.

  2. Determination of migration pathways of DNAPL and dissolved phase volatile organic compounds in heterogeneous aquifer systems

    SciTech Connect

    Lamb, B. ); Prucha, R.

    1993-10-01

    Before an effective ground-water extraction system can be designed, it is essential to determine the distribution of chemicals of concern in ground-water and preferential pathways for chemical migration. At the study site, determining the chemical migration pathways and spatial distribution of chemicals are complicated by the presence of halogenated volatile organic compounds (VOCs) and dense nonaqueous phase liquids (DNAPL) coupled with the heterogeneous nature of the aquifer. DNAPL is denser than ground water and therefore sinks due to gravity while the dissolved components tend to be dominated by regional ground-water advective flow. The study area is a former industrial site. The aquifer is a low permeability unit with thin lenses of sandy material. Dissolved phase chemicals preferentially migrate in these sand units. To determine pathways for the migration of chemicals both laterally and horizontally, borehole lithologic data, hydraulic data, and chemical data were synthesized into a computer database and used as input for graphical illustrations using computer aided drafting (CAD). The CAD software was also used to provide the basis for 2-D and 3-D visualization to interpret field data which aided in development of a detailed conceptual site model and in construction of a numerical ground-water flow model for the site.

  3. Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

    PubMed

    Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

    2015-05-01

    Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

  4. 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

  5. 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.

  6. Dust inputs and bacteria influence dissolved organic matter in clear alpine lakes.

    PubMed

    Mladenov, N; Sommaruga, R; Morales-Baquero, R; Laurion, I; Camarero, L; Diéguez, M C; Camacho, A; Delgado, A; Torres, O; Chen, Z; Felip, M; Reche, I

    2011-01-01

    Remote lakes are usually unaffected by direct human influence, yet they receive inputs of atmospheric pollutants, dust, and other aerosols, both inorganic and organic. In remote, alpine lakes, these atmospheric inputs may influence the pool of dissolved organic matter, a critical constituent for the biogeochemical functioning of aquatic ecosystems. Here, to assess this influence, we evaluate factors related to aerosol deposition, climate, catchment properties, and microbial constituents in a global dataset of 86 alpine and polar lakes. We show significant latitudinal trends in dissolved organic matter quantity and quality, and uncover new evidence that this geographic pattern is influenced by dust deposition, flux of incident ultraviolet radiation, and bacterial processing. Our results suggest that changes in land use and climate that result in increasing dust flux, ultraviolet radiation, and air temperature may act to shift the optical quality of dissolved organic matter in clear, alpine lakes.

  7. Dust inputs and bacteria influence dissolved organic matter in clear alpine lakes

    PubMed Central

    Mladenov, N.; Sommaruga, R.; Morales-Baquero, R.; Laurion, I.; Camarero, L.; Diéguez, M.C.; Camacho, A.; Delgado, A.; Torres, O.; Chen, Z.; Felip, M.; Reche, I.

    2011-01-01

    Remote lakes are usually unaffected by direct human influence, yet they receive inputs of atmospheric pollutants, dust, and other aerosols, both inorganic and organic. In remote, alpine lakes, these atmospheric inputs may influence the pool of dissolved organic matter, a critical constituent for the biogeochemical functioning of aquatic ecosystems. Here, to assess this influence, we evaluate factors related to aerosol deposition, climate, catchment properties, and microbial constituents in a global dataset of 86 alpine and polar lakes. We show significant latitudinal trends in dissolved organic matter quantity and quality, and uncover new evidence that this geographic pattern is influenced by dust deposition, flux of incident ultraviolet radiation, and bacterial processing. Our results suggest that changes in land use and climate that result in increasing dust flux, ultraviolet radiation, and air temperature may act to shift the optical quality of dissolved organic matter in clear, alpine lakes. PMID:21792184

  8. 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

  9. 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.

  10. 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.

  11. 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,...

  12. 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 ...

  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. 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.

  15. 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.

  16. 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

  17. Complexation of silver and dissolved organic matter in soil water extracts.

    PubMed

    Settimio, Lara; McLaughlin, Mike J; Kirby, Jason K; Langdon, Kate A; Janik, Les; Smith, Scott

    2015-04-01

    An important aspect of the behaviour and fate of silver (Ag) in soils is the interaction with dissolved organic matter (DOM). The complexation and strength of binding of Ag(+) with DOM in soil water extracts was examined and modelled based on a range of chemical and quality DOM measurements. Silver ion binding measured by addition of the (110m)Ag radioisotope in addition to a cation exchange resin technique were used to determine strongly complexed Ag in solutions. Silver was found to be up to 70% strongly complexed. The variability in Ag(+) binding by DOM across different soils was closely related (R(2) = 0.8) to the mid-infrared spectra of these extracts. The affinity of Ag(+) for DOM was stronger in solutions containing a greater content of humic and aromatic structures. The ability of Ag(+) to complex with DOM could result in increased mobilisation of this metal in the soil environment. PMID:25660071

  18. Complexation of silver and dissolved organic matter in soil water extracts.

    PubMed

    Settimio, Lara; McLaughlin, Mike J; Kirby, Jason K; Langdon, Kate A; Janik, Les; Smith, Scott

    2015-04-01

    An important aspect of the behaviour and fate of silver (Ag) in soils is the interaction with dissolved organic matter (DOM). The complexation and strength of binding of Ag(+) with DOM in soil water extracts was examined and modelled based on a range of chemical and quality DOM measurements. Silver ion binding measured by addition of the (110m)Ag radioisotope in addition to a cation exchange resin technique were used to determine strongly complexed Ag in solutions. Silver was found to be up to 70% strongly complexed. The variability in Ag(+) binding by DOM across different soils was closely related (R(2) = 0.8) to the mid-infrared spectra of these extracts. The affinity of Ag(+) for DOM was stronger in solutions containing a greater content of humic and aromatic structures. The ability of Ag(+) to complex with DOM could result in increased mobilisation of this metal in the soil environment.

  19. 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.

  20. 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. PMID:23424099

  1. 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.

  2. Size characteristics of chromophoric dissolved organic matter in the Chukchi Sea

    NASA Astrophysics Data System (ADS)

    Lin, Hui; Chen, Min; Zeng, Jian; Li, Qi; Jia, Renming; Sun, Xiuwu; Zheng, Minfang; Qiu, Yusheng

    2016-08-01

    With the Arctic warming, terrestrial input plays a more important role in carbon cycle in the Arctic Ocean than before. Chromophoric dissolved organic matter (CDOM) as a tracer of terrestrial dissolved organic matter (tDOM) becomes more valuable in elucidating the source and compositions of DOM. Although measurements of DOM in the Arctic Ocean have been widely reported, characteristics of high molecular weight colloids are still poorly understood. In this study, the bulk absorbance and size fractograms of CDOM were measured in the Chukchi Seas using an asymmetrical flow field-flow fractionation (AF4) coupled online with UV-vis detectors. Both CDOM a254, absorption coefficient at 254 nm, and the integrated UV254 (from AF4 UV-vis detector) of three colloidal fractions (1-10, 10-100, and >100 kDa) significantly correlated with the fraction of meteoric water (fmw) calculated from δ18O in seawater, which indicates that the CDOM was mainly derived from terrestrial input and a254 is a potential tracer of tDOM in the Chukchi Sea. Compared with the larger colloidal fractions (10-100 and >100 kDa), the smaller colloidal fraction (1-10 kDa) showed a stronger correlation with the fmw, suggesting the smaller colloids were of mostly terrigenous origin. Values of field measured spectral slope at 275-295 nm (s275-295), a tDOM proxy, were significantly lower than the model-estimated s275-295 calculated from the MODIS Aqu satellite remote sensing data, which indicated that terrestrial input of CDOM derived from model calculation was likely underestimated in the Chukchi Sea.

  3. Importance of microbial soil organic matter processing in dissolved organic carbon production.

    PubMed

    Malik, Ashish; Gleixner, Gerd

    2013-10-01

    Soil dissolved organic carbon (DOC) sources and its seasonal dynamics are poorly known. We aimed to determine the contribution of plant and soil organic matter (SOM) to size classes of DOC in a field experiment with C3 to C4 vegetation change on two soil types through different seasons. Stable isotope ratios of DOC size classes were measured using size exclusion chromatography (SEC) coupled online to liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). SEC resolved DOC into three size classes: very high molecular weight/vHMW (> 10 kDa), high molecular weight/HMW (0.4-10 kDa), and low molecular weight/LMW (< 0.4 kDa). HMW DOC was most abundant in all seasons, soil types, and depths. In contrast, vHMW DOC was only seen postsnowmelt in upper 20 cm and was mainly (87 ± 9%) plant-derived. Through all seasons, HMW and LMW DOC had less than 30% recent plant contribution. Similar size range and source of DOC size classes and soil chloroform fumigation extracts suggest microbial origin of DOC. Thus, microbial SOM recycling is an important process in DOC production. We suggest that DOC molecules get partitioned manifold between soil solution and the mineral matrix (chromatography), thereby getting constantly decomposed, altered, or produced anew by soil microorganisms (reactive transport).

  4. Effect of pH on dynamic and equilibrium surface tension of dissolve organic matter

    NASA Astrophysics Data System (ADS)

    Arye, Gilboa; Trifonov, Pavel; Ilani, Talli

    2014-05-01

    Dissolved organic matter (DOM) in the terrestrial environment may originate from the decomposition of soil organic matter accumulated from the degradation of vegetative residues, the release of root exudates, the lysis of microorganisms and addition of organic wastes, such as livestock manure, biosolids, and different composted organic residues, or from irrigation with wastewater. The structure of DOM macromolecules is known to vary with the following aqueous solution properties: ionic strength, the nature of the inorganic ions, pH and dissolved organic carbon (DOC) concentration. In aqueous solution, the DOM molecules are amphiphilic, that is, it possesses both hydrophilic and hydrophobic functional groups in the same molecule. This simultaneous presence, gave rise to the conceptual surfactant like model for DOM which has been studies in conjunction with the equilibrium surface tension at the liquid-air interface (STeq, mN/m). Measurements of STeq of DOM solution were reported in a relatively small number of studies for the conditions of the aqueous solution (e.g., temperature, pH, ionic strength, the valence of the metal ions, and DOC concentration). All studies demonstrate the decrease in STeq with increase aqueous concentration of the DOC. The effect of pH, however, exhibit contradictory results. Specifically, for a given DOC concentration, the patterns reported for STeq versus pH were different. With increasing pH values, STeq has been reported to decrease, increase or exhibit a minimum. These contradictory results have been attributed to the different DOC concentration examined in each of the studies. In current study we hypothesized that the inconsistent results of STeq vs. pH may also stem from the adsorption kinetics of the DOM amphiphilic molecules at the liquid air interface, which can be evaluated form dynamic surface tension measurements (STt). The STt is approaching STeq values and commonly exhibiting an exponential decay pattern. If for different p

  5. Assessing the nonconservative fluvial fluxes of dissolved organic carbon in North America

    NASA Astrophysics Data System (ADS)

    Lauerwald, Ronny; Hartmann, Jens; Ludwig, Wolfgang; Moosdorf, Nils

    2012-03-01

    Fluvial transport of dissolved organic carbon (DOC) is an important link in the global carbon cycle. Previous studies largely increased our knowledge of fluvial exports of carbon to the marine system, but considerable uncertainty remains about in-stream/in-river losses of organic carbon. This study presents an empirical method to assess the nonconservative behavior of fluvial DOC at continental scale. An empirical DOC flux model was trained on two different subsets of training catchments, one with catchments smaller than 2,000 km2 (n = 246, avg. 494 km2) and one with catchments larger than 2,000 km2 (n = 207, avg. 26,525 km2). A variety of potential predictors and controlling factors of fluvial DOC fluxes is discussed. The predictors retained for the final DOC flux models are runoff, slope gradient, land cover, and areal proportions of wetlands. According to the spatially explicit extrapolation of the models, in North America south of 60°N, the total fluvial DOC flux from small catchments (25.8 Mt C a-1, std. err.: 12%) is higher than that from large catchments (19.9 Mt C a-1, std. err.: 10%), giving a total DOC loss of 5.9 Mt C a-1 (std. err.: 78%). As DOC losses in headwaters are not represented in this budget, the estimated DOC loss is rather a minimum value for the total DOC loss within the fluvial network.

  6. Toxicity of dissolved Cu, Zn, Ni and Cd to developing embryos of the blue mussel (Mytilus trossolus) and the protective effect of dissolved organic carbon.

    PubMed

    Nadella, Sunita R; Fitzpatrick, John L; Franklin, Natasha; Bucking, Carol; Smith, Scott; Wood, Chris M

    2009-04-01

    Marine water quality criteria for metals are largely driven by the extremely sensitive embryo-larval toxicity of Mytilus sp. Here we assess the toxicity of four dissolved metals (Cu, Zn, Ni, Cd) in the mussel Mytilus trossolus, at various salinity levels while also examining the modifying effects of dissolved organic carbon (DOC) on metal toxicity. In 48 h embryo development tests in natural seawater, measured EC50 values were 6.9-9.6 microg L(-1) (95% C.I.=5.5-10.8 microg L(-1)) for Cu, 99 microg L(-1) (86-101) for Zn, 150 microg L(-1) (73-156) for Ni, and 502 microg L(-1) (364-847) for Cd. A salinity threshold of >20 ppt (approximately 60% full strength seawater) was required for normal control development. Salinity in the 60-100% range did not alter Cu toxicity. Experimental addition of dissolved organic carbon (DOC) from three sources reduced Cu toxicity; for example the EC50 of embryos developing in seawater with 20 mg C L(-1) was 39 microg Cu L(-1) (35.2-47.2) a 4-fold increase in Cu EC50. The protective effects of DOC were influenced by their distinct physicochemical properties. Protection appears to be related to higher fulvic acid and lower humic acid content as operationally defined by fluorescence spectroscopy. The fact that DOC from freshwater sources provides protection against Cu toxicity in seawater suggests that extrapolation from freshwater toxicity testing may be possible for saltwater criteria development, including development of a saltwater Biotic Ligand Model for prediction of Cu toxicity.

  7. Sorption and desorption of dissolved organic phosphorus onto iron (oxyhydr)oxides in seawater

    NASA Astrophysics Data System (ADS)

    Ruttenberg, K. C.; Sulak, D. J.

    2011-08-01

    Sorption of phosphorus (P) onto particulate surfaces significantly influences dissolved P concentrations in aquatic environments. We present results of a study contrasting the sorption behavior of several dissolved organic phosphorus (DOP) compounds and phosphate onto three commonly occurring iron (oxyhydr)oxides (Fe ox): ferrihydrite, goethite, and hematite. The DOP compounds were chosen to represent a range of molecular weights and structures, and include: adenosine triphosphate (ATP), adenosine monophosphate (AMP), glucose-6-phosphate (G6P), and aminoethylphosphonic acid (AEP). All P compounds displayed decreasing sorption as a function of crystallinity of the Fe ox substrate, with ferrihydrite adsorbing the most, hematite the least. In general, maximum sorption density decreased with increasing molecular weight of P compound; sorption of G6P onto goethite and hematite excepted. P compound size and structure, and the nature of the Fe ox substrate all appear to play a role dictating relative sorption capacity. Failure of a simple, 1-step sorption-desorption model to describe the data suggests that P sorption cannot be explained by a simple balance between sorption and desorption. Instead, the data are consistent with a 2-step sorption model consisting of an initial rapid surface sorption, followed by a slow, solid-state diffusion of P from surface sites into particle interiors. Desorption experiments provide additional support for the 2-step sorption model. Without exception, DOP compounds showed less efficient sorption than did orthophosphate. This suggests that in aquatic systems enriched in reactive Fe ox, whether as suspended particulates in the water column or in benthic sediments, DOP bioavailability may exceed that of orthophosphate. Since biological uptake of P from DOP requires enzymatic cleavage of orthophosphate, a system enriched in DOP relative to orthophosphate may impact ecosystem community structure.

  8. 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.

  9. 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.

  10. Dissolved organic nitrogen: an overlooked pathway of nitrogen loss from agricultural systems?

    PubMed

    van Kessel, Chris; Clough, Tim; van Groenigen, Jan Willem

    2009-01-01

    Conventional wisdom postulates that leaching losses of N from agriculture systems are dominated by NO(3)(-). Although the export of dissolved organic nitrogen (DON) into the groundwater has been recognized for more than 100 yr, it is often ignored when total N budgets are constructed. Leaching of DON into stream and drinking water reservoirs leads to eutrophication and acidification, and can pose a potential risk to human health. The main objective of this review was to determine whether DON losses from agricultural systems are significant, and to what extent they pose a risk to human health and the environment. Dissolved organic N losses across agricultural systems varied widely with minimum losses of 0.3 kg DON ha(-1)yr(-1) in a pasture to a maximum loss of 127 kg DON ha(-1)yr(-1) in a grassland following the application of urine. The mean and median values for DON leaching losses were found to be 12.7 and 4.0 kg N ha(-1)yr(-1), respectively. On average, DON losses accounted for 26% of the total soluble N (NO(3)(-) plus DON) losses, with a median value of 19%. With a few exceptions, DON concentrations exceeded the criteria recommendations for drinking water quality. The extent of DON losses increased with increasing precipitation/irrigation, higher total inputs of N, and increasing sand content. It is concluded that DON leaching can be an important N loss pathway from agricultural systems. Models used to simulate and predict N losses from agricultural systems should include DON losses.

  11. Salinity and dissolved organic carbon both affect copper toxicity in mussel larvae: Copper speciation or competition cannot explain everything.

    PubMed

    Deruytter, David; Vandegehuchte, Michiel B; Garrevoet, Jan; De Laender, Frederik; Vergucht, Eva; Delbeke, Katrien; Blust, Ronny; De Schamphelaere, Karel A C; Vincze, Laszlo; Janssen, Colin R

    2015-06-01

    Predicting copper (Cu) toxicity in marine and estuarine environments is challenging because of the influence of anions on Cu speciation, competition between Cu(2+) and other cations at the biotic ligand and the effect of salinity on the physiology of the organism. In the present study the combined effect of salinity and dissolved organic carbon (DOC) on Cu toxicity to larvae of Mytilus galloprovincialis was assessed. Two statistical models were developed and used to elucidate the relationship between Cu toxicity, salinity, and DOC. All models based on dissolved Cu indicate a decrease in Cu toxicity with increasing DOC concentrations, which can partly be explained by complexation of Cu(2+) ions with DOC. These models also indicate an increase in Cu toxicity (modeled with dissolved Cu or Cu(2+) activity) with increasing salinity, suggesting a salinity-induced alteration in the physiology of the mussel larvae. When based on Cu body burdens, neither of the models indicates an effect of salinity or DOC. This shows that the Cu body burden is a more constant predictor of Cu toxicity, regardless of the water chemistry influencing Cu speciation or competition and possible physiological alterations or changes in Cu speciation or competition.

  12. 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

  13. 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

  14. Diagenetic transformation of dissolved organic nitrogen compounds under contrasting sedimentary redox conditions in the Black Sea.

    PubMed

    Schmidt, Frauke; Koch, Boris P; Elvert, Marcus; Schmidt, Gunnar; Witt, Matthias; Hinrichs, Kai-Uwe

    2011-06-15

    Remineralization of organic matter in reactive marine sediments releases nutrients and dissolved organic matter (DOM) into the ocean. Here we focused on the molecular-level characterization of DOM by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sediment pore waters and bottom waters from contrasting redox regimes in the northern Black Sea with particular emphasis on nitrogen-bearing compounds to derive an improved understanding of the molecular transformations involved in nitrogen release. The number of nitrogen-bearing molecules is generally higher in pore waters than in bottom waters. This suggests intensified degradation of nitrogen-bearing precursor molecules such as proteins in anoxic sediments: No significant difference was observed between sediments deposited under oxic vs anoxic conditions (average O/C ratios of 0.55) suggesting that the different organic matter quality induced by contrasting redox conditions does not impact protein diagenesis in the subseafloor. Compounds in the pore waters were on average larger, less oxygenated, and had a higher number of unsaturations. Applying a mathematical model, we could show that the assemblages of nitrogen-bearing molecular formulas are potential products of proteinaceous material that was transformed by the following reactions: (a) hydrolysis and deamination, both reducing the molecular size and nitrogen content of the products and intermediates; (b) oxidation and hydration of the intermediates; and (c) methylation and dehydration.

  15. 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.

  16. Functional and Structural Responses of Hyporheic Biofilms to Varying Sources of Dissolved Organic Matter

    PubMed Central

    Wagner, Karoline; Bengtsson, Mia M.; Besemer, Katharina; Sieczko, Anna; Burns, Nancy R.; Herberg, Erik R.

    2014-01-01

    Headwater streams are tightly connected with the terrestrial milieu from which they receive deliveries of organic matter, often through the hyporheic zone, the transition between groundwater and streamwater. Dissolved organic matter (DOM) from terrestrial sources (that is, allochthonous) enters the hyporheic zone, where it may mix with DOM from in situ production (that is, autochthonous) and where most of the microbial activity takes place. Allochthonous DOM is typically considered resistant to microbial metabolism compared to autochthonous DOM. The composition and functioning of microbial biofilm communities in the hyporheic zone may therefore be controlled by the relative availability of allochthonous and autochthonous DOM, which can have implications for organic matter processing in stream ecosystems. Experimenting with hyporheic biofilms exposed to model allochthonous and autochthonous DOM and using 454 pyrosequencing of the 16S rRNA (targeting the “active” community composition) and of the 16S rRNA gene (targeting the “bulk” community composition), we found that allochthonous DOM may drive shifts in community composition whereas autochthonous DOM seems to affect community composition only transiently. Our results suggest that priority effects based on resource-driven stochasticity shape the community composition in the hyporheic zone. Furthermore, measurements of extracellular enzymatic activities suggest that the additions of allochthonous and autochthonous DOM had no clear effect on the function of the hyporheic biofilms, indicative of functional redundancy. Our findings unravel possible microbial mechanisms that underlie the buffering capacity of the hyporheic zone and that may confer stability to stream ecosystems. PMID:25063654

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    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.

  19. The XAS model of dissolved Cu(II) and its significance to biological electron transfer

    NASA Astrophysics Data System (ADS)

    Frank, Patrick; Benfatto, Maurizio; Hedman, Britt; Hodgson, Keith O.

    2009-11-01

    The standard model for dissolved Cu(II) portrays the complex ion as an axially elongated, equatorially planar octahedron. Using EXAFS and MXAN analyses of copper K-edge XAS spectra, new structural models for dissolved [Cu(aq)]2+ and [Cu(amm)]2+ have been determined. These structures uniformly depart from the octahedral model in favour of an axially elongated square pyramidal core. MXAN results also indicate that the equatorial ligands need not be coplanar with copper. Further structural elements include a -z axially localized scatterer at ~3 Å. Even more distant scatterers imply second shell solvent organization, which can vary with the medium. Preliminary results from new extended, k = 18 Å-1, higher resolution copper K-edge XAS data sets are reported. The low symmetry of dissolved Cu(II) ion contradicts the central thesis of the rack-induced bonding hypothesis of copper electron transfer proteins. The asymmetry of biological copper is not a frozen vibronic excited state enforced by a rigid protein scaffold, but is entirely in harmony with the structural ground state of the dissolved aqueous Cu(II) complex ion.

  20. Results of the 2008 dissolved organic matter fluorescence intercalibration study

    NASA Astrophysics Data System (ADS)

    Murphy, K. R.; Butler, K.; Spencer, R. G.; Boehme, J.; Aiken, G.

    2009-12-01

    In 2008, 20 laboratories around the world participated in an intercalibration study of organic matter fluorescence measurements via Excitation-Emission Matrix Spectroscopy (EEMS). The goal was to assess the variability of fluorescence measurements obtained for identical samples (n = 5 natural samples, Suwanee River Fulvic Acid, quinine sulphate and four Starna Fluorescence Reference cells) by different laboratories, and to examine potential sources of this variability. Operator error was found to be a significant source of variability, with 6 laboratories submitting erroneous EEMs in an initial round. Uncorrected EEMs were significantly different from corrected EEMs, particularly at relatively low and relatively high excitation (λex) and emission (λem) wavelengths. When data from each lab were corrected according to a standard set of algorithms, the variability between EEMs for the same sample measured by different labs was wavelength dependent, with EEMs normalized to raman areas more similar at low λex and λem, and EEMs normalized to quinine sulphate equivalents more similar at higher wavelengths. The results confirm the importance of (1) applying spectral corrections prior to comparing fluorescence data acquired on different instruments, (2) full reporting of correction procedures and implementation according to an agreed standard protocol, and (3) strict implementation of quality assurance protocols prior to reporting EEMs.

  1. 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

  2. Nitrogen loss from unpolluted South American forests mainly via dissolved organic compounds

    NASA Astrophysics Data System (ADS)

    Perakis, Steven S.; Hedin, Lars O.

    2002-01-01

    Conceptual and numerical models of nitrogen cycling in temperate forests assume that nitrogen is lost from these ecosystems predominantly by way of inorganic forms, such as nitrate and ammonium ions. Of these, nitrate is thought to be particularly mobile, being responsible for nitrogen loss to deep soil and stream waters. But human activities-such as fossil fuel combustion, fertilizer production and land-use change-have substantially altered the nitrogen cycle over large regions, making it difficult to separate natural aspects of nitrogen cycling from those induced by human perturbations. Here we report stream chemistry data from 100 unpolluted primary forests in temperate South America. Although the sites exhibit a broad range of environmental factors that influence ecosystem nutrient cycles (such as climate, parent material, time of ecosystem development, topography and biotic diversity), we observed a remarkably consistent pattern of nitrogen loss across all forests. In contrast to findings from forests in polluted regions, streamwater nitrate concentrations are exceedingly low, such that nitrate to ammonium ratios were less than unity, and dissolved organic nitrogen is responsible for the majority of nitrogen losses from these forests. We therefore suggest that organic nitrogen losses should be considered in models of forest nutrient cycling, which could help to explain observations of nutrient limitation in temperate forest ecosystems.

  3. 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.

  4. Nitrogen loss from unpolluted South American forests mainly via dissolved organic compounds.

    PubMed

    Perakis, Steven S; Hedin, Lars O

    2002-01-24

    Conceptual and numerical models of nitrogen cycling in temperate forests assume that nitrogen is lost from these ecosystems predominantly by way of inorganic forms, such as nitrate and ammonium ions. Of these, nitrate is thought to be particularly mobile, being responsible for nitrogen loss to deep soil and stream waters. But human activities-such as fossil fuel combustion, fertilizer production and land-use change-have substantially altered the nitrogen cycle over large regions, making it difficult to separate natural aspects of nitrogen cycling from those induced by human perturbations. Here we report stream chemistry data from 100 unpolluted primary forests in temperate South America. Although the sites exhibit a broad range of environmental factors that influence ecosystem nutrient cycles (such as climate, parent material, time of ecosystem development, topography and biotic diversity), we observed a remarkably consistent pattern of nitrogen loss across all forests. In contrast to findings from forests in polluted regions, streamwater nitrate concentrations are exceedingly low, such that nitrate to ammonium ratios were less than unity, and dissolved organic nitrogen is responsible for the majority of nitrogen losses from these forests. We therefore suggest that organic nitrogen losses should be considered in models of forest nutrient cycling, which could help to explain observations of nutrient limitation in temperate forest ecosystems.

  5. Dissolved organic sulfur in streams draining forested catchments in southern China.

    PubMed

    Wang, Zhanyi; Zhang, Xiaoshan; Wang, Zhangwei; Zhang, Yi; Li, Bingwen; Vogt, Rolf

    2012-01-01

    Dissolved organic sulfur (DOS) is an important fraction for sulfur mobilization in ecosystem. In this work stream waters were sampled in 25 forested sites in southern China to study the dissolved sulfur fractions. Dissolved sulfur was fractionated into dissolved organic sulfur (DOS) and inorganic sulfate (SO4(2-)) for 95 stream water samples. The results showed that the concentration of DOS ranged from 0 to 13.1 mg/L (average 1.3 mg/L) in all the streams. High concentrations of DOS in stream waters were found in the sites with high concentrations of sulfate. DOS constituted less than 60.1% of dissolved sulfur (average 17.9%). Statistical analysis showed that DOS concentration was correlated with SO4(2-) in streams waters and total sulfur in surface layer soils. The results also showed that DOS concentration in stream waters had a seasonal variation, but no trends were found with it. The implication was that the long term sulfur deposition had led the increase of the concentration and fraction of DOS in stream waters in acid rain prevailing regions

  6. Dissolved organic sulfur in streams draining forested catchments in southern China.

    PubMed

    Wang, Zhanyi; Zhang, Xiaoshan; Wang, Zhangwei; Zhang, Yi; Li, Bingwen; Vogt, Rolf

    2012-01-01

    Dissolved organic sulfur (DOS) is an important fraction for sulfur mobilization in ecosystem. In this work stream waters were sampled in 25 forested sites in southern China to study the dissolved sulfur fractions. Dissolved sulfur was fractionated into dissolved organic sulfur (DOS) and inorganic sulfate (SO4(2-)) for 95 stream water samples. The results showed that the concentration of DOS ranged from 0 to 13.1 mg/L (average 1.3 mg/L) in all the streams. High concentrations of DOS in stream waters were found in the sites with high concentrations of sulfate. DOS constituted less than 60.1% of dissolved sulfur (average 17.9%). Statistical analysis showed that DOS concentration was correlated with SO4(2-) in streams waters and total sulfur in surface layer soils. The results also showed that DOS concentration in stream waters had a seasonal variation, but no trends were found with it. The implication was that the long term sulfur deposition had led the increase of the concentration and fraction of DOS in stream waters in acid rain prevailing regions PMID:22894106

  7. 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.

  8. 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...

  9. 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...

  10. Response to Comment on “Dilution limits dissolved organic carbon utilization in the deep ocean”

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  11. 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...

  12. 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...

  13. 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 ...

  14. 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...

  15. ESTIMATING THE POTENTIAL FOR FACILITATED TRANSPORT OF NAPROPAMIDE BY DISSOLVED ORGANIC MATTER

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic matter (DOM) has been found to significantly affect the soil sorption/desorption of napropamide [2-(a-naphthoxy-N, N-diethylpropionamide] and to enhance its transport through soil columns. A method to qualitatively predict if DOM will enhance the transport of napropamide based on e...

  16. 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.

  17. 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...

  18. 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...

  19. 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...

  20. Dissolved Organic Nitrogen Hydrolysis Rates in Axenic Cultures of Aureococcus anophagefferens (Pelagophyceae): Comparison with Heterotrophic Bacteria

    PubMed Central

    Berg, Gry Mine; Repeta, Daniel J.; Laroche, Julie

    2002-01-01

    The marine autotroph Aureococcus anophagefferens (Pelagophyceae) was rendered axenic in order to investigate hydrolysis rates of peptides, chitobiose, acetamide, and urea as indicators of the ability to support growth on dissolved organic nitrogen. Specific rates of hydrolysis varied between 8 and 700% of rates observed in associated heterotrophic marine bacteria. PMID:11772651

  1. 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...

  2. 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...

  3. Dissolved Organic Carbon Fluxes in Rivers of the Conterminous United States: Influence of Terrestrial - Aquatic Linkages

    NASA Astrophysics Data System (ADS)

    Stackpoole, S. M.; Butman, D. E.; Stets, E.; Striegl, R. G.; Bachelet, D. M.; Zhu, Z.; Liu, S.

    2015-12-01

    Management of terrestrial carbon stocks in natural ecosystems has been proposed as a sustainable approach to counteracting the anthropogenic contribution of carbon dioxide to the atmosphere. One factor of uncertainty in carbon accounting is that a portion of carbon assumed to be sequestered in soils may in fact be transported to river networks. The primary objectives of this study are to: 1) determine if the magnitude of empirical estimates of dissolved organic carbon (DOC) export in rivers correlates with simulated soil DOC leachate values from terrestrial carbon models, and 2) quantify terrestrial loading of DOC to river networks across the conterminous US. We evaluated the magnitude of riverine DOC fluxes relative to carbon storage in terrestrial biomass and soils using the aggregated results from the terrestrial carbon models included in the LandCarbon and Multi-scale Synthesis and Terrestrial Model Intercomparison Projects. We also compared gridded terrestrial DOC leaching values to downstream DOC fluxes in rivers estimated by the USGS LOADEST model. Quantification of terrestrial-aquatic linkages is necessary to better evaluate ecosystem carbon sequestration as a potential tool for mitigating anthropogenic perturbance to the global carbon cycle.

  4. Production and stabilization of dissolved organic matter throughout the entire soil profile

    NASA Astrophysics Data System (ADS)

    Kalbitz, Karsten; Kaiser, Klaus

    2010-05-01

    Dissolved organic matter (DOM) is the most mobile and rapidly cycling organic fraction in soil, affecting biogeochemical processes and linking terrestrial and aquatic ecosystems. Although representing just a small portion of total organic, it seems to be a key player in processes ultimately resulting in stabilization of organic matter against microbial decay. Recent studies have pointed out that up to 90% of the organic C in the mineral soil could derive from DOM. Most studies assume DOM to derive from surface horizons having large contents of organic matter such as peats, forest floor layers and mineral topsoils. Once biologically produced or physico-chemically released, DOM is transported into the subsoils characterized by smaller contents of organic matter. Here, DOM is retained by adsorption and/or (co)precipitation, resulting in stabilization against microbial decay. This concept assumes, DOM exported to the hydrosphere is that portion of DOM either not respired or not stabilized within the mineral soil. We think that this conceptual model is oversimplified and not made up to explain all aspects of organic matter transport and stabilization in soils. All organic matter in soil derives from primary production, entering the soil as leaves, roots and root exudates. The biological decomposition of the primary sources will provide a large variety of compounds of differing reactivity, solubility and stability, with microbial metabolites representing a prominent part of the stable fraction. Microbial decomposition will not ultimately convert all organic material into CO2 but render a certain portion soluble. Also, DOM seems capable to replace sorbed organic matter, thus allowing also for retention in parts of the mineral soil with large contents of organic matter. Therefore, we think that throughout the entire soil profile, production and release of DOM is possible, as well as retention and stabilization. In organic-rich horizons, especially those close or at the

  5. 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

  6. 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. PMID:27556278

  7. 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

  8. Release dynamics of dissolved organic matter in soil amended with biosolids

    NASA Astrophysics Data System (ADS)

    Trifonov, Pavel; Ilani, Talli; Arye, Gilboa

    2014-05-01

    Among the soil organic matter (SOM) components, dissolved organic matter (DOM) is the link between the solid phase and the soil solution. Previous studies emphasize the turnover of dissolved organic carbon (DOC) and nitrogen (DON) in soils as major pathways of element cycling. In addition to DOM contribution to carbon, nitrogen and other nutrient budgets, it also influence soil biological activity, reduces metal-ion toxicity, increase the transport of some compounds and contribute to the mineral weathering. Amending soils with biosolids originated from sludge have become very popular in the recent years. Those additions significantly affect the quantity and the composition of the DOM in agricultural soils. It should be noted that under most irrigation habitants, the soil is subjected to drying and re-wetting cycles, inducing a complex changes of soil structure, aggregation, SOM quality and micro-flora. However, most studies that addressed the above issues (directly or indirectly) are engaged with soils under cover of naturally occurring forests of relatively humid areas rather than agricultural soils in arid areas. In the current study we examined the DOC and DON release dynamic of sand and loess soils sampled from the Negev Desert of Israel. Each one of the soils were mixing with 5% (w/w) of one of the biosolids and packed into a Plexiglass column (I.d. 5.2 cm, L=20 cm). The flow-through experiments were conducted under low (1 ml/min) or high (10 ml/min) flow rates in a continuous or interrupted manner. The leachates were collected in time intervals equivalent to about 0.12 pore volume of a given soil-biosolids mixture. The established leaching curves of DOC, DON, NO3-, NH4+ and Cl- are analyzed by water flow and solute transport model for saturate (continuous runs) or variably saturate water flow conditions (interrupted runs). The chemical equilibrium or non-equilibrium (i.e. equilibrium and/or kinetics adsorption/desorption) versions of the convection dispersion

  9. The Relationship Between Dissolved Organic Matter Composition and Organic Matter Optical Properties in Freshwaters

    NASA Astrophysics Data System (ADS)

    Aiken, G.; Spencer, R. G.; Butler, K.

    2010-12-01

    Dissolved organic matter (DOM) chemistry and flux are potentially useful, albeit, underutilized, indicators of watershed characteristics, climate influences on watershed hydrology and soils, and changes associated with resource management. Source materials, watershed geochemistry, oxidative processes and hydrology exert strong influences on the nature and reactivity of DOM in aquatic systems. The molecules that comprise DOM, in turn, control a number of environmental processes important for ecosystem function including light penetration and photochemistry, microbial activity, mineral dissolution/precipitation, and the transport and reactivity of hydrophobic compounds and metals (e.g. Hg). In particular, aromatic molecules derived from higher plants exert strong controls on aquatic photochemistry, and on the transport and biogeochemistry of metals. Assessment of DOM composition and transport, therefore, can provide a basis for understanding watershed processes and biogeochemistry of rivers and streams. Here we present results of multi-year studies designed to assess the seasonal and spatial variability of DOM quantity and quality for 57 North American Rivers. DOM concentrations and composition, based on DOM fractionation on XAD resins, ultraviolet (UV)/visible absorption and fluorescence spectroscopic analyses, and specific compound analyses, varied greatly both between sites and seasonally within a given site. DOM in these rivers exhibited a wide range of concentration (<80 to >4000 µM C* L-1) and specific ultra-violet absorbance at 254 nm (SUVA254) (0.6 to 5 L *mg C-1 *m-1), an optical measurement that is an indicator of aromatic carbon content. In almost all systems, UV absorbance measured at specific wavelengths (e.g. 254 nm) correlated strongly with DOM and hydrophobic organic acid (HPOA) content (aquatic humic substances). The relationships between dissolved organic carbon (DOC) concentration and absorbance for the range of systems were quite variable due to

  10. 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.

  11. 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.

  12. Heat as a tracer to estimate dissolved organic carbon flux from a restored wetland

    USGS Publications Warehouse

    Burow, K.R.; Constantz, J.; Fujii, R.

    2005-01-01

    Heat was used as a natural tracer to characterize shallow ground water flow beneath a complex wetland system. Hydrogeologic data were combined with measured vertical temperature profiles to constrain a series of two-dimensional, transient simulations of ground water flow and heat transport using the model code SUTRA (Voss 1990). The measured seasonal temperature signal reached depths of 2.7 m beneath the pond. Hydraulic conductivity was varied in each of the layers in the model in a systematic manual calibration of the two-dimensional model to obtain the best fit to the measured temperature and hydraulic head. Results of a series of representative best-fit simulations represent a range in hydraulic conductivity values that had the best agreement between simulated and observed temperatures and that resulted in simulated pond seepage values within 1 order of magnitude of pond seepage estimated from the water budget. Resulting estimates of ground water discharge to an adjacent agricultural drainage ditch were used to estimate potential dissolved organic carbon (DOC) loads resulting from the restored wetland. Estimated DOC loads ranged from 45 to 1340 g C/(m2 year), which is higher than estimated DOC loads from surface water. In spite of the complexity in characterizing ground water flow in peat soils, using heat as a tracer provided a constrained estimate of subsurface flow from the pond to the agricultural drainage ditch. Copyright ?? 2005 National Ground Water Association.

  13. Hydro-climatic forcing of dissolved organic carbon in two boreal lakes of Canada.

    PubMed

    Diodato, Nazzareno; Higgins, Scott; Bellocchi, Gianni; Fiorillo, Francesco; Romano, Nunzio; Guadagno, Francesco M

    2016-11-15

    The boreal forest of the northern hemisphere represents one of the world's largest ecozones and contains nearly one third of the world's intact forests and terrestrially stored carbon. Long-term variations in temperature and precipitation have been implied in altering carbon cycling in forest soils, including increased fluxes to receiving waters. In this study, we use a simple hydrologic model and a 40-year dataset (1971-2010) of dissolved organic carbon (DOC) from two pristine boreal lakes (ELA, Canada) to examine the interactions between precipitation and landscape-scale controls of DOC production and export from forest catchments to surface waters. Our results indicate that a simplified hydrologically-based conceptual model can enable the long-term temporal patterns of DOC fluxes to be captured within boreal landscapes. Reconstructed DOC exports from forested catchments in the period 1901-2012 follow largely a sinusoidal pattern, with a period of about 37years and are tightly linked to multi-decadal patterns of precipitation. By combining our model with long-term precipitation estimates, we found no evidence of increasing DOC transport or in-lake concentrations through the 20th century. PMID:27459253

  14. Predicting export of dissolved organic carbon from forested catchments in glaciated landscapes with shallow soils

    NASA Astrophysics Data System (ADS)

    Creed, I. F.; Beall, F. D.; Clair, T. A.; Dillon, P. J.; Hesslein, R. H.

    2008-12-01

    This study presents a simple model of dissolved organic carbon (DOC) loading to surface waters that is applicable to headwater catchments in forested regions on glaciated landscapes. Average annual DOC export was highly variable among the 33 experimental catchments along an east-west transect, ranging from 0.90 to 13.74 g C/m2/a. It was hypothesized that the proportion of wetlands within the catchments would explain the majority of variation in average annual DOC export. To test this hypothesis, digital terrain analysis was used to derive wetlands automatically under both open and closed forest canopies by identifying the probability of a grid cell being a depression and/or flat. Using a 10 m digital elevation model (DEM) derived from readily available sources, the proportion of wetlands explained 63% of the variance in average annual DOC export among the 33 experimental catchments. Inclusion of regional climatic indicators, including the number of growing degree days (with a base of 10°C) and the runoff coefficient, increased explanation of variance from 63% to 89%, once catchments with lakes (>5% of catchment area) adjacent to the catchment outlets were removed. This study shows that DOC export can be predicted accurately from headwater catchments in forested regions on glaciated landscapes using a simple model based on the proportion of wetlands and easily calculated climatic variables.

  15. Competitive Coadsorption Dynamics of Viruses and Dissolved Organic Matter to Positively Charged Sorbent Surfaces.

    PubMed

    Armanious, Antonius; Münch, Melanie; Kohn, Tamar; Sander, Michael

    2016-04-01

    Adsorption onto solid-water interfaces is a key process governing the fate and transport of waterborne viruses. Although negatively charged viruses are known to extensively adsorb onto positively charged adsorbent surfaces, virus adsorption in such systems in the presence of negatively charged dissolved organic matter (DOM) as coadsorbate remains poorly studied and understood. This work provides a systematic assessment of the adsorption dynamics of negatively charged viruses (i.e., bacteriophages MS2, fr, GA, and Qβ) and polystyrene nanospheres onto a positively charged model sorbent surface in the presence of varying DOM concentrations. In all systems studied, DOM competitively suppressed the adsorption of the viruses and nanospheres onto the model surface. Electrostatic repulsion of the highly negatively charged MS2, fr, and the nanospheres impaired their adsorption onto DOM adlayers that formed during the coadsorption process. In contrast, the effect of competition on overall adsorption was attenuated for less-negatively charged GA and Qβ because these viruses also adsorbed onto DOM adlayer surfaces. Competition in MS2-DOM coadsorbate systems were accurately described by a random sequential adsorption model that explicitly accounts for the unfolding of adsorbed DOM. Consistent findings for viruses and nanospheres suggest that the coadsorbate effects described herein generally apply to systems containing negatively charged nanoparticles and DOM. PMID:26901121

  16. 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...

  17. Diminished Stream Nitrate Concentrations Linked to Dissolved Organic Carbon Dynamics After Leaf Fall

    NASA Astrophysics Data System (ADS)

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

    2004-05-01

    Thermodynamic coupling of the nitrogen and carbon cycles has broad implications for controls on catchment nutrient fluxes. In the northeast US, leaf fall occurs in early October and the availability of organic carbon increases as the leaves decompose. At the Sleepers River Research Watershed in northeastern Vermont (USA), we sampled stream chemistry from seven nested catchments to determine how stream dissolved organic carbon (DOC) and nitrate vary as a function of flow conditions, land-use, and basin size in response to leaf fall. Following leaf fall, nitrate concentration patterns were quantitatively different from other times of the year. Under baseflow conditions, stream and soil water DOC concentrations were higher than normal, whereas nitrate concentrations declined sharply at the five smallest catchments and more modestly at the two largest catchments. Under high flow conditions, flushing of nitrate was observed, as is typical for stormflow response at Sleepers River. Our field data suggest that in-stream processing of nitrate is likely thermodynamically and kinetically favorable under baseflow but not at higher flow conditions when expanding variable source areas make hydrological connections between nitrate source areas and streams. We are working to evaluate this hypothesis with isotopic and other monitoring data, and to model the coupled interactions of water, DOC, and nitrate fluxes in these nested catchments.

  18. Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes.

    PubMed

    Zhu, Fei-Die; Choo, Kwang-Ho; Chang, Hyun-Shik; Lee, Byunghwan

    2012-05-01

    The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels. PMID:22330311

  19. Water Dynamics and Its Role in Structural Hysteresis of Dissolved Organic Matter.

    PubMed

    Conte, Pellegrino; Kucerik, Jiri

    2016-03-01

    Knowledge of structural dynamics of dissolved organic matter (DOM) is of paramount importance for understanding DOM stability and role in the fate of solubilized organic and inorganic compounds (e.g., nutrients and pollutants), either in soils or aquatic systems. In this study, fast field cycling (FFC) (1)H NMR relaxometry was applied to elucidate structural dynamics of terrestrial DOM, represented by two structurally contrasting DOM models such as Suwanee River (SRFA) and Pahokee peat (PPFA) fulvic acids purchased by the International Humic Substance Society. Measurement of NMR relaxation rate of water protons in heating-cooling cycles revealed structural hysteresis in both fulvic acids. In particular, structural hysteresis was related to the delay in re-establishing water network around fulvic molecules as a result of temperature fluctuations. The experiments revealed that the structural temperature dependency and hysteresis were more pronounced in SRFA than in PPFA. This was attributed to the larger content of hydrogel-like structure in SRFA stabilized, at a larger extent, by H-bonds between carboxylic and phenolic groups. Moreover, results supported the view that terrestrial DOM consist of a hydrophobic rigid core surrounded by progressively assembling amphiphilic and polar molecules, which form an elastic structure that can mediate reactivity of the whole DOM.

  20. Relative copper binding capacities of dissolved organic compounds in a coastal-plain estuary. [Thalassiosira pseudonana

    SciTech Connect

    Newell, A.D.; Sanders, J.G.

    1986-08-01

    Naturally occurring organics in samples taken from the mesohaline portion of a Chesapeake Bay tributary were separated into four nominal molecular weight fractions and analyzed for their ability to bind copper by using an algal bioassay. The organics exhibited a relatively high capacity for copper, with the binding capacity directly proportional to dissolved organic carbon (DOC) concentrations. The relationship between binding capacity and DOC is similar in the Chesapeake Bay and in other estuaries and marine ecosystems. Such correlation is not found in freshwater ecosystems. The strong relationship between DOC concentrations and binding capacities in marine ecosystems may be due to the autochthonous origin of marine organics. 44 references, 3 figures, 2 tables.

  1. 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. PMID:24078053

  2. 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

  3. 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.

  4. 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. PMID:26783366

  5. Uncertainty analysis in dissolved oxygen modeling in streams.

    PubMed

    Hamed, Maged M; El-Beshry, Manar Z

    2004-08-01

    Uncertainty analysis in surface water quality modeling is an important issue. This paper presents a method based on the first-order reliability method (FORM) to assess the exceedance probability of a target dissolved oxygen concentration in a stream, using a Streeter-Phelps prototype model. Basic uncertainty in the input parameters is considered by representing them as random variables with prescribed probability distributions. Results obtained from FORM analysis compared well with those of the Monte Carlo simulation method. The analysis also presents the stochastic sensitivity of the probabilistic outcome in the form of uncertainty importance factors, and shows how they change with changing simulation time. Furthermore, a parametric sensitivity analysis was conducted to show the effect of selection of different probability distribution functions for the three most important parameters on the design point, exceedance probability, and importance factors.

  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. 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

  8. 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.

  9. Tracing the long-term microbial production of recalcitrant fluorescent dissolved organic matter in seawater

    NASA Astrophysics Data System (ADS)

    Jørgensen, Linda; Stedmon, Colin A.; Granskog, Mats A.; Middelboe, Mathias

    2014-04-01

    The majority of dissolved organic matter (DOM) in the ocean is resistant to microbial degradation, yet its formation remains poorly understood. The fluorescent fraction of DOM can be used to trace the formation of recalcitrant DOM (RDOM). A long-term (> 1 year) experiment revealed 27-52% removal of dissolved organic carbon and a nonlinear increase in RDOM fluorescence associated with microbial turnover of semilabile DOM. This fluorescence was also produced using glucose as the only initial carbon source, suggesting that degradation of prokaryote remnants contributes to RDOM. Our results indicate that the formation of a fluorescent RDOM component depends on the bioavailability of the substrate: the less labile, the larger the production of fluorescent RDOM relative to organic carbon remineralized. The anticipated increase in microbial carbon demand due to ocean warming can potentially force microbes to degrade less labile substrates, thereby increasing RDOM production and stimulating ocean carbon storage.

  10. Continuous hyperspectral absorption measurements of colored dissolved organic material in aquatic systems

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, Gary J.; Orrico, Cristina; Moline, Mark A.; Oliver, Matthew; Schofield, Oscar M.

    2003-11-01

    The majority of organic carbon in the oceans is present as dissolved organic matter (DOM) therefore understanding the distribution and dynamics of DOM is central to understanding global carbon cycles. Describing the time-space variability in colored dissolved organic matter (CDOM) has been difficult, as standard spectrophotometric methods for CDOM determination are laborious and susceptible to methodological biases. Previously, measurements of CDOM absorption in discrete water samples by use of a liquid-waveguide capillary cell (LWCC) compared favorably with measurements made with a benchtop spectrophotometer. Given this, we focused on automating the LWCC technique to improve our spatial and temporal sampling capabilities for CDOM. We found strong correlations between CDOM absorption spectra collected from discrete water samples using standard methods and selected corresponding CDOM spectra collected by the automated LWCC system. The near-continuous measurements by the LWCC system made it possible to map the temporal, spatial, and spectral variability of CDOM absorption along the ship track.

  11. Removal of dissolved organic carbon and nitrogen during simulated soil aquifer treatment.

    PubMed

    Essandoh, H M K; Tizaoui, C; Mohamed, M H A

    2013-07-01

    Soil aquifer treatment was simulated in 1 m laboratory soil columns containing silica sand under saturated and unsaturated soil conditions to examine the effect of travel length through the unsaturated zone on the removal of wastewater organic matter, the effect of soil type on dissolved organic carbon removal and also the type of microorganisms involved in the removal process. Dissolved organic carbon removal and nitrification did enhance when the wastewater travelled a longer length through the unsaturated zone. A similar consortium of microorganisms was found to exist in both saturated and unsaturated columns. Microbial concentrations however were lowest in the soil column containing silt and clay in addition to silica sand. The presence of silt and clay was detrimental to DOC removal efficiency under saturated soil conditions due to their negative effect on the hydraulic performance of the soil column and microbial growth.

  12. Modeling impact of storage zones on stream dissolved oxygen

    USGS Publications Warehouse

    Chapra, S.C.; Runkel, R.L.

    1999-01-01

    The Streeter-Phelps dissolved oxygen model is modified to incorporate storage zones. A dimensionless number reflecting enhanced decomposition caused by the increased residence time of the biochemical oxygen demand in the storage zone parameterizes the impact. This result provides a partial explanation for the high decomposition rates observed in shallow streams. An application suggests that the storage zone increases the critical oxygen deficit and moves it closer to the point source. It also indicates that the storage zone should have lower oxygen concentration than the main channel. An analysis of a dimensionless enhancement factor indicates that the biochemical oxygen demand decomposition in small streams could be up to two to three times more than anticipated based on the standard Streeter-Phelps model without storage zones. For larger rivers, enhancements of up to 1.5 could occur.The Streeter-Phelps dissolved oxygen model is modified to incorporate storage zones. A dimensionless number reflecting enhanced decomposition caused by the increased residence time of the biochemical oxygen demand in the storage zone parameterizes the impact. This result provides a partial explanation for the high decomposition rates observed in shallow streams. An application suggests that the storage zone increases the critical oxygen deficit and moves it closer to the point source. It also indicates that the storage zone should have lower oxygen concentration than the main channel. An analysis of a dimensionless enhancement factor indicates that the biochemical oxygen demand decomposition in small streams could be up to two to three times more than anticipated based on the standard Streeter-Phelps model without storage zones. For larger rivers, enhancements of up to 1.5 could occur.

  13. 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...

  14. 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

  15. Nitrogen and dissolved organic carbon (DOC) losses from an artificially drained grassland on organic soils

    NASA Astrophysics Data System (ADS)

    Tiemeyer, B.; Kahle, P.

    2014-02-01

    Nitrate-nitrogen (NO3-N) as well as dissolved organic carbon (DOC) and nitrogen (DON) concentrations and losses were studied for three respectively two years in a small catchment dominated by a degraded peatland used as intensive grassland. Concentrations in the shallow groundwater were spatially and temporally very variable with NO3-N being the most dynamic component (7.3 ± 12.5 mg L-1). Average NO3-N concentrations of 10.3 ± 5.4 mg L-1 in the ditch draining the catchment and annual NO3-N losses of 19, 35 and 26 kg ha-1 confirmed drained peatlands as an important source of diffuse N pollution. The highest NO3-N losses occurred during the wettest year. Resulting from concentrations of 2.4 ± 0.8 mg L-1, DON added further 4.5 to 6.4 kg ha-1 to the N losses and thus formed a relevant component of the total N losses. Ditch DOC concentrations of 24.9 ± 5.9 mg L-1 resulted in DOC losses of 66 kg ha-1 in the wet year 2006/07 and 39 kg ha-1 in the dry year 2007/08. Both DOC and N concentrations were governed by hydrological conditions, but NO3-N reacted much faster and clearer on rising discharge rates than DOC which tended to be higher under dryer conditions. In the third year of the study, the superposition of a very wet summer and land use changes from grassland to arable land in a part of the catchment suggests that under re-wetting conditions with a high groundwater table in summer, NO3-N would diminish quickly, while DOC would remain on a similar level. Further intensification of the land use, on the other hand, would increase N losses to receiving water bodies.

  16. Optical signatures of dissolved organic matter from the Endeavour and Axial vent fields

    NASA Astrophysics Data System (ADS)

    Stubbins, A.; Butterfield, D.; Rossel, P. E.; Dittmar, T.

    2011-12-01

    Recent studies have revealed that hydrothermal systems in the deep ocean are both sources and processors of dissolved organic matter (DOM). Sub-floor stores of fossil organic carbon may be exported to the deep ocean directly adding fossil C to the deep ocean dissolved organic carbon (DOC) pool and altering its apparent age. Fossil methane and carbon dioxide are also exported from vents. These C sources can then be utilized by chemotrophs and later enter the DOM pool as fossil DOC. Finally, when deep ocean waters are entrained into vent systems, the resultant heating may alter the chemical and optical properties of the DOM in these deep ocean waters. Dissolved organic matter (DOM) samples were collected from vents ranging in temperature from 10 to over 300 degrees centigrade across the Endeavour and Axial fields along the Juan de Fuca ridge. Elevated DOC and protein-like fluorescence reveal the vents to fuel the chemotrophic production of organic matter either in the adjacent water column or local sediments. High DOC and increased humic-like fluorescence in the hottest vent fluids, suggests the thermal degradation of DOM either from buried fossil sources or the entrainment of local waters enriched in DOC due to chemotrophic productivity. Natural and radio-carbon analyses are underway and will provide further insight into the ultimate source of this colored, fluorescent hydrothermal DOM.

  17. Efficient export of carbon to the deep ocean through dissolved organic matter.

    PubMed

    Hopkinson, Charles S; Vallino, Joseph J

    2005-01-13

    Oceanic dissolved organic carbon (DOC) constitutes one of the largest pools of reduced carbon in the biosphere. Estimated DOC export from the surface ocean represents 20% of total organic carbon flux to the deep ocean, which constitutes a primary control on atmospheric carbon dioxide levels. DOC is the carbon component of dissolved organic matter (DOM) and an accurate quantification of DOM pools, fluxes and their controls is therefore critical to understanding oceanic carbon cycling. DOC export is directly coupled with dissolved organic nitrogen and phosphorus export. However, the C:N:P stoichiometry (by atoms) of DOM dynamics is poorly understood. Here we study the stoichiometry of the DOM pool and of DOM decomposition in continental shelf, continental slope and central ocean gyre environments. We find that DOM is remineralized and produced with a C:N:P stoichiometry of 199:20:1 that is substantially lower than for bulk pools (typically >775:54:1), but greater than for particulate organic matter (106:16:1--the Redfield ratio). Thus for a given mass of new N and P introduced into surface water, more DOC can be exported than would occur at the Redfield ratio. This may contribute to the excess respiration estimated to occur in the interior ocean. Our results place an explicit constraint on global carbon export and elemental balance via advective pathways. PMID:15650735

  18. INFLUENCE OF METHOD FOR REMOVAL OF SESTON ON THE DISSOLVED ORGANIC MATTER(1).

    PubMed

    Parker, B C

    1967-12-01

    Comparisons of various methods and method modifications for treating water samples to render them free of seston prior to analysis of dissolved organic matter have corroborated a number of suspected sources of error. Among the more important points arising from this study arc: 1. All cellulose ester filters must be washed to remove elutable carbon. 2. In some instances filtration to dryness may produce artifacts resulting from cell injury. 3. A significant difference in filter retention can result between 0.45 and 0.22 μ membranes. 4. Among the methods most satisfactory are wet filtration through 0.22 μ pre-washed Millipore membranes and continuous-flow centrifugation at ca. 10,000 x g and 100 cc/min flow rate, both of which have their inherent weaknesses and limitations. 5. Regular centrifugation does not remove some planktonic organisms which have considerable buoyancy, or organic substances may somehow be released by cells without producing morphological damage. The newly developed bio dialysis technique for dissolved organic matter collection consistently yielded lower values than continuous-flow centrifugation. In contrast, biodialysis yielded lower values for pond water and higher values for Scenedesmus cultures than the best filtration method. Evidence suggests that biodialysis will be useful as both a supplementary and, in some zuays, more accurate method in studies of dissolved organic matter. PMID:27065026

  19. 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.

  20. Influence of dissolved organic matter on acute toxicity of zinc to larval fathead minnows (Pimephales promelas).

    PubMed

    Bringolf, Robert B; Morris, Brady A; Boese, Connie J; Santore, Robert C; Allen, Herbert E; Meyer, Joseph S

    2006-10-01

    We conducted laboratory toxicity tests in support of the development of a biotic ligand model (BLM) to predict acute toxicity of zinc (Zn) to fathead minnows (Pimephales promelas). To test the effect of dissolved organic matter (DOM) on Zn toxicity, we exposed larval fathead minnows to Zn in water containing elevated concentrations of dissolved organic carbon (DOC) in 96-h static-renewal toxicity tests. We tested DOM isolated from four surface waters: Cypress Swamp, Delaware; Edisto River, South Carolina; Suwannee River, Georgia; and Wilmington, Delaware, wastewater treatment effluent. The DOM isolates from the Edisto River and Wilmington wastewater treatment effluent contained elevated concentrations of NaCl (20-110x control NaCl) due to the use of a Na+-exchange resin to remove Ca2+ and Mg2+ during the DOM isolation process. Therefore, we also performed Zn toxicity tests in which we added up to 20 mM NaCl to exposure solutions containing Cypress Swamp and Suwannee River DOM. A threshold concentration of 11 mg DOC/L was needed to decrease Zn toxicity, after which the 96 h Zn LC50 was positively correlated with DOC concentration. Elevated NaCl concentrations did not alter Zn toxicity in the presence of DOM. In conjunction with data from other studies with fish and invertebrates, results of this study were used to calibrate Version 2.1.1 of the Zn BLM. BLM-predicted LC50s for our exposure waters containing elevated DOM concentrations were within the range of acceptable deviation relative to the observed LC50s (i.e., 0.5-2x observed LC50s); however, BLM-predicted LC50s for our exposure waters containing < 1 mg DOC/L were 2-3x lower than the observed LC50s (i.e., the BLM over-predicted the toxicity). Therefore, the current composite-species BLM for Zn could be improved for fathead minnows if that species were modeled separately from the other species used to calibrate Version 2.1.1. PMID:16788742

  1. 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

  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. Functional variability of dissolved organic matter from the surface water of a productive lake.

    PubMed

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

    2008-01-01

    Functional variability of dissolved organic matter (DOM) from the surface water of Esthwaite Water (N. England) was investigated using a series of 12 standardised assays, which provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo(a)pyrene binding, hydrophilicity, and adsorption to alumina. Ten lakewater samples were collected at different times of year during 2003-2005, and DOM concentrates obtained by low-temperature rotary evaporation. Suwannee River Fulvic Acid was used as a quality control standard. For nine of the assays, variability among DOM samples was significantly (p<0.01) greater than could be explained by analytical error. Seasonal trends observed for six of the assays could be explained by a simple mixing model in which the two end-members were DOM from the catchment (allochthonous) and DOM produced within the lake (autochthonous). The fraction of autochthonous DOM predicted by the model is significantly correlated (p<0.01) with chlorophyll concentration, consistent with production from phytoplankton. Autochthonous DOM is less light-absorbing, less fluorescent, more hydrophilic, and possesses fewer proton-dissociating groups, than allochthonous material. PMID:17675206

  4. 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.

  5. 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. PMID:26404069

  6. Quantifying dissolved organic carbon concentrations in upland catchments using phenolic proxy measurements

    NASA Astrophysics Data System (ADS)

    Peacock, Mike; Burden, Annette; Cooper, Mark; Dunn, Christian; Evans, Chris D.; Fenner, Nathalie; Freeman, Chris; Gough, Rachel; Hughes, David; Hughes, Steve; Jones, Tim; Lebron, Inma; West, Mike; Zieliński, Piotr

    2013-01-01

    SummaryConcentrations of dissolved organic carbon (DOC) in soil and stream waters in upland catchments are widely monitored, in part due to the potential of DOC to form harmful by-products when chlorinated during treatment of water for public supply. DOC can be measured directly, though this is expensive and time-consuming. Light absorbance in the UV-vis spectrum is often used as a surrogate measurement from which a colour-carbon relationship between absorbance and DOC can be derived, but this relationship can be confounded by numerous variables. Through the analysis of data from eight sites in England and Wales we investigate the possibility of using the concentration of phenolic compounds in water samples as a proxy for DOC concentration. A general model using data from all the sites allowed DOC to be calculated from phenolics at an accuracy of 81-86%. A detailed analysis at one site revealed that a site-specific calibration was more accurate than the general model, and that this compared favourably with a colour-carbon calibration. We therefore recommend this method for use where estimates of DOC concentration are needed, but where time and money are limiting factors, or as an additional method to calculate DOC alongside colour-carbon calibrations. Tests demonstrated only small amounts of phenolic degradation over time; a loss of 0.92 mg L-1 after 8 months in storage, and so this method can be used on older samples with limited loss of accuracy.

  7. Interactions of dissolved organic matter with natural and engineered inorganic colloids: a review.

    PubMed

    Philippe, Allan; Schaumann, Gabriele E

    2014-08-19

    This contribution critically reviews the state of knowledge on interactions of natural colloids and engineered nanoparticles with natural dissolved organic materials (DOM). These interactions determine the behavior and impact of colloids in natural system. Humic substances, polysaccharides, and proteins present in natural waters adsorb onto the surface of most colloids. We outline major adsorption mechanisms and structures of adsorption layers reported in the literature and discuss their generality on the basis of particle type, DOM type, and media composition. Advanced characterization methods of both DOM and colloids are needed to address insufficiently understood aspects as DOM fractionation upon adsorption, adsorption reversibility, and effect of capping agent. Precise knowledge on adsorption layer helps in predicting the colloidal stability of the sorbent. While humic substances tend to decrease aggregation and deposition through electrostatic and steric effects, bridging-flocculation can occur in the presence of multivalent cations. In the presence of DOM, aggregation may become reversible and aggregate structure dynamic. Nonetheless, the role of shear forces is still poorly understood. If traditional approaches based on the DLVO-theory can be useful in specific cases, quantitative aggregation models taking into account DOM dynamics, bridging, and disaggregation are needed for a comprehensive modeling of colloids stability in natural media.

  8. 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).

  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. 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...

  11. 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...

  12. 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

  13. 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).

  14. Cellulase activity and dissolved organic carbon release from lignocellulose macrophyte-derived in four trophic conditions.

    PubMed

    Bottino, Flávia; Cunha-Santino, Marcela Bianchessi; Bianchini, Irineu

    2016-01-01

    Considering the importance of lignocellulose macrophyte-derived for the energy flux in aquatic ecosystems and the nutrient concentrations as a function of force which influences the decomposition process, this study aims to relate the enzymatic activity and lignocellulose hydrolysis in different trophic statuses. Water samples and two macrophyte species were collected from the littoral zone of a subtropical Brazilian Reservoir. A lignocellulosic matrix was obtained using aqueous extraction of dried plant material (≈40°C). Incubations for decomposition of the lignocellulosic matrix were prepared using lignocelluloses, inoculums and filtered water simulating different trophic statuses with the same N:P ratio. The particulate organic carbon and dissolved organic carbon (POC and DOC, respectively) were quantified, the cellulase enzymatic activity was measured by releasing reducing sugars and immobilized carbon was analyzed by filtration. During the cellulose degradation indicated by the cellulase activity, the dissolved organic carbon daily rate and enzyme activity increased. It was related to a fast hydrolysable fraction of cellulose that contributed to short-term carbon immobilization (ca. 10 days). After approximately 20 days, the dissolved organic carbon and enzyme activity were inversely correlated suggesting that the respiration of microorganisms was responsible for carbon mineralization. Cellulose was an important resource in low nutrient conditions (oligotrophic). However, the detritus quality played a major role in the lignocelluloses degradation (i.e., enzyme activity) and carbon release. PMID:26991278

  15. 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

  16. Dynamics of Dissolved Organic Matter in Amazon Basin: Insights into Negro River Contribution

    NASA Astrophysics Data System (ADS)

    Moreira-Turcq, P.; Perez, M. P.; Benedetti, M.; Oliveira, M. A.; Lagane, C.; Seyler, P.; Oliveira, E.

    2006-12-01

    The study of global carbon cycle requires a precise knowledge of spatial and temporal distributions and exportation from continents to oceans. Organic carbon fluxes represent approximately half of the total carbon budget carried by rivers. Tropical rivers transport two third of the total organic carbon discharged into the world oceans but important gaps still exist in the knowledge of the tropical river carbon biochemistry. The Amazon River is responsible for 10% of the annual amount of organic carbon transported from rivers to oceans. The most important portion of total organic matter transported in the Amazon Basin is the dissolved fraction (between 80% and 95%). Amazonian annual flux of dissolved organic matter is directly related to hydrological variations. All rivers in the Amazon basin are characterized by monomodal hydrograms, with a low water period in october/november and a high water period in may/june. Temporal variations in Amazon dissolved organic carbon (3.0 to 9.1 mg l^{- 1}) are mainly controled by Negro River inputs. DOC and DON contributions from the Negro River can vary between 120 kgC s-1 and 520 kg C s-1, and between 5 kgN s--1 and 15 kgN s-1, during low and high water period, respectivelly. In the Negro River, during high water stages, while DOC concentrations are stable from the upstream stations to the downstream ones (about 11 mg l-1), discharge increases from 16000 to 46000 m3 s-1 and NOD can quintuple from upstream (0.071 mg l-1) to downstream (0.341 mg l-1). Then the nature of dissolved organic matter is variable (C/N ratio varied from 33 to 120 from upstream to downstream). During low water stages DOC concentrations are lower (mean DOC of 8.1 mg l-1) while DON is in the same range, discharge is about 10000 m3 s-1 at downstream stations of Negro River and the C/N ratio is lower and steadier along the River. Finaly, despite a low basin surface (12%) compared with the two other main Amazon tributaries, Solimões and Madeira Rivers, and a

  17. Dissolved organic carbon trends resulting from changes in atmospheric deposition chemistry.

    PubMed

    Monteith, Donald T; Stoddard, John L; Evans, Christopher D; de Wit, Heleen A; Forsius, Martin; Høgåsen, Tore; Wilander, Anders; Skjelkvåle, Brit Lisa; Jeffries, Dean S; Vuorenmaa, Jussi; Keller, Bill; Kopácek, Jiri; Vesely, Josef

    2007-11-22

    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 mechanisms related to climate change, nitrogen deposition or changes in land use, and by implication suggest that current concentrations and fluxes are without precedent. All of these hypotheses imply that DOC levels will continue to rise, with unpredictable consequences for the global carbon cycle. Alternatively, it has been proposed that DOC concentrations are returning toward pre-industrial levels as a result of a gradual decline in the sulphate content of atmospheric deposition. Here we show, through the assessment of time series data from 522 remote lakes and streams in North America and northern Europe, that rising trends in DOC between 1990 and 2004 can be concisely explained by a simple model based solely on changes in deposition chemistry and catchment acid-sensitivity. We demonstrate that DOC concentrations have increased in proportion to the rates at which atmospherically deposited anthropogenic sulphur and sea salt have declined. We conclude that acid deposition to these ecosystems has been partially buffered by changes in organic acidity and that the rise in DOC is integral to recovery from acidification. Over recent decades, deposition-driven increases in organic matter solubility may have increased the export of DOC to the oceans, a potentially important component of regional carbon balances. The increase in DOC concentrations in these regions appears unrelated to other climatic factors. PMID:18033294

  18. 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.

  19. Simulating Streamflow and Dissolved Organic Matter Export from small Forested Watersheds

    NASA Astrophysics Data System (ADS)

    Xu, N.; Wilson, H.; Saiers, J. E.

    2010-12-01

    Coupling the rainfall-runoff process and solute transport in catchment models is important for understanding the dynamics of water-quality-relevant constituents in a watershed. To simulate the hydrologic and biogeochemical processes in a parametrically parsimonious way remains challenging. The purpose of this study is to quantify the export of water and dissolved organic matter (DOM) from a forested catchment by developing and testing a coupled model for rainfall-runoff and soil-water flushing of DOM. Natural DOM plays an important role in terrestrial and aquatic systems by affecting nutrient cycling, contaminant mobility and toxicity, and drinking water quality. Stream-water discharge and DOM concentrations were measured in a first-order stream in Harvard Forest, Massachusetts. These measurements show that stream water DOM concentrations are greatest during hydrologic events induced by rainfall or snowmelt and decline to low, steady levels during periods of baseflow. Comparison of the stream-discharge data to calculations of a simple rainfall-runoff model reveals a hysteretic relationship between stream-flow rates and the storage of water within the catchment. A modified version of the rainfall-runoff model that accounts for hysteresis in the storage-discharge relationship in a parametrically simple way is capable of describing much, but not all, of the variation in the time-series data on stream discharge. Our ongoing research is aimed at linking the new rainfall-runoff formulation with coupled equations that predict soil-flushing and stream-water concentrations of DOM as functions of the temporal change in catchment water storage. This model will provide a predictive tool for examining how changes in climatic variables would affect the runoff generation and DOM fluxes from terrestrial landscape.

  20. Fluxes of dissolved organic matter and mineral weathering products from Corn Belt landscapes dominated by subsurface drainage: large-scale soil and hydrologic change

    NASA Astrophysics Data System (ADS)

    Jelinski, N. A.; Yoo, K.; Strock, J.; Dalzell, B. J.; Finlay, J. C.

    2011-12-01

    The human alteration of agricultural landscapes is one of the most important factors in pedologic and geomorphic change, and can influence hydrology and aquatic chemistry at large scales. Most of the Midwestern Corn Belt that is currently dominated by subsurface tile drainage (such as southern Minnesota) was historically prairie and wetland which had hydrologic flow-paths through organic-rich surface soil horizons, a condition that favored the export of dissolved organic matter. When hydrology is altered through subsurface drainage, adsorption of organic materials to mineral surfaces and increases in mineral weathering may result because more water is flowing through subsurface mineral soils. We suggest that the alteration of hydrologic flowpaths in agricultural landscapes can dramatically alter the rate of mineral weathering as well as surface export of weathering products and dissolved organic matter. This could be at least one contributing factor to observed increases in Mississippi River alkalinity over the past four decades. Here, we examine trends in dissolved organic carbon, total dissolved nitrogen, dissolved organic nitrogen, total suspended solids, and indicators of mineral weathering (Si, Ca, Na, K) from subsurface drainage systems located in southwestern MN. Then, using a simple conceptual model, we estimate the effects of subsurface drainage on the regional fluxes of these parameters and present directions for future research.

  1. 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.

  2. Elevated atmospheric CO2 fuels leaching of old dissolved organic matter at the alpine treeline

    NASA Astrophysics Data System (ADS)

    Hagedorn, Frank; van Hees, Patrick A. W.; Handa, I. Tanya; HäTtenschwiler, Stephan

    2008-06-01

    Dissolved organic matter (DOM), the mobile form of soil organic matter (SOM), plays an important role in soil C cycling and in nutrient transport. We investigated the effects of 5 years of CO2 enrichment (370 versus 570 μmol CO2 mol-1) on DOM dynamics at the alpine treeline, including the analysis of fast-cycling components such as low molecular weight organic acids (LMWOAs), dissolved organic carbon (DOC) biodegradability, and the decomposition of 14C-labeled oxalate. Concentrations of DOC in canopy throughfall were 20% higher at elevated CO2, probably driven by higher carbohydrate concentrations in leaves. In the organic soil layer, 5 years of CO2 enrichment increased water-extractable organic C by 17% and soil solution DOC at 5 cm depth by 20%. The 13C tracing of recently assimilated CO2 revealed that the input of recent plant-derived C (<15% of total DOC) was smaller than the CO2-induced increase in DOC. This strongly suggests that CO2 enrichment enhanced the mobilization of native DOC, which is supported by significant increases in dissolved organic nitrogen (DON). We mainly attribute these increases to a stimulated microbial activity as indicated by higher basal and soil respiration rates (+27%). The 14C-labeled oxalate was more rapidly mineralized from high CO2 soils. The concentrations of LMWOAs, but also those of "hydrophilic" DOC and biodegradable DOC (6% of total DOC), were, however, not affected by elevated CO2, suggesting that production and consumption of "labile" DOC were in balance. In summary, our data suggest that 5 years of CO2 enrichment speeded up the cycling of "labile" DOM and SOM in a late successional treeline ecosystem and increased the mobilization of older DOM through a stimulated microbial activity. Such a "priming effect" implies that elevated CO2 can accelerate the turnover of native SOM, and thus, it may induce increasing losses of old C from thick organic layers.

  3. 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.

  4. 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

  5. [The qualitative analysis method of the dissolved organic matter (DOM) for ABS wastewater].

    PubMed

    Lai, Bo; Zhou, Yue-xi; Song, Yu-dong; Xi, Hong-bo; Sun, Li-dong; Chen, Jia-yun

    2011-03-01

    The dissolved organic matter (DOM) of acrylonitrile-butadiene-styrene (ABS) resin wastewater was qualitatively analysed by gas chromatography with mass spectrometry(GC-MS), Fourier transform infrared spectrometer(FTIR) and three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy. The detected results shows that the GC-MS qualitatively analysed 21 dissolved organic pollutants, such as acetophenone, styrene, alpha, alpha-dimethyl-benzenemethanol, 3,3'oxybis-propanenitrile, 3, 3'-iminobis-propanenitrile, 3,3'-thiobis-propanenitrile, 3-(dimethylamino)-propanenitrile and 2-propenenitrile. The results of Fourier transform infrared spectrometer (FTIR) and three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy could examine and certify the accuracy and integrity for the qualitative analysis of GC-MS. The results of this study provides an important guiding role for the development of wastewater treatment process.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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

  11. Effects of dissolved organic carbon on sorption and mobility of imidacloprid in soil.

    PubMed

    Flores-Céspedes, F; González-Pradas, E; Fernández-Pérez, M; Villafranca-Sánchez, M; Socías-Viciana, M; Ureña-Amate, M D

    2002-01-01

    To evaluate the effects of dissolved organic carbon on sorption and mobility of the insecticide imidacloprid [1-(6-chloro-3-pyridinyl) methyl-N-nitro-2-imidazolidinimine] in soils, adsorption and column experiments were performed by using a typical calcareous soil from southeastern Spain and two different types of dissolved organic carbon, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 to 100 mg L(-1), produces in all cases a decreasing amount of imidacloprid adsorbed in the soil studied. From the column experiments the retardation coefficients (RC) were calculated for imidacloprid by using either 0.01 M CaCl2 aqueous solution (RC = 2.10), 0.01 M CaCl2 DOC-PE solution (RC = 1.65), or 0.01 M CaCl2 DOC-TA solution (RC = 1.87). The results indicate that mobility of imidacloprid is increased 21.4 and 11.0% in the presence of DOC-PE and DOC-TA solutions, respectively. Dissolved organic carbon reduces imidacloprid sorption by competing with the pesticide molecules for sorption sites on the soil surface, allowing enhanced leaching of imidacloprid and potentially increasing ground water contamination.

  12. Nitrogen and dissolved organic carbon (DOC) losses from an artificially drained grassland on organic soils

    NASA Astrophysics Data System (ADS)

    Tiemeyer, B.; Kahle, P.

    2014-08-01

    Nitrate-nitrogen (NO3-N) as well as dissolved organic carbon (DOC) and nitrogen (DON) concentrations and losses were studied for three and two years, respectively, in a small catchment dominated by a degraded peatland used as intensive grassland. Concentrations in the shallow groundwater were spatially and temporally very variable, with NO3-N being the most dynamic component (7.3 ± 12.5 mg L-1) and ranging from 0 to 79.4 mg L-1. Average NO3-N concentrations of 10.3 ± 5.4 mg L-1 (0 to 25.5 mg L-1) in the ditch draining the catchment and annual NO3-N losses of 19, 35 and 26 kg ha-1 confirmed drained peatlands as an important source of diffuse N pollution. The highest NO3-N losses occurred during the wettest year. Resulting from concentration of 2.4 ± 0.8 mg L-1 (0.7 to 6.2 mg L-1), DON added a further 4.5 to 6.4 kg ha-1 to the N losses and thus formed a relevant (15%) component of the total N losses. Ditch DOC concentrations of 24.9 ± 5.9 mg L-1 (13.1 to 47.7 mg L-1) resulted in DOC losses of 66 kg ha-1 in the wet year of 2006/2007 and 39 kg ha-1 in the dry year of 2007/2008. Ditch DOC concentration were lower than the groundwater DOC concentration of 50.6 ± 15.2 mg L-1 (14.9 to 88.5 mg L-1). Both DOC and N concentrations were governed by hydrological conditions, but NO3-N reacted much faster and clearer on rising discharge rates than DOC, which tended to be higher under drier conditions. In the third year of the study, the superposition of a very wet summer and land use changes from grassland to arable land in a part of the catchment suggests that, under re-wetting conditions with a high groundwater table in summer, NO3-N would diminish quickly, while DOC would remain on a similar level. Further intensification of the land use, on the other hand, would increase N losses to receiving water bodies.

  13. Photochemical mineralization of dissolved organic nitrogen to ammonium in the Baltic sea.

    PubMed

    Vahätalo, Anssi V; Zepp, Richard G

    2005-09-15

    Solar-radiation-induced photochemistry can be considered as a new source of nutrients when photochemical reactions release bioavailable nitrogen from biologically nonreactive dissolved organic nitrogen (DON). Pretreatments of Baltic Sea waters in the dark indicated that >72% of DON was recalcitrant to biological mineralization. When this DON (16-21.5 microM) was exposed to simulated solar radiation, the concentration of NH4+ increased 0.5-2.5 microM more in irradiated waters than in the dark controls. The photochemical production of NH4+ and the dose of absorbed photons were used to calculate the apparent quantum yield spectrum for photoammonification [mol NH4+ (mol photons)(-1) nm(-1)] at wavelengths (lambda) of 290-700 nm (phiNH4,lambda). The modeled mean rates of photoammonification based on phiNH4,lambda were 143 and 53 micromol NH4+ m(-2) d(-1) at the surface and in the whole water column, respectively, of Baltic Sea stations during summer. The results of this study indicate thatthe rate of photoammonification approximately equals and periodically exceeds the rate of atmospheric deposition of reactive inorganic nitrogen to the northern Baltic Sea. Forthese stratified surface waters beyond riverine input of labile nitrogen, photoammonification can periodically be the largest source of new bioavailable nitrogen. PMID:16201620

  14. Fate of terrestrial colored dissolved organic matter (CDOM) in the Arctic Ocean: exported or removed?

    NASA Astrophysics Data System (ADS)

    Granskog, M. A.; Stedmon, C. A.; Dodd, P. A.; Amon, R. M. W.; Pavlov, A. K.; de Steur, L.; Hansen, E.

    2012-04-01

    Colored dissolved organic matter (CDOM) was measured with hydrographic parameters (salinity, d18O and inorganic nutrients) across Fram Strait. East Greenland Current (EGC) surface waters showed a pronounced CDOM absorption maximum between 30 and 120 m depth associated with both river and sea ice brine-enriched water, characteristic of polar mixed layer water and upper halocline water. Lowest CDOM was found in the Atlantic inflow within the West Spitsbergen Current (WSC). Although applied elsewhere in the Arctic, we show that the salinity-CDOM relationship not suitable for evaluating the mixing behavior of CDOM (conservative vs. non-conservative) in Fram Strait. The strong correlation between meteoric water and optical properties of CDOM are indicative of the terrigenous origin of CDOM in the EGC and marine origin in WSC. Based on CDOM absorption in Polar Water and comparison with an Arctic river discharge weighted mean, we estimate that a 68% integrated loss of CDOM absorption across 250-600 nm has occurred, with a preferential removal of absorption at longer wavelengths reflecting the loss of high molecular weight material. Budget calculations of CDOM exports through Fram Strait using modeled volume transports indicate that the net southward export of CDOM in Fram Strait equals to 8 to 14% of the total riverine CDOM inputs to the Arctic Ocean, thus physical export is not a major sink of CDOM. We propose that CDOM can aid in discriminating glacial melt waters from Arctic riverine freshwater on the east Greenland shelf.

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

    PubMed

    Simsek, Halis; Kasi, Murthy; Ohm, Jae-Bom; Murthy, Sudhir; Khan, Eakalak

    2016-04-01

    Dissolved organic nitrogen (DON) and its biodegradability in treated wastewater have recently gained attention due to increased regulatory requirements on effluent quality to protect receiving waters. Laboratory scale chemostat experiments were conducted at 9 different solids retention times (SRTs) (0.3, 0.7, 2, 3, 4, 5, 7, 8, and 13 days) to examine whether SRT could be used to control DON, biodegradable DON (BDON), and DON biodegradability (BDON/DON) levels in treated wastewater. Results indicated no trend between effluent DON and SRTs. Effluent BDON was comparable for SRTs of 0.3-4 days and had a decreasing trend with SRT after that. Effluent DON biodegradability (effluent BDON/effluent DON) ranging from 23% to 59% tended to decrease with SRT. Chemostat during longer SRTs, however, was contributing to non-biodegradable DON (NBDON) and this fraction of DON increased with SRT above 4 days. Model calibration results indicated that ammonification rate, and growth rates for ordinary heterotrophs, ammonia oxidizing bacteria and nitrite oxidizing bacteria were not constants but have a decreasing trend with increasing SRT. This study indicates the benefit of high SRTs in term of producing effluent with less DON biodegradability leading to relatively less oxygen consumption and nutrient support in receiving waters. PMID:26841227

  16. Dissolved organic matter composition drives the marine production of brominated very short-lived substances.

    PubMed

    Liu, Yina; Thornton, Daniel C O; Bianchi, Thomas S; Arnold, William A; Shields, Michael R; Chen, Jie; Yvon-Lewis, Shari A

    2015-03-17

    Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean. PMID:25723123

  17. 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.

  18. Differential utilization patterns of dissolved organic phosphorus compounds by heterotrophic bacteria in two mountain lakes

    PubMed Central

    Rofner, Carina; Sommaruga, Ruben; Pérez, María Teresa

    2016-01-01

    Although phosphorus limitation is common in freshwaters and bacteria are known to use dissolved organic phosphorus (DOP), little is known about how efficiently DOP compounds are taken up by individual bacterial taxa. Here, we assessed bacterial uptake of three model DOP substrates in two mountain lakes and examined whether DOP uptake followed concentration-dependent patterns. We determined bulk uptake rates by the bacterioplankton and examined bacterial taxon-specific substrate uptake patterns using microautoradiography combined with catalyzed reporter deposition–fluorescence in situ hybridization. Our results show that in the oligotrophic alpine lake, bacteria took up ATP, glucose-6-phosphate and glycerol-3-phosphate to similar extents (mean 29.7 ± 4.3% Bacteria), whereas in the subalpine mesotrophic lake, ca. 40% of bacteria took up glucose-6-phosphate, but only ∼20% took up ATP or glycerol-3-phosphate. In both lakes, the R-BT cluster of Betaproteobacteria (lineage of genus Limnohabitans) was over-represented in glucose-6-phosphate and glycerol-3-phosphate uptake, whereas AcI Actinobacteria were under-represented in the uptake of those substrates. Alphaproteobacteria and Bacteroidetes contributed to DOP uptake proportionally to their in situ abundance. Our results demonstrate that R-BT Betaproteobacteria are the most active bacteria in DOP acquisition, whereas the abundant AcI Actinobacteria may either lack high affinity DOP uptake systems or have reduced phosphorus requirements. PMID:27312963

  19. Differential utilization patterns of dissolved organic phosphorus compounds by heterotrophic bacteria in two mountain lakes.

    PubMed

    Rofner, Carina; Sommaruga, Ruben; Pérez, María Teresa

    2016-09-01

    Although phosphorus limitation is common in freshwaters and bacteria are known to use dissolved organic phosphorus (DOP), little is known about how efficiently DOP compounds are taken up by individual bacterial taxa. Here, we assessed bacterial uptake of three model DOP substrates in two mountain lakes and examined whether DOP uptake followed concentration-dependent patterns. We determined bulk uptake rates by the bacterioplankton and examined bacterial taxon-specific substrate uptake patterns using microautoradiography combined with catalyzed reporter deposition-fluorescence in situ hybridization. Our results show that in the oligotrophic alpine lake, bacteria took up ATP, glucose-6-phosphate and glycerol-3-phosphate to similar extents (mean 29.7 ± 4.3% Bacteria), whereas in the subalpine mesotrophic lake, ca. 40% of bacteria took up glucose-6-phosphate, but only ∼20% took up ATP or glycerol-3-phosphate. In both lakes, the R-BT cluster of Betaproteobacteria (lineage of genus Limnohabitans) was over-represented in glucose-6-phosphate and glycerol-3-phosphate uptake, whereas AcI Actinobacteria were under-represented in the uptake of those substrates. Alphaproteobacteria and Bacteroidetes contributed to DOP uptake proportionally to their in situ abundance. Our results demonstrate that R-BT Betaproteobacteria are the most active bacteria in DOP acquisition, whereas the abundant AcI Actinobacteria may either lack high affinity DOP uptake systems or have reduced phosphorus requirements. PMID:27312963

  20. 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.

  1. Dissolved organic matter processing within the Atchafalaya basin: from river to backwater swamps

    NASA Astrophysics Data System (ADS)

    Jones, C. N.; Edwards, B.; Keim, R.; Scott, D.

    2013-12-01

    Hydrologic complexity in large floodplains makes examining the fate of nutrients and carbon challenging. We used a combination of stable isotopes (δ18O-H2O, δD-H2O, δ13C-DOC, and δ13C-DIC) and carbon characterization (PARAFAC modeling, SUVA, flurescence index) to identify the fate of both allochthonous (externally produced) and autochthonous (internally produced) dissolved organic matter (DOM) in the Atchafalaya swamp. Three separate synoptic sampling campaigns were completed across an annual flood pulse (rising limb, peak, and falling limb), in which the stable isotopic content of water was used to quantify the gradient of hydrologic connectivity from river to backwater swamp. The carbon characterization and isotopic content provided insight into sources and processing of DOM along that gradient. Results reveal autochthonous and allochthonous carbon signatures across the gradient from backwater swamp to river water during the rising limb. However, as sites become hydrologically connected during the peak, DOM was dominated by allochthonous sources. Following the flood pulse, we expect to once again see stratification across the sites altering the DOM sources, composition, and bioavailability.

  2. 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.

  3. 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.

  4. Effects of pH on Dissolved Organic Matter From Freshwater Algal Species

    NASA Astrophysics Data System (ADS)

    Kehret, Y.; Gueguen, C.

    2009-05-01

    Dissolved organic matter (DOM) is ubiquitous in all natural waters. The nature and composition of aquatic DOM depends on its origin (autochthonous vs. allochthonous) and the physical chemical conditions (pH) of the system. It is clear that autochthonous DOM of algal origin is an important contributor to the DOM pool in most aquatic systems. Little is known on its nature and composition. In this study, algal monocultures of S. acutus and F. crotonensis were grown at two different pHs (pH 7 and 5). The production of exudates was monitored over time and characterized by dissolved organic carbon content, absorbance and synchronous fluorescence. Results indicate a significant difference in the concentration of dissolved organic carbon (DOC) formed per species. The ratio of DOC to chlorophyll a is ten times greater in S. acutus than F. crotonensis. In terms of composition, the production of humic-like compounds varies between species with F. crotonensis producing up to four fold more at natural pH. At lower pH, the production of algal DOM is less but there were more proteins and humic materials generated by both species under decreasing pH, with a significant increase in the S. acutus species. Therefore, the concentration and composition of DOM depends not only on algal species but also on the physical chemical condition (pH level) indicating that water acidification would have a major impact on DOM composition.

  5. 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. PMID:26309797

  6. The surface Arctic Ocean: A dynamic reservoir of terrigenous dissolved organic carbon

    NASA Astrophysics Data System (ADS)

    Hansell, D. A.; Letscher, R. T.

    2012-04-01

    The upper mixed layer of the Arctic Ocean is a globally important sink for dissolved organic matter mobilized from adjacent continents, which in turn are subject to substantial changes with warming of the Arctic system. Understanding the dynamics and fate of this terrigenous material has become critical for our understanding the contributions of the Arctic to the global carbon cycle. Terrigenous dissolved organic carbon (tDOC) had long been viewed as highly conserved within the Arctic Ocean, yet only a fraction of that entering from the rivers survived for export to the North Atlantic. Extensive surveys of tDOC and other tracers between the shelves and the waters overlying the deep basins indicate that a large fraction of the tDOC is subject to slow mineralization. The extent of removal within the Arctic system depends then on the time scale for water mass retention; the longer the retention, the greater the remineralization within the Arctic. Remineralization of tDOC adds to the inorganic carbon inventory and seawater pCO2, thus impacting exchange of CO2 with the atmosphere. This talk will begin with a global view of marine dissolved organic carbon (DOC), from which the context for tDOC in the Arctic Ocean will be established. The surface Arctic Ocean distribution of tDOC will be presented, along with consideration of its dynamics and export to the North Atlantic.

  7. 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.

  8. 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

  9. Reconciling stream dissolved organic matter with snowmelt-driven subsurface flowpaths in a montane, headwater catchment.

    NASA Astrophysics Data System (ADS)

    Barnard, H. R.; Burns, M. A.; McKnight, D. M.; Gabor, R. S.; Brooks, P. D.

    2014-12-01

    Dissolved organic matter (DOM) transport is a key biogeochemical link across the terrestrial-aquatic interface in headwater catchments, and therefore is intimately linked with the hydrologic connectivity of the catchment to the stream. This study evaluated the mobility of specific chemical constituents of DOM during snowmelt in a montane, semi-arid catchment in the Boulder Creek CZO. Dissolved organic matter quality was monitored using fluorescence spectroscopy on a daily basis from water sampled from the soil (10 - 25 cm depth) via tension lysimeters and from the stream during snowmelt and was compared to approximately bi-monthly groundwater samples (~18 m depth). In the stream, a transition occurred from fluorescent DOM (FDOM) being dominated by protein-like material to FDOM being dominated by more humic-like material. The FDOM in the interstitial water of the soils and the groundwater did not change in character. Thus, the stream transition is indicative of an engagement of DOM originating from hillslope soils during snowmelt. Dissolved organic carbon (DOC) normalization of these fluorescent loadings suggest that the peak in DOC concentration seen in the stream is mainly controlled by the non-fluorescent fraction of DOM. These results indicate that shifts in hydrologic connectivity of different watershed units to the stream are a major control on DOM export from the watershed.

  10. 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.

  11. Biogeochemistry of dissolved organic matter in an anoxic intertidal creek bank

    NASA Astrophysics Data System (ADS)

    Seidel, Michael; Beck, Melanie; Riedel, Thomas; Waska, Hannelore; Suryaputra, I. G. N. A.; Schnetger, Bernhard; Niggemann, Jutta; Simon, Meinhard; Dittmar, Thorsten

    2014-09-01

    Seawater circulation in permeable coastal sediments is driven by tidal changes in hydraulic gradients. The resulting submarine groundwater discharge is a source of nutrients and dissolved organic matter (DOM) to the water column. Yet, little is known about the cycling of DOM within tidal sediments, because the molecular DOM characterization remains analytically challenging. One technique that can dissect the multitude of molecules in DOM is ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). To aim at a high resolution DOM analysis we study the seasonal turnover and marine and terrestrial sources of DOM in an intertidal creek bank of the southern North Sea down to 3 m depth and link the biogeochemical processes to FT-ICR-MS data and the analyses of inorganic porewater chemistry, δ13C of solid-phase extracted dissolved organic carbon (SPE-DOC), dissolved black carbon (DBC) and dissolved carbohydrates (DCHO). Increasing concentrations of dissolved Fe, Mn, P, total alkalinity, dissolved nitrogen, DOC and a concomitant decrease of sulfate along the seawater circulation path from the upper tidal flat to the tidal flat margin indicate continuous microbial activity. The relative increase of Si concentrations, unsaturated aliphatics, peptide molecular formulae and isotopically more 13C-enriched SPE-DOC towards the tidal flat margin suggests that remineralization processes mobilize DOM from buried algal (diatoms) and microbial biomass. Porewater in sediments <100 cm depth contains 13C-depleted SPE-DOC and highly unsaturated compounds which are probably derived from eroded peats, suggesting rapid removal of bioavailable marine DOM such as DCHO from the water column and selective enrichment of terrestrial DOM. DBC concentrations are highest in the discharging porewater close to the tidal creek suggesting that the intertidal flat is an important DBC source to the coastal ocean. Porewater DOM accumulating at the low water line is

  12. 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. PMID:26192081

  13. 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.

  14. Uptake of dissolved organic carbon and trace elements by zebra mussels

    NASA Astrophysics Data System (ADS)

    Roditi, Hudson A.; Fisher, Nicholas S.; Sañudo-Wilhelmy, Sergio A.

    2000-09-01

    Zebra mussels (Dreissena polymorpha) are widespread and abundant in major freshwater ecosystems in North America, even though the phytoplankton food resources in some of these systems seem to be too low to sustain them. Because phytoplankton biomass is greatly depleted in ecosystems with large D. polymorpha populations and bacteria do not seem to be an important food source for this species, exploitation of alternative carbon sources may explain the unexpected success of D. polymorpha in such environments. Here we examine the possibility that absorption of dissolved organic carbon (DOC) from water could provide a nutritional supplement to zebra mussels. We find that mussels absorb 14C-labelled DOC produced by cultured diatoms with an efficiency of 0.23%; this indicates that DOC in natural waters could contribute up to 50% of the carbon demand of zebra mussels. We also find that zebra mussels absorb some dissolved metals that have been complexed by the DOM; although absorption of dissolved selenium was unaffected by DOC, absorption of dissolved cadmium, silver and mercury by the mussels increased 32-, 8.7- and 3.6-fold, respectively, in the presence of high-molecular-weight DOC.

  15. Uptake of dissolved organic carbon and trace elements by zebra mussels.

    PubMed

    Roditi, H A; Fisher, N S; Sañudo-Wilhelmy, S A

    2000-09-01

    Zebra mussels (Dreissena polymorpha) are widespread and abundant in major freshwater ecosystems in North America, even though the phytoplankton food resources in some of these systems seem to be too low to sustain them. Because phytoplankton biomass is greatly depleted in ecosystems with large D. polymorpha populations and bacteria do not seem to be an important food source for this species, exploitation of alternative carbon sources may explain the unexpected success of D. polymorpha in such environments. Here we examine the possibility that absorption of dissolved organic carbon (DOC) from water could provide a nutritional supplement to zebra mussels. We find that mussels absorb 14C-labelled DOC produced by cultured diatoms with an efficiency of 0.23%; this indicates that DOC in natural waters could contribute up to 50% of the carbon demand of zebra mussels. We also find that zebra mussels absorb some dissolved metals that have been complexed by the DOM; although absorption of dissolved selenium was unaffected by DOC, absorption of dissolved cadmium, silver and mercury by the mussels increased 32-, 8.7- and 3.6-fold, respectively, in the presence of high-molecular-weight DOC.

  16. 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

  17. Effect of biomass adaptation to biodegradation of dissolved organic carbon in water.

    PubMed

    Tihomirova, K; Briedis, A; Rubulis, J; Juhna, T

    2012-04-01

    In the present study the time of adaptation of fixed biomass for biodegradation of natural organic matter was investigated. The experiments were done in columns that are usually used for rapid determination of biodegradable dissolved organic carbon (BDOC). The biomass was adapted to samples with different concentrations of organic substances before measurements by pumping water to be investigated through the columns for several days. The time of adaptation was dependent on the initial concentration of the organic matter in the water sample. The adaptation time increased from 6 to 24 h with increase of concentration of acetate solution from 2 to 10 mg/l, thus adaptation rate decreased simultaneously from 0.28 to 0.11 min(-1). In natural water samples with the initial concentration in the range from 4.61-10.82 mg/l of dissolved organic carbon (DOC) the maximal adaptation time was less than 24 h. During the adaptation period the increase in reproducibility and decrease in the standard deviation was observed. The study showed that adaptation of column to the different concentration of organic matter in water sample is necessary in order to decrease the bias in BDOC measurements when using columns tests. PMID:21892664

  18. 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.

  19. Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater.

    PubMed

    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 (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. PMID:27481013

  20. Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater.

    PubMed

    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 (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.

  1. 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.

  2. 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. PMID:24704143

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. Determination of Dissolved Organic Sulfur in Seawater, and its Distribution in the Chesapeake Bay

    NASA Astrophysics Data System (ADS)

    Chavous, B.; Filippino, K. C.; Cutter, G. A.

    2001-12-01

    Although there are measurements of specific organic sulfur compounds in marine waters, the total concentration of dissolved organic sulfur (DOS) is unknown. However, this poorly quantified component in the global sulfur cycle is the precursor to the radiatively important gas, carbonyl sulfide, and contains very strong ligands that complex trace metals, affecting their bioavailability/cycling. Nevertheless, the high concentration of sulfate in seawater (28 mM) has hampered efforts to determine DOS. In order to obtain DOS data for different marine regimes, we have developed a novel analytical method that employs: (1) sulfate removal using Ba, followed by ion exchange; (2) determination of the nanomolar concentrations of residual sulfate; and (3) reductive pyrolysis (combustion at 1050 C in pure hydrogen) of a treated (as in (1)) sample to quantitatively produce hydrogen sulfide from all forms of sulfur, which is then quantified using GC/flame photometric detection. A wide variety of model S compounds (e.g., DMSP, glutathione, taurine, marine and freshwater humics) have been analyzed to test the efficiency of the method with good results. The method's detection limit is 15 nM S, the precision is <10% RSD at 100 nM S, and it is highly linear (>2000 nM S). To examine the estuarine distribution of DOS, water samples from the Chesapeake Bay were taken in July 1997 (earlier version of the method) and June 2001. These were 0.4 um filtered, placed in glass vials, and quick frozen for temporary storage (<2 months). In 2001, DOS concentrations in the Bay averaged 312+/-75 nM S, in close agreement with those in 1997 except in the uppermost (riverine) Bay. The distributions show slightly decreasing concentrations from the riverine to the seaward end of the Bay. No obvious correlations with nutrients or chlorophyll are apparent. However, the distributions do appear to be affected by higher concentrations in the rivers (S-containing humic acids?).

  9. 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.

  10. Spatial and Temporal Variations of Dissolved Organic Matter in Florida Coastal Everglades

    NASA Astrophysics Data System (ADS)

    Chen, M.; Maie, N.; Jaffe, R.

    2010-12-01

    The Florida Everglades is a coastal wetland, which is characterized by a freshwater to marine gradient ranging from freshwater marshes, through mangrove fringe to the seagrass dominated Florida Bay estuary. Dissolved organic matter (DOM) in this system is am important biogeochemical component as most of the N and P are in an organic form. The dynamics of DOM in the Everglades is complex given its versatile sources and the effects of geomorphology, hydrology, water chemistry, and degradation processes on DOM composition and fate. Here we present long-term DOM characterization data (4 yrs) from monthly surface water samples collected at fourteen sampling stations within the Everglades. We applied a high throughput and sensitive spectroscopic method, namely Excitation Emission Matrix (EEM) fluorescence coupled with Parallel Factor Analysis (PARAFAC) in an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales. Eight fluorescence components were modeled through PARAFAC with six humic-like and two protein-like components being identified. The results presented clear spatial clustering and seasonal variations. For example, freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, while estuarine sites were more enriched in algae- and microbial-derived humic-like and protein-like inputs. Coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. Peat-based sites could be clearly differentiated from marl-based sites based on EEM-PARAFAC data. Bulk DOC data and proxies like FI, SR, and a (254nm m-1)* displayed clear spatial and seasonal variations as well. This study highlights the use of optical properties monitoring and in particular EEM-PARAFAC as an effective technique to investigate the DOM dynamics in the aquatic ecosystems.

  11. Field-scale fluorescence fingerprinting of biochar-borne dissolved organic carbon.

    PubMed

    Uchimiya, Minori; Liu, Zhongzhen; Sistani, Karamat

    2016-03-15

    Biochar continues to receive worldwide enthusiasm as means of augmenting recalcitrant organic carbon in agricultural soils. Realistic biochar amendment rate (typically less than 1 wt%) in the field scale, and subsequent loss by sizing, rain, and other transport events demand reliable methods to quantify the remaining portions of amended biochar. This study employed fluorescence excitation-emission (EEM) spectrophotometry and parallel factor analysis (PARAFAC) to specifically target pyrogenic dissolved organic carbon (DOC) released by amended biochar during the course of a field trial at Bowling Green, KY experimental site. Toluene/methanol (1:6 v/v) extracts of surface (0-15 cm) soils amended with 21.28 t ha(-1) fast pyrolysis biochar afforded PARAFAC fingerprints representing different degrees of aromaticity. Compared to the control without treatments, biochar treatment (with and without poultry manure or chemical fertilizer) increased the relative contribution of PARAFAC fingerprint attributable to labile polyaromatic DOC structures. Poultry manure or chemical fertilizer alone (without biochar) did not influence the amounts of polyaromatic DOC structures. Existence of biochar could be further validated by the changes in %DOC (relative to the total carbon), fixed C content, and UV absorbance (360 nm), whereas FTIR, %O, and sorption of model agrochemical (deisopropylatrazine) did not reflect the presence of biochar in the soil samples. Developed toluene/methanol-based EEM-PARAFAC technique will provide a sensitive, rapid, and cost-competitive method to validate the long-term carbon sequestration by the biochar soil amendment.

  12. Field-scale fluorescence fingerprinting of biochar-borne dissolved organic carbon.

    PubMed

    Uchimiya, Minori; Liu, Zhongzhen; Sistani, Karamat

    2016-03-15

    Biochar continues to receive worldwide enthusiasm as means of augmenting recalcitrant organic carbon in agricultural soils. Realistic biochar amendment rate (typically less than 1 wt%) in the field scale, and subsequent loss by sizing, rain, and other transport events demand reliable methods to quantify the remaining portions of amended biochar. This study employed fluorescence excitation-emission (EEM) spectrophotometry and parallel factor analysis (PARAFAC) to specifically target pyrogenic dissolved organic carbon (DOC) released by amended biochar during the course of a field trial at Bowling Green, KY experimental site. Toluene/methanol (1:6 v/v) extracts of surface (0-15 cm) soils amended with 21.28 t ha(-1) fast pyrolysis biochar afforded PARAFAC fingerprints representing different degrees of aromaticity. Compared to the control without treatments, biochar treatment (with and without poultry manure or chemical fertilizer) increased the relative contribution of PARAFAC fingerprint attributable to labile polyaromatic DOC structures. Poultry manure or chemical fertilizer alone (without biochar) did not influence the amounts of polyaromatic DOC structures. Existence of biochar could be further validated by the changes in %DOC (relative to the total carbon), fixed C content, and UV absorbance (360 nm), whereas FTIR, %O, and sorption of model agrochemical (deisopropylatrazine) did not reflect the presence of biochar in the soil samples. Developed toluene/methanol-based EEM-PARAFAC technique will provide a sensitive, rapid, and cost-competitive method to validate the long-term carbon sequestration by the biochar soil amendment. PMID:26751812

  13. 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.

  14. Differences in spectroscopic characteristics between dissolved and particulate organic matters in sediments: Insight into distribution behavior of sediment organic matter.

    PubMed

    He, Wei; Jung, Heonjae; Lee, Jong-Hyun; Hur, Jin

    2016-03-15

    In this study, we examined the distribution behavior of sediment organic matter (SOM) between dissolved and particulate phases and the potential influencing factors by comparing the spectroscopic features of pore water organic matter (PWOM) and alkaline-extractable organic matter (AEOM) of river sediments. The characteristics of SOM were described by several selected spectral indicators and fluorescence excitation emission matrix (EEM)-parallel factor analysis (PARAFAC). The spectral indicators showed that larger sized SOM molecules with a higher aromatic content were more enriched in sediment particles than in pore water. The relative ratios of humification index between dissolved and particulate phases revealed that the SOM constituents with a higher degree of structural condensation were preferentially distributed onto sediment particles. EEM-PARAFAC demonstrated different distribution behaviors of protein-like (tyrosine-like and tryptophan-like) and humic-like substances in sediments. The relative abundance of tyrosine-like component was much higher in PWOM than in AEOM, whereas the other three components tended to be more abundant in AEOM. The predominant presence of tyrosine-like component suggests its potential operation as a discriminant indicator between PWOM and AEOM. Spearman correlations and non-metric multidimensional scaling further revealed that distribution of protein-like components onto sediment particles might be associated with reductive environments, aluminum minerals, and anthropogenic activities of upstream watersheds. This study demonstrated a successful application of using EEM-PARAFAC to examine the distribution behavior of different SOM constitutes between dissolved and solid phases.

  15. 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

  16. 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

  17. 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.

  18. 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. PMID:27372131

  19. 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

  20. 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

  1. 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.

  2. Characterisation of dissolved organic matter fluorescence properties by PARAFAC analysis and thermal quenching.

    PubMed

    Carstea, Elfrida M; Baker, Andy; Bieroza, Magdalena; Reynolds, Darren M; Bridgeman, John

    2014-09-15

    The fluorescence intensity of dissolved organic matter (DOM) in aqueous samples is known to be highly influenced by temperature. Although several studies have demonstrated the effect of thermal quenching on the fluorescence of DOM, no research has been undertaken to assess the effects of temperature by combining fluorescence excitation - emission matrices (EEM) and parallel factor analysis (PARAFAC) modelling. This study further extends previous research on thermal quenching by evaluating the impact of temperature on the fluorescence of DOM from a wide range of environmental samples, in the range 20 °C - 0 °C. Fluorescence intensity increased linearly with respect to temperature decrease at all temperatures down to 0 °C. Results showed that temperature affected the PARAFAC components associated with humic-like and tryptophan-like components of DOM differently, depending on the water type. The terrestrial humic-like components, C1 and C2 presented the highest thermal quenching in rural water samples and the lowest in urban water samples, while C3, the tryptophan-like component, and C4, a reprocessed humic-like component, showed opposite results. These results were attributed to the availability and abundance of the components or to the degree of exposure to the heat source. The variable thermal quenching of the humic-like components also indicated that although the PARAFAC model generated the same components across sites, the DOM composition of each component differed between them. This study has shown that thermal quenching can provide additional information on the characteristics and composition of DOM and highlighted the importance of correcting fluorescence data collected in situ.

  3. Fate of allochthonous dissolved organic carbon in lakes: a quantitative approach.

    PubMed

    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.

  4. 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

  5. [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. PMID:22870644

  6. Carbon dynamics and their link to dissolved organic matter quality across contrasting stream ecosystems.

    PubMed

    Bodmer, Pascal; Heinz, Marlen; Pusch, Martin; Singer, Gabriel; Premke, Katrin

    2016-05-15

    Streams represent active components of the carbon cycle as emitters of carbon dioxide (CO2) and methane to the atmosphere at a global scale. However, the mechanisms and governing factors of these emissions are still largely unknown, especially concerning the effect of land use. We compared dissolved and gaseous carbon dynamics in streams bordered by contrasting types of land use, specifically agriculture and forest. Carbon dioxide and methane partial pressures (pCO2 and pCH4, respectively) in the water body and carbon emissions via both gases were studied for 24h during four field expeditions. pCH4 did not differ between the two system types. pCO2 was constantly oversaturated in all streams and significantly higher in agricultural streams (annual mean 4282 ppm) compared to forest streams (annual mean 2189 ppm) during all seasons. However, emissions of CO2 were not significantly different between the stream types due to significantly higher gas transfer velocity in forest compared to agricultural streams. pCO2 was significantly positively correlated to the concentrations of dissolved organic carbon, dissolved nitrogen and soluble reactive phosphorus in the water. Furthermore, pCO2 was correlated to optical parameters of dissolved organic matter (DOM) quality, e.g., it increased with indicators of molecular size and an allochthonous fluorescent component identified by Parallel Factor Analysis (PARAFAC). This study demonstrates that different forms of land use may trigger a cascade of effects on the carbon production and emission of streams linked to changes in DOM quality. PMID:26938320

  7. Bacterial Contribution to Dissolved Organic Matter in Eutrophic Lake Kasumigaura, Japan

    PubMed Central

    Komatsu, Kazuhiro; Kohzu, Ayato; Tomioka, Noriko; Shinohara, Ryuichiro; Satou, Takayuki; Watanabe, Fumiko Nara; Tada, Yuya; Hamasaki, Koji; Kushairi, M. R. M.; Imai, Akio

    2013-01-01

    Incubation experiments using filtered waters from Lake Kasumigaura were conducted to examine bacterial contribution to a dissolved organic carbon (DOC) pool. Bacterial abundance, bacterial production, concentrations of DOC, total dissolved amino acids (TDAA), and total dissolved neutral sugars (TDNS) were monitored during the experiments. Bacterial production during the first few days was very high (20 to 35 μg C liter−1 day−1), accounting for 40 to 70% of primary production. The total bacterial production accounted for 34 to 55% of the DOC loss during the experiment, indicating high bacterial activities in Lake Kasumigaura. The DOC degradation was only 12 to 15%, whereas the degradation of TDAA and TDNS ranged from 30 to 50%, suggesting the preferential usage of TDAA and TDNS. The contribution of bacterially derived carbon to a DOC pool in Lake Kasumigaura was estimated using d-amino acids as bacterial biomarkers and accounted for 30 to 50% of the lake DOC. These values were much higher than those estimated for the open ocean (20 to 30%). The ratio of bacterially derived carbon to bulk carbon increased slightly with time, suggesting that the bacterially derived carbon is more resistant to microbial degradation than bulk carbon. This is the first study to estimate the bacterial contribution to a DOC pool in freshwater environments. These results indicate that bacteria play even more important roles in carbon cycles in freshwater environments than in open oceans and also suggests that recent increases in recalcitrant DOC in various lakes could be attributed to bacterially derived carbon. The potential differences in bacterial contributions to dissolved organic matter (DOM) between freshwater and marine environments are discussed. PMID:24038686

  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. Lake transparency: a window into decadal variations in dissolved organic carbon concentrations in Lakes of Acadia National Park, Maine

    USGS Publications Warehouse

    Collin Roesler,; 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. Dissolved Organic Carbon Mobilisation in a Groundwater System Stressed by Pumping.

    PubMed

    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

  15. Bioavailability of riverine dissolved organic matter to phytoplankton in the marine coastal waters

    NASA Astrophysics Data System (ADS)

    Jurgensone, Iveta; Aigars, Juris

    2012-07-01

    Nutrient inputs from catchments with intensive agriculture are mostly dominated by inorganic nutrients, whereas the contribution of organic nutrients from catchments with natural forests can be considerable but there is a pooere understanding of this nutrient source. Consequently this study investigated spring, summer and autumn phytoplankton community responses to enrichment by riverine dissolved organic matter (DOM). Dissolved organic substances were extracted from the Daugava River, fractionated into three molecular size classes: 1) 5-100 kDa, 2) 100-1000 kDa, and 3) >1000 kDa, and added to a microcosm with natural assemblages from the Gulf of Riga. During the spring the phytoplankton community was dominated (97%) by diatoms and the species composition did not change over the course of the experiment. Specific species and functional groups of the summer and autumn phytoplankton communities responded positively to these treatments. Small-celled cyanobacteria and Monoraphidium contortum responded to almost all size fractions of DOM for the summer and autumn experiments. Oocystis spp. characteristic for the summer and Chaetoceros wighamii, Cyclotella spp., Thalassiosira baltica for the autumn responded to treatment by two and three size classes of organic substances, respectively, while Merismopedia spp. shifted from one food source to another during the summer experiment.

  16. 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

  17. 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

  18. 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

  19. 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...

  20. 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...

  1. SPATIAL AND TEMPORAL DISTRIBUTION OF COLOURED DISSOLVED ORGANIC MATTER (CDOM) IN NARRAGANSETT BAY, RI: IMPLICATIONS FOR PHYTOPLANKTON IN COASTAL WATERS

    EPA Science Inventory

    One indicator of health in estuarine and coastal ecosystems is the ability of local waters to transmit sunlight to planktonic, macrophytic, and other submerged vegetation for photosynthesis. The concentration of coloured dissolved organic matter (CDOM) is a primary factor affecti...

  2. 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...

  3. INTERACTIONS BETWEEN PHOTOCHEMICAL AND MICROBIAL DECOMPOSITION IN MODIFYING THE BIOLOGICAL AVAILABILITY AND OPTICAL PROPERTIES OF ESTUARINE DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    Direct photodecomposition and photochemically-mediated bacterial degradation (via photochemical modification of otherwise refractory DOM into biologically labile forms) provide
    important pathways for the loss of dissolved organic matter in coastal waters. Here we report
    lab...

  4. Partitioning of tetra- and pentabromo diphenyl ether and benzo[a]pyrene among water and dissolved and particulate organic carbon along a salinity gradient in coastal waters.

    PubMed

    Kuivikko, Miika; Sorsa, Karoliina; Kukkonen, Jussi V K; Akkanen, Jarkko; Kotiaho, Tapio; Vähätalo, Anssi V

    2010-11-01

    This study assessed the partitioning of 2,2',4,4'-tetrabromo diphenyl ether (BDE-47), 2,2',4,4',5-pentabromo diphenyl ether (BDE-99) and benzo[a]pyrene (BaP) among water, dissolved organic carbon (DOC: 4.93-8.72 mg/L), and particulate organic carbon (POC: 191-462 µg/L) along the salinity gradient (0-5.5‰) of the Baltic Sea off the coast of Finland. Equilibrium dialysis and two solid-phase extraction techniques using polyoxymethylene polymer (POM) were used to determine partitioning coefficients. Experiments using artificial coastal water (ACW) with Nordic fulvic (FAs) and humic acids (HAs) were used to assess the effect of salinity (0 and 5.5‰) on the DOC-water partitioning of the model compounds. All three compounds bound more (2.2-3.8-fold) to the HAs than to the FAs. Increasing salinity from 0 to 5.5‰ decreased sorption to dissolved humic substances in the ACW and Baltic Sea water samples. Along the salinity gradient, the sorption of compounds to organic material decreased when the salinity increased. Particulate organic matter sorbed model compounds per unit of carbon more than dissolved organic matter. Along the studied salinity gradient, the freely dissolved portion increased from 10 to 29% to 52 to 80% in the coastal water samples, mainly because of the increasing salinity and changes in DOC and quality of POC. PMID:20886501

  5. Watershed scale spatial variability in dissolved and total organic and inorganic carbon in contrasting UK catchments

    NASA Astrophysics Data System (ADS)

    Cumberland, S.; Baker, A.; Hudson, N. J.

    2006-12-01

    Approximately 800 organic and inorganic carbon analyses have been undertaken from watershed scale and regional scale spatial surveys in various British catchments. These include (1) a small (<100 sq-km) urban catchment (Ouseburn, N England); (2) a headwater, lowland agricultural catchment (River Tern, C England) (3) a large UK catchment (River Tyne, ~3000 sq-km) and (4) a spatial survey of ~300 analyses from rivers from SW England (~1700 sq-km). Results demonstrate that: (1) the majority of organic and inorganic carbon is in the dissolved (DOC and DIC) fractions; (2) that with the exception of peat rich headwaters, DIC concentration is always greater than DOC; (3) In the rural River Tern, riverine DOC and DIC are shown to follow a simple end- member mixing between DIC (DOC) rich (poor) ground waters and DOC (DIC) rich (poor) riparian wetlands for all sample sites. (4) In the urbanized Ouseburn catchment, although many sample sites also show this same mixing trend, some tributaries follow a pollutant trend of simultaneous increases in both DOC and DIC. The Ouseburn is part of the larger Tyne catchment: this larger catchment follows the simple groundwater DIC- soil water DOC end member mixing model, with the exception of the urban catchments which exhibit an elevated DIC compared to rural sites. (5) Urbanization is demonstrated to increase DIC compared to equivalent rural catchments; this DIC has potential sources including diffuse source inputs from the dissolution of concrete, point sources such as trade effluents and landfill leachates, and bedrock derived carbonates relocated to the soil dissolution zone by urban development. (6) DIC in rural SW England demonstrates that spatial variability in DIC can be attributed to variations in geology; but that DIC concentrations in the SW England rivers dataset are typically lower than the urbanized Tyne catchments despite the presence of carbonate bedrock in many of the sample catchments in the SW England dataset. (7

  6. Characterization of dissolved organic materials in surface waters within the blast zone of Mount St Helens, Washington

    USGS Publications Warehouse

    McKnight, Diane M.; Pereira, W.E.; Ceazan, M.L.; Wissmar, Robert C.

    1982-01-01

    After the May 18, 1980, eruption of Mount St Helens, the concentration of dissolved organic material in surface waters near the volcano increased significantly as a result of the destruction of the surrounding conifer forest. Low molecular weight organic compounds identified in the blast zone surface waters were derived from pyrolysis of plant and soil organic materials incorporated into pyroclastic flow, mud flow and debris avalanche deposits. A major fraction of the dissolved organic material consisted of high molecular weight, colored, organic acids that are similar in their general properties to aquatic fulvic acids found in more typical surface waters except for greater sulfur contents. The other major fraction of the dissolved organic material consisted of hydrophilic acids, which may include compounds capable of supporting heterotrophic microorganisms, and precursors in the formation of aquatic fulvic acids. The organic chemistry of blast zone surface waters will probably be greatly influenced by the May 18, 1980, eruption for many years. ?? 1982.

  7. 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

  8. Effects of reverse osmosis isolation on reactivity of naturally occurring dissolved organic matter in physicochemical processes.

    PubMed

    Kilduff, James E; Mattaraj, Supatpong; Wigton, Andrew; Kitis, Mehmet; Karanfil, Tanju

    2004-02-01

    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 measured value of rejection predicted the concentration within the closed-loop isolation system. The effect of operating pressure and solution flux on mass recovery of DOM was evaluated in laboratory and field trials. Under controlled laboratory conditions, >99% of a lacustrine DOM could be accounted for. A fraction of the isolated DOM was not recoverable using hydrodynamic cleaning; however, this fraction was recovered by using a pH 10 NaOH wash solution. The mass recovered in the NaOH solution increased from <1% to >6% with increasing transmembrane pressures from 414 kPa (60 psi) to1000 kPa (145 psi), respectively. This is consistent with fouling that results from an increase in solution flux, and a decrease in tangential crossflow velocity. Under field conditions, mass balances were generally >95% and mass recovery was >90% in all cases. The effects of temperature on solution flux were consistent with changes in fluid viscosity; effects of temperature on membrane diffusivity or morphological properties were small. RO isolation under low pressure conditions designed to maximize DOM recovery had little effect on DOM reactivity evaluated in terms of nanofiltration membrane fouling, XAD-8 resin adsorption, activated carbon adsorption, competition with trichloroethylene for adsorption sites on activated carbon, and molecular weight distribution measured using size exclusion chromatography.

  9. 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

  10. 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

  11. 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. PMID:24793113

  12. Climate Change-Related Hydrologic Variation Affects Dissolved Organic Carbon Export to the Gulf of Maine

    NASA Astrophysics Data System (ADS)

    Huntington, T. G.; Balch, W. M.; Aiken, G.; Butler, K. D.; Billmire, M.; Roesler, C. S.; Camill, P.; Bourakovsky, A.

    2014-12-01

    Ongoing climate change is affecting the timing and amount of dissolved organic carbon (DOC) exported to the Gulf of Maine (GoM) through effects on hydrologic conditions. Climate warming in the northeast United States has resulted in decreases in snowfall amount and increases in the proportion of annual precipitation that falls as rain compared with snow. Warming has resulted in an increase in runoff during winter and earlier snowmelt and associated high spring flow. Increases in annual precipitation have resulted in increases in annual runoff. Increases in flashiness in some rivers have resulted in higher variability in daily runoff. DOC fluxes were estimated for water years 1950 through 2012 in eight rivers draining to the GoM that had long-term discharge data and data for DOC during all months of the year. These estimates used LOADEST to fit a seasonally-adjusted concentration - discharge relation. The adjusted maximum likelihood estimation (AMLE) method was used to estimate loads. One of several predefined regression models evaluated in LOADEST was selected based on the Akaike information criterion (AIC) for each river. This analysis assumed stationarity in the concentration - discharge relations. The proportion of total annual DOC exported during winter has increased. The proportion of DOC exported during March and April has also increased and the proportion exported during May has decreased in association with earlier snowmelt runoff and earlier recession to summer low flow. The total annual DOC exported by these rivers increased significantly from 1950 to 2012. The increase in flashiness has increased daily variability in DOC export in some rivers. Changes in the timing and amount of DOC exported to the near coastal ocean may influence marine biogeochemistry including the development of nuisance and harmful algal blooms, carbon sequestration, and the interpretation of satellite-derived ocean color. Terrestrially derived DOC exported to the marine environment

  13. Dissolved Organic Matter (DOM) Transport in Watersheds: Controls of Sources, Flowpaths and DOM Quality

    NASA Astrophysics Data System (ADS)

    Inamdar, S.; Finger, N.; Mitchell, M.

    2008-12-01

    We investigated the factors and processes influencing the transport of dissolved organic carbon (DOC) and nitrogen (DON) in forested watersheds. Key questions that we addressed are: What are the sources and flowpaths for DOC and DON in the watershed? Does DOM quality influence the concentrations and transport of DOC and DON? How do DOC and DON concentrations change between baseflow and storm event conditions and across the seasons? How do DOM concentrations and quality change with catchment scale? These questions are being addressed in a 12 ha unglaciated, forested watershed located in the Piedmont province of Maryland, USA. Watershed sources being sampled include - rainfall, throughfall, litter, soil water, groundwater, hillslope seeps and hyporheic zone water. Watershed sources are sampled manually during non-storm periods (every two weeks) while automated samplers are used for storm events. Water samples are analyzed for cations, anions, DOC, DON, Silica and O18. DOM quality is characterized using specific ultraviolet absorbance (SUVA), Fluorescence Index (FI), Excitation-Emission Matrices (EMMs), hydrophobic and hydrophilic fractions, and concentrations of phenols, carboxylic acids, flavanoids, and amino acids. Hydrologic monitoring includes discharge and groundwater elevations. Our initial results from endmember mixing analysis (EMMA) indicate that stream chemistry is regulated by seep runoff, litter, and riparian soil water with individual endmember contributions varying with size of the storm events and wetness conditions. Highest DOC and DON concentrations were recorded for throughfall and litter layer. SUVA values were highest and most variable for litter leachate followed by riparian water. Concentrations of DOC and DON in streamflow increased dramatically during events and peaked at or after the discharge peak. While SUVA values followed a similar trend, there were slight differences among events. DOM concentrations in stream baseflow were influenced

  14. Character and chlorine reactivity of dissolved organic matter from a mountain pine beetle impacted watershed.

    PubMed

    Beggs, Katherine M H; Summers, R Scott

    2011-07-01

    Lodgepole pine needle leachates from trees killed by the mountain pine beetle epidemic in Colorado were evaluated for dissolved organic matter (DOM) character, biodegradation, treatability by coagulation and disinfection byproduct (DBP) formation. An average of 8.0 (±0.62) mg-DOC/g-dry weight of litter was leached from three sets of needle samples representing different levels of forest floor degradation. Fluorescence analysis included collection of excitation and emission matrices, examination of peak intensities and development of a 4-component parallel factor (PARAFAC) analysis model. Peak intensity and PARAFAC analyses provided complementary results showing that fresh leachates were initially dominated by polyphenolic/protein-like components (60-70%) and humic-like fluorescence increased (40-70%) after biodegradation. Humic-like components were removed by coagulation (20-64%), while polyphenolic/protein-like components were not, which may create challenges for utilities required to meet OM removal regulations. DBP formation yields after 24 h chlorination were 20.5-26.4 μg/mg-DOC for trihalomethanes and 9.0-14.5 μg/mg-DOC for haloacetic acids for fresh leachates; increased after biodegradation to 19.2-64.2 and 7.1-30.9 μg/mg-DOC, respectively; and decreased after coagulation (fresh: 11.3-17.7;5.7-7.6 μg/mg-DOC, respectively; biodegraded: 12.0-27.3 and 2.9-7.2 μg/mg-DOC, respectively), reflective of changes in concentration of humic material. Humic-like PARAFAC components and peak intensities were positively correlated (R(2) ≥ 0.45) to DBP concentrations, while polyphenolic/protein-like components were not (R(2) ≤ 0.17).

  15. Dissolved organic carbon export and internal cycling in small, headwater lakes

    USGS Publications Warehouse

    Stets, Edward G.; Striegl, Rob; 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. 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

  1. Characteristics of riverine dissolved organic carbon export in subtropical island, Taiwan

    NASA Astrophysics Data System (ADS)

    Lee, Li-Chin; Huang, -Chuan, Jr.; Lee, Tsung-Yu; Lin, Chuan-Yao; Jien, Shih-Hao

    2016-04-01

    Carbon transporting from the terrestrial to the marine systems via rivers represents a crucial link in the global carbon cycle. Riverine dissolved organic carbon (DOC) which is responsible for maintaining the estuarine, coastal and marine ecosystems, is one of the main concerns in nutrient flux from land to ocean. Numerous studies have shown that the POC export in small mountainous rivers, like Taiwan, is disproportionally higher compared with global rivers; however, few studies have focused on the contribution of riverine DOC from the small mountainous tropical/sub-tropical islands. In this study, an intensive and extensive sampling scheme of DOC was conducted in Dan-Shui (DS), Chi-Chia-Wan (CJW) and Li-Wu (LW) River in Taiwan, and the characteristics of DOC concentration and flux were investigated. Meanwhile, the regressive estimation of DOC flux based on the landscape setting was applied and compared with research results proposed worldwide. Our results show that the annual mean DOC concentration in LW is ~0.51 ppm, thelowest among the three watersheds while the other two, DS and CJW, are ~0.97 ppm and ~0.90ppm, respectively. The seasonal variation in DS watershed is significant, yet insignificant for the other two watersheds with higher elevation. In terms of flux, the DOC yield in LW is ~1.01 ton-C km-2 yr-1, and the DOC yield in DS and CJW are ~3.01 ton-C km-2 yr-1 and ~4.28 ton-C km-2 yr-1, respectively. The DOC yield in CJW presents a distinct seasonal variability. Since the DOC concentration in CJW is stable, the seasonal variation in DOC yield is strongly controlled by streamflow, revealing hydrological regulation at work. Besides, the multiple regressive model (Ludwig et al., 1996) which includes the variables of runoff, soil organic carbon and slope was applied. The model gave a good relationship between observation and simulation with a high R2 = 0.72, yet it overestimated the yield by ~3.5 times. It suggests that the controlling factors in small

  2. 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}.

  3. 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].

  4. Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer

    USGS Publications Warehouse

    Aravena, R.; Wassenaar, L.I.; Spiker, E. C.

    2004-01-01

    This study demonstrates the advantage of a combined use of chemical and isotopic tools to understand the dissolved organic carbon (DOC) cycle in a regional confined methanogenic aquifer. DOC concentration and carbon isotopic data demonstrate that the soil zone is a primary carbon source of groundwater DOC in areas close to recharge zones. An in-situ DOC source linked to organic rich sediments present in the aquifer matrix is controlling the DOC pool in the central part of the groundwater flow system. DOC fractions, 13C-NMR on fulvic acids and 14C data on DOC and CH4 support the hypothesis that the in-situ DOC source is a terrestrial organic matter and discard the Ordovician bedrock as a source of DOC. ?? 2004 Taylor and Francis Ltd.

  5. Dissolved and particulate organic carbon fluxes from an agricultural watershed during consecutive tropical storms

    NASA Astrophysics Data System (ADS)

    Caverly, Emma; Kaste, James M.; Hancock, Gregory S.; Chambers, Randolph M.

    2013-10-01

    Low-frequency high-magnitude hydrologic events mobilize a disproportionate amount of dissolved organic carbon (DOC) from watersheds, but few studies measure the role of extreme storms in exporting organic carbon from croplands. We use high-resolution measurements of storm runoff to quantify DOC and particulate organic carbon (POC) fluxes from an agricultural field during consecutive tropical storms that delivered 41 cm of rainfall to the Virginia Coastal Plain. Over a 2 week period, we measured exports of 22 kg DOC ha-1 and 11.3 kg POC ha-1. Ultraviolet absorbance measurements indicate that the aromatic DOC fraction systematically increased as plant-derived aliphatic carbon was depleted during the initial event. Croplands can have event-scale carbon losses that equal or exceed published estimates of annual export for perennial streams draining forested and mixed land use watersheds. We quantify aromatic DOC fractions approaching 50%, indicating that agricultural stormflow can produce a significant load of relatively photoreactive carbon.

  6. Dynamics of dissolved organic matter: A view from two dimensional correlation spectroscopy techniques

    NASA Astrophysics Data System (ADS)

    Abdulla, Hussain A. N.; Hatcher, Patrick G.

    2014-07-01

    Dissolved organic matter (DOM) is the most reactive organic carbon pool in earth. However, the heterogeneity of this organic mixture makes it difficult to investigate its dynamics under different external perturbations. In this review, we present the potential of using the two dimensional correlation spectroscopy analysis (2D correlations) as a tool to study the dynamic of DOM. We demonstrate the application of the 2D correlation analysis on high molecular weight DOM (HMW-DOM) with the salinity as perturbation parameter. We used four different chemical probes: Carbon nuclear magnetic resonance spectroscopy (13C NMR), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS).

  7. 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.

  8. Characterization of Rainwater Dissolved Organic Matter by Ultrahigh Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Mead, R. N.; Podgorski, D. C.; Mullaugh, K. M.; Avery, B.; Kieber, R. J.; Willey, J. D.; Cooper, W. T.

    2011-12-01

    Rainwater is a complex, heterogeneous mixture of dissolved organic matter (DOM) that remains largely uncharacterized at the molecular level. Rainwater with dissolved organic carbon values ranging from 3 to 450 μM was collected during 40 separate rain events from 2007-2011 that included coastal and terrestrial storms based upon 36 hour back trajectories. Individual rain samples were lypholized and solvent added in preparation for analysis by negative electrospray ionization and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This data set is unique in that each rain event was analyzed individually and not combined allowing for unprecedented insight into rainwater DOM at the molecular level on an episodic basis. Unique elemental compositions were assigned for compounds belonging to CHO, CHOS and CHON classes. Data visualization by van Krevelen diagrams showed clear differences in coastal and terrestrial storm events with a majority of coastal storms having high H/C (1.5-2.0) relative to terrestrial storms. Further inspection of the data revealed that rainwater has relatively high O/C (1.4) and low H/C (<0.5) which suggests