Dissolved organic matter (DOM) in pore water of Arctic Ocean sediments: linking DOM molecular composition with microbial community structure

NASA Astrophysics Data System (ADS)

Rossel, P. E.; Bienhold, C.; Boetius, A.; Dittmar, T.

2016-02-01

Marine organic matter (OM) that sinks from surface waters to the seafloor is the energy and carbon source for benthic communities. These communities produce dissolved organic matter (DOM) in the process of remineralization, enriching the sediment porewater with fresh DOM compounds. In the Arctic Ocean, primary production is limited by nutrients and light and is thus strongly influenced by sea ice cover. Ice cover is expected to further decrease due to global warming, which may have important consequences for primary production and the quantity and quality of OM exported to the seafloor. This study focused on: 1) the molecular composition of the DOM in sediment pore waters of the deep Eurasian Arctic basins, 2) whether there is any relation between Arctic Ocean ice cover and DOM composition and 3) whether the DOM composition correlates with microbial community structure. Molecular data, obtained via 15 Tesla Fourier transform ion cyclotron resonance mass spectrometry, were statistically correlated with environmental parameters. The productive ice margin stations showed higher abundances of molecular formulae of peptides, unsaturated aliphatics and saturated fatty acids. This molecular trend is indicative of fresh OM and phytodetritus deposition, compared to the northernmost, ice-covered stations which had stronger aromatic signals. Benthic bacterial community structure, as assessed with the fingerprinting method ARISA, was significantly correlated with DOM molecular composition. Further analyses using Illumina next-generation sequencing will enable the taxonomic identification of specific bacterial groups and their interdependence with DOM compounds. This study contributes to the understanding of the coupling between Arctic Ocean productivity and its depositional regime, and provides first insights into potential links between microbial community structure and DOM molecular composition in Arctic sediments

The effect of advanced secondary municipal wastewater treatment on the molecular composition of dissolved organic matter.

PubMed

Maizel, Andrew C; Remucal, Christina K

2017-10-01

There is a growing interest in water reuse and in recovery of nutrients from wastewater. Because many advanced treatment processes are designed to remove organic matter, a better understanding of the composition of dissolved organic matter (DOM) in wastewater is needed. To that end, we assessed DOM in the Nine Springs Wastewater Treatment Plant in Madison, Wisconsin by UV-visible spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry. Samples were collected from the influent and effluent of two different secondary treatment processes and their respective secondary clarifiers, the UV disinfection unit, and an Ostara treatment system, which produces struvite via chemical precipitation. The optical properties reveal that DOM throughout the plant is relatively aliphatic and is low in molecular weight compared to DOM in freshwater systems. Furthermore, the DOM is rich in heteroatoms (e.g., N, S, P, and Cl) and its molecular formulas are present in the lipid-, protein-, carbohydrate-, and lignin-like regions of van Krevelen diagrams. Secondary treatment produces DOM that is more aromatic and more complex, as shown by the loss of highly saturated formulas and the increase in the number of CHO, CHON, and CHOP formulas. The two secondary treatment processes produce DOM with distinct molecular compositions, while the secondary clarifiers and UV disinfection unit result in minimal changes in DOM composition. The Ostara process decreases the molecular weight of DOM, but does not otherwise alter its composition. The optical properties agree with trends in the molecular composition of DOM within the main treatment train of the Nine Springs plant. Copyright © 2017 Elsevier Ltd. All rights reserved.

Phylogenetic and structural response of heterotrophic bacteria to dissolved organic matter of different chemical composition in a continuous culture study.

PubMed

Landa, M; Cottrell, M T; Kirchman, D L; Kaiser, K; Medeiros, P M; Tremblay, L; Batailler, N; Caparros, J; Catala, P; Escoubeyrou, K; Oriol, L; Blain, S; Obernosterer, I

2014-06-01

Dissolved organic matter (DOM) and heterotrophic bacteria are highly diverse components of the ocean system, and their interactions are key in regulating the biogeochemical cycles of major elements. How chemical and phylogenetic diversity are linked remains largely unexplored to date. To investigate interactions between bacterial diversity and DOM, we followed the response of natural bacterial communities to two sources of phytoplankton-derived DOM over six bacterial generation times in continuous cultures. Analyses of total hydrolysable neutral sugars and amino acids, and ultrahigh resolution mass spectrometry revealed large differences in the chemical composition of the two DOM sources. According to 454 pyrosequences of 16S ribosomal ribonucleic acid genes, diatom-derived DOM sustained higher levels of bacterial richness, evenness and phylogenetic diversity than cyanobacteria-derived DOM. These distinct community structures were, however, not associated with specific taxa. Grazing pressure affected bacterial community composition without changing the overall pattern of bacterial diversity levels set by DOM. Our results demonstrate that resource composition can shape several facets of bacterial diversity without influencing the phylogenetic composition of bacterial communities, suggesting functional redundancy at different taxonomic levels for the degradation of phytoplankton-derived DOM. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

Further insight into the roles of the chemical composition of dissolved organic matter (DOM) on ultrafiltration membranes as revealed by multiple advanced DOM characterization tools.

PubMed

Ly, Quang Viet; Hur, Jin

2018-06-01

This study assessed the relative contributions of different constitutes in dissolved organic matter (DOM) with two different sources (i.e., urban river and effluent) to membrane fouling on three types of ultrafiltration (UF) membranes via excitation emission matrix - parallel factor analysis (EEM-PARAFAC), size exclusion chromatography (SEC), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Two polyethersulfone membranes with different pore sizes and one regenerated cellulose membrane were used as representative hydrophobic (HPO) and hydrophilic (HPI) UF membranes, respectively. Although size exclusion effect was found to be the most prevailing rejection mechanism, the behaviors of individual fluorescent components (one tryptophan-like, one microbial-humic-like, and terrestrial humic-like) and different size fractions upon the UF filtration revealed that chemical interactions (e.g., hydrophobic interactions and hydrogen bonding) between DOM and membrane might play important roles in UF membrane fouling, especially for small sized DOM molecules. Based on the molecular level composition determined by FT-ICR-MS, the CHOS formula group showed a greater removal tendency toward the HPO membrane, while the CHONS group was prone to be removed by the HPI membrane. The changes in the overall molecular composition of DOM upon UF filtration were highly dependent on the sources of DOM. The molecules of more acidic nature tended to remain in the permeate of effluent DOM, while the river DOM was shifted into more nitrogen-enriched composition after filtration. Regardless of the DOM sources, the HPO membrane with a smaller pore size led to the most pronounced changes in the molecular composition of DOM. Copyright © 2018 Elsevier Ltd. All rights reserved.

Reactivity of Triplet Excited States of Dissolved Natural Organic Matter in Stormflow from Mixed-Use Watersheds.

PubMed

McCabe, Andrew J; Arnold, William A

2017-09-05

Dissolved organic matter (DOM) quantity and composition control the rate of formation (R f,T ) of triplet excited states of dissolved natural organic matter ( 3 DOM*) and the efficiency of 3 DOM* formation (the apparent quantum yield, AQY T ). Here, the reactivity of 3 DOM* in stormflow samples collected from watersheds with variable land covers is examined. Stormflow DOM reflects variability in DOM quantity and composition as a function of land cover and may be important in controlling the fate of cotransported pollutants. R f,T and AQY T were measured using 2,4,6-trimethylphenol in stormflow samples under simulated sunlight. The DOM source and composition was characterized using absorbance and fluorescence spectroscopies and high-resolution mass spectrometry. R f,T and the total rate of light absorption by the water samples (R a ) increased with the dissolved organic carbon (DOC) concentration. AQY T was independent of DOC concentration, but varied with DOM source: developed land cover (4-6%) ≈ open water > vegetated land cover (3%). AQY T was positively related to an index for microbial/algal DOM content and negatively related to DOM molecular weight, DOM aromaticity, and the content of polyphenols. This work demonstrates that TMP is an effective probe for the determination of R f,T and AQY T in whole water samples after accounting for the inhibition of TMP photodegradation by DOM.

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 showed that also the event-mobilized DOM had higher radiocarbon content. Overall, hydrology not only controls the quantity of exported carbon from temperate catchments but also strongly influences the molecular composition by mobilizing distinct compound classes in conjunction with dissolved iron and aluminum. From these results future compositional changes in temperate river DOM can be assessed, given an expected increase in the magnitude of hydrologic events, and technical advice for drinking water production may be inferred.

The role of reactive oxygen species in the degradation of lignin derived dissolved organic matter

NASA Astrophysics Data System (ADS)

Waggoner, Derek C.; Wozniak, Andrew S.; Cory, Rose M.; Hatcher, Patrick G.

2017-07-01

Evidence suggests that reactive oxygen species (ROS) are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. In this work, terrestrial DOM was independently exposed to singlet oxygen (1O2), and superoxide (O2-rad under controlled laboratory conditions). Using ultra-high resolution mass spectrometry to track molecular level alterations of DOM by ROS, these findings suggest exposure to 1O2 (generated using Rose Bengal and visible light) removed formulas with an O/C > 0.3, and primarily resulted in DOM comprised of formulas with higher oxygen content, while O2-rad exposure (from KO2 in DMSO) removed formulas with O/C < 0.3 and produced aliphatic formulas (H/C > 1.5). Comparison of DOM altered by ROS in this study to riverine and coastal DOM showed that (20-80%) overlap in formulas, providing evidence for the role of ROS in shaping the composition of DOM exported from rivers to oceans.

Molecular characteristics of continuously released DOM during one year of root and leaf litter decomposition

NASA Astrophysics Data System (ADS)

Altmann, Jens; Jansen, Boris; Kalbitz, Karsten; Filley, Timothy

2013-04-01

Dissolved organic matter (DOM) is one of the most dynamic carbon pools linking the terrestrial with the aquatic carbon cycle. Besides the insecure contribution of terrestrial DOM to the greenhouse effect, DOM also plays an important role for the mobility and availability of heavy metals and organic pollutants in soils. These processes depend very much on the molecular characteristics of the DOM. Surprisingly the processes that determine the molecular composition of DOM are only poorly understood. DOM can originate from various sources, which influence its molecular composition. It has been recognized that DOM formation is not a static process and DOM characteristics vary not only between different carbon sources. However, molecular characteristics of DOM extracts have scarcely been studied continuously over a longer period of time. Due to constant molecular changes of the parent litter material or soil organic matter during microbial degradation, we assumed that also the molecular characteristics of litter derived DOM varies at different stages during root and needle decomposition. For this study we analyzed the chemical composition of root and leaf samples of 6 temperate tree species during one year of litter decomposition in a laboratory incubation. During this long-term experiment we measured continuously carbon and nitrogen contents of the water extracts and the remaining residues, C mineralization rates, and the chemical composition of water extracts and residues by Curie-point pyrolysis mass spectrometry with TMAH We focused on the following questions: (I) How mobile are molecules derived from plant polymers like tannin, lignin, suberin and cutin? (II) How does the composition of root and leaf derived DOM change over time in dependence on the stage of decomposition and species? Litter derived DOM was generally dominated by aromatic compounds. Substituded fatty acids as typically cutin or suberin derived were not detected in the water extracts. Fresh leaf and needle samples released a much higher amount of tannins than fresh root samples. At later litter decomposition stages the influence of tannins decreased and lignin derived phenols dominated the extracts. With ongoing litter degradation the degree of oxidation for the litter material increased, which was also reflected by the water extracted molecules.

Evaluation of forest disturbance legacy effects on dissolved organic matter characteristics in streams at the Hubbard Brook Experimental Forest, New Hampshire

Treesearch

Kaelin M. Cawley; John Campbell; Melissa Zwilling; Rudolf. Jaffé

2014-01-01

Dissolved organic matter (DOM) source and composition are critical drivers of its reactivity, impact microbial food webs and influence ecosystem functions. It is believed that DOM composition and abundance represent an integrated signal derived from the surrounding watershed. Recent studies have shown that land-use may have a long-term effect on DOM composition....

Uncoupling of Bacterial and Terrigenous Dissolved Organic Matter Dynamics in Decomposition Experiments

PubMed Central

Herlemann, Daniel P. R.; Manecki, Marcus; Meeske, Christian; Pollehne, Falk; Labrenz, Matthias; Schulz-Bull, Detlef; Dittmar, Thorsten; Jürgens, Klaus

2014-01-01

The biodegradability of terrigenous dissolved organic matter (tDOM) exported to the sea has a major impact on the global carbon cycle, but our understanding of tDOM bioavailability is fragmentary. In this study, the effects of preparative tDOM isolation on microbial decomposition were investigated in incubation experiments consisting of mesocosms containing mesohaline water from the Baltic Sea. Dissolved organic carbon (DOC) consumption, molecular DOM composition, bacterial activities, and shifts in bacterial community structure were compared between mesocosms supplemented with riverine tDOM, either as filtered, particle-free river water or as a concentrate obtained by lyophilization/tangential ultrafiltration, and those containing only Baltic Sea water or river water. As shown using ultra-high-resolution mass spectrometry (15 Tesla Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) covering approximately 4600 different DOM compounds, the three DOM preparation protocols resulted in distinct patterns of molecular DOM composition. However, despite DOC losses of 4–16% and considerable bacterial production, there was no significant change in DOM composition during the 28-day experiment. Moreover, tDOM addition affected neither DOC degradation nor bacterial dynamics significantly, regardless of the tDOM preparation. This result suggested that the introduced tDOM was largely not bioavailable, at least on the temporal scale of our experiment, and that the observed bacterial activity and DOC decomposition mainly reflected the degradation of unknown, labile, colloidal and low-molecular weight DOM, both of which escape the analytical window of FT-ICR-MS. In contrast to the different tDOM preparations, the initial bacterial inoculum and batch culture conditions determined bacterial community succession and superseded the effects of tDOM addition. The uncoupling of tDOM and bacterial dynamics suggests that mesohaline bacterial communities cannot efficiently utilize tDOM and that in subarctic estuaries other factors are responsible for the removal of imported tDOM. PMID:24718626

Composition and transformation of dissolved organic matter in the Baltic Sea

NASA Astrophysics Data System (ADS)

Seidel, Michael; Manecki, Marcus; Herlemann, Daniel P. R.; Deutsch, Barbara; Schulz-Bull, Detlef; Jürgens, Klaus; Dittmar, Thorsten

2017-05-01

The processing of terrestrial dissolved organic matter (DOM) in coastal shelf seas is an important part of the global carbon cycle, yet, it is still not well understood. One of the largest brackish shelf seas, the Baltic Sea in northern Europe, is characterized by high freshwater input from sub-arctic rivers and limited water exchange with the Atlantic Ocean via the North Sea. We studied the molecular and isotopic composition and turnover of solid-phase extractable (SPE) DOM and its transformation along the salinity and redox continuum of the Baltic Sea during spring and autumn. We applied ultrahigh-resolution mass spectrometry and other geochemical and biological approaches. Our data demonstrate a large influx of terrestrial riverine DOM, especially into the northern part of the Baltic Sea. The DOM composition in the central Baltic Sea changed seasonally and was mainly related to autochthonous production by phytoplankton in spring. Especially in the northern, river-dominated basins, a major fraction of riverine DOM was removed, likely by bio- and photo-degradation. We estimate that the removal rate of terrestrial DOM in the Baltic Sea (Bothnian Bay to the Danish Straits/Kattegat area) is 1.6 - 1.9 Tg C per year which is 43 to 51% of the total riverine input. The export of terrestrial DOM from the Danish Straits/Kattegat area towards the North Sea is 1.8 - 2.1 Tg C per year. Due to the long residence time of terrestrial DOM in the Baltic Sea (total of ca. 12 years), seasonal variations caused by bio- and photo-transformations and riverine discharge are dampened, resulting in a relatively invariant DOM molecular and isotopic signature exported to the North Sea. In the deep stagnant basins of the Baltic Sea, the DOM composition and dissolved organic nitrogen concentrations changed seasonally, likely because of vertical particle transport and subsequent degradation releasing DOM. DOM in the deep anoxic basins was also enriched in sulfur-containing organic molecules, pointing to abiotic sulfurization of DOM under sulfidic conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schumacher,M.; Christl, I.; Vogt, R.

The chemical composition and carbon isotope signature of aquatic dissolved organic matter (DOM) in five boreal forest catchments in Scandinavia were investigated. The DOM was isolated during spring and fall seasons using a reverse osmosis technique. The DOM samples were analyzed by elemental analysis, FT-IR, solid-state CP-MAS {sup 13}C-NMR, and C-1s NEXAFS spectroscopy. In addition, the relative abundance of carbon isotopes ({sup 12}C, {sup 13}C, {sup 14}C) in the samples was measured. There were no significant differences in the chemical composition or carbon isotope signature of the DOM sampled in spring and fall seasons. Also, differences in DOM composition betweenmore » the five catchments were minor. Compared to reference peat fulvic and humic acids, all DOM samples were richer in O-alkyl carbon and contained less aromatic and phenolic carbon, as shown by FT-IR, {sup 13}C-NMR, and C-1s NEXAFS spectroscopy. The DOM was clearly enriched in {sup 14}C relative to the NBS oxalic acid standard of 1950, indicating that the aquatic DOM contained considerable amounts of organic carbon younger than about 50 years. The weight-based C:N ratios of 31 {+-} 6 and the {delta}{sup 13}Cvalues of -29 {+-} 2{per_thousand}indicate that the isolated DOM is of terrestrial rather than aquatic origin. We conclude that young, hydrophilic carbon compounds of terrestrial origin are predominant in the samples investigated, and that the composition of the aquatic DOM in the studied boreal forest catchments is rather stable during low to intermediate flow conditions.« less

Spatio-temporal variability of the molecular fingerprint of soil dissolved organic matter in a headwater agricultural catchment

NASA Astrophysics Data System (ADS)

Jeanneau, Laurent; Pierson-Wickmann, Anne-Catherine; Jaffrezic, Anne; Lambert, Thibault; Gruau, Gérard

2013-04-01

Dissolved organic matter (DOM) is implied in (i) ecosystem services such as the support of biodiversity, (ii) the alteration of the drinkable water quality by formation of trihalomethane and (iii) the transfer of micropollutants from soils to rivers. Moreover, since DOM connects soils and oceans that are interacting with the atmosphere, understanding its biogeochemistry will help in investigating the carbon cycle and in creating strategies to mitigate climate change. DOM in headwater stream ecosystems is mainly inherited from allochtonous inputs with different reservoirs being mobilized during storm and interstorm events at the scale of an hydrological year. Those changes in DOM reservoirs, if accompanied by composition and reactivity changes, may impact DOM ecosystem services and drinking water production processes. Elucidating the compositional changes due to changes in the source of DOM in rivers has thus become a important axis of DOM research. The aim of this study is to test the ability of the molecular tools of the organic geochemistry and more specifically the combination of thermochemiolysis and gas chromatography - mass spectrometry (THM-GC-MS) to (i) link the variability of the river DOM composition to different DOM reservoirs in catchment soils and (ii) provide hypothesis on the nature and the mechanisms of formation (microbial growth, litter decomposition) of those reservoirs. This analytical method seems particularly adapted since it allows the differentiation between vegetal and microbial inputs and the determination of the extent of the biodegradation process of biomolecules such as lignin. To test this method, the molecular fingerprint of soil DOM has been investigated in the wetland area of a small (500 ha) agricultural catchment (the so-called Kervidy-Naizin catchment) located in Brittany, western France. The soil DOM was sampled fortnightly at three depths using zero-tension lysimeters during the hydrological year 2010-2011. The samples were freeze-dried and analyzed for their molecular composition using THM-GC-MS. Three chemical classes of compounds were investigated including lignin, polysaccharides and fatty acids. The combination of those results at the molecular scale with the results of investigations on spectroscopic (specific UV absorbance at 254 nm, SUVA) fingerprints, the isotopic (d13C) fingerprint of DOM and the hydrological data (water table depth) has highlighted (i) the correlation between molecular and bulk scales investigated using the SUVA and the proportion of lignin markers and (ii) the evolution of the molecular composition of soil DOM related to the changes of the water table depth, which could be linked to the mobilization of different reservoirs and/or to the succession of different mechanisms of production governed by the changes in hydrological regimes. This study highlights THM-GC-MS as a valuable tool to investigate the molecular composition of DOM. By differentiating the vegetal and the microbial components of DOM, it allows the investigation of the sources and mechanisms of DOM formation. Finally, its application to a catchment with hydrological data emphasizes the hydrological regime as a main driver of the evolution of the molecular composition of DOM.

Production and transformation of dissolved neutral sugars and amino acids by bacteria in seawater

NASA Astrophysics Data System (ADS)

Jørgensen, L.; Lechtenfeld, O. J.; Benner, R.; Middelboe, M.; Stedmon, C. A.

2014-10-01

Dissolved organic matter (DOM) in the ocean consists of a heterogeneous mixture of molecules, most of which are of unknown origin. Neutral sugars and amino acids are among the few recognizable biomolecules in DOM, and the molecular composition of these biomolecules is shaped primarily by biological production and degradation processes. This study provides insight into the bioavailability of biomolecules as well as the chemical composition of DOM produced by bacteria. The molecular compositions of combined neutral sugars and amino acids were investigated in DOM produced by bacteria and in DOM remaining after 32 days of bacterial degradation. Results from bioassay incubations with natural seawater (sampled from water masses originating from the surface waters of the Arctic Ocean and the North Atlantic Ocean) and artificial seawater indicate that the molecular compositions following bacterial degradation are not strongly influenced by the initial substrate or bacterial community. The molecular composition of neutral sugars released by bacteria was characterized by a high glucose content (47 mol %) and heterogeneous contributions from other neutral sugars (3-14 mol %). DOM remaining after bacterial degradation was characterized by a high galactose content (33 mol %), followed by glucose (22 mol %) and the remaining neutral sugars (7-11 mol %). The ratio of D-amino acids to L-amino acids increased during the experiments as a response to bacterial degradation, and after 32 days, the D/L ratios of aspartic acid, glutamic acid, serine and alanine reached around 0.79, 0.32, 0.30 and 0.51 in all treatments, respectively. The striking similarity in neutral sugar and amino acid compositions between natural (representing marine semi-labile and refractory DOM) and artificial (representing bacterially produced DOM) seawater samples, suggests that microbes transform bioavailable neutral sugars and amino acids into a common, more persistent form.

Environmental drivers of dissolved organic matter molecular composition in the Delaware Estuary

NASA Astrophysics Data System (ADS)

Osterholz, Helena; Kirchman, David L.; Niggemann, Jutta; Dittmar, Thorsten

2016-11-01

Estuaries as connectors of freshwater and marine aquatic systems are hotspots of biogeochemical element cycling. In one of the best studied temperate estuaries, the Delaware Estuary (USA), we investigated the variability of dissolved organic matter (DOM) over five sampling cruises along the salinity gradient in August and November of 3 consecutive years. Dissolved organic carbon (DOC) concentrations were more variable in the upper reaches of the estuary (245±49 µmol L-1) than at the mouth of the estuary (129±14 µmol L-1). Bulk DOC decreased conservatively along the transect in November but was non-conservative with increased DOC concentrations mid-estuary in August. Detailed analysis of the solid-phase extractable DOM pool via ultrahigh resolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) revealed compositional differences at the molecular level that were not reflected in changes in concentration. Besides the mixing of terrestrial and marine endmember signatures, river discharge levels and biological activity were found to impact DOM molecular composition. DOM composition changed less between August and November than along the salinity gradient. Relative contributions of presumed photolabile DOM compounds did not reveal non-conservative behavior indicative of photochemical processing; suggesting that on the timescales of estuarine mixing photochemical removal of molecules plays a minor role in the turbid Delaware Bay. Overall, a large portion of molecular formulae overlapped between sampling campaigns and persisted during estuarine passage. Extending the analysis to the structural level via the fragmentation of molecular masses in the FT-ICR-MS cell, we found that the relative abundance of isomers along the salinity gradient did not change, indicating a high structural similarity of aquatic DOM independent of the origin. These results point towards a recalcitrant character of the DOM supplied by the Delaware River. We demonstrate that in addition to bulk DOC quantification, detailed information on molecular composition is essential for constraining sources of DOM and to identify the processes that impact estuarine DOM, thereby controlling amount and composition of DOM eventually discharged to the ocean through estuaries.

Illuminating the dark side of DOM: A bottom up approach to understanding the structure and composition of DOM.

NASA Astrophysics Data System (ADS)

Zito, P.; Tarr, M. A.; Spencer, R. G.; Podgorski, D. C.

2017-12-01

Dissolved organic matter (DOM) is one of the most complex natural mixtures on Earth. It is generally comprised of hydrocarbons incorporating a diverse subset of oxygen-containing functional groups along with a small amount of nitrogen, sulfur and phosphorous heteroatoms all of which make it very difficult to chromatographically separate. The only way to directly characterize and quantify these structural and compositional changes is by separating the DOM continuum into defined bins of structure and chemistry. In this study, we take an alternate bottom-up approach that utilizes petroleum to work toward identifying the molecular structures of DOM. Although petroleum is the most structurally diverse mixture in nature, it is almost exclusively comprised of hydrocarbons with only trace quantities of heteroatoms, including oxygen. Here, crude oil was chromatographically separated into bins based on the number of aromatic rings to be used as a starting carbon source. Photochemically produced DOM from these aromatic ring bins provides unique opportunities to gain insight in the compositional controls associated with transport, processing and fate of DOM in natural systems. Here, we present EEMs data from individual ring fractions that were subjected to 24 hours of sunlight to use as a model to fingerprint specific aromatic regions in the DOM fraction. Results illustrate that the 1-, 2-, 3-, 4- and 5- ring fractions exhibit a wide range of structurally dependent excitation and emission spectra. A well-known red-shift in the emission and excitation occurs as the number of rings increase. In order to understand changes in the elemental composition of the data, ultra high-resolution mass spectrometry was used to obtain molecular level information. Together, these data will provide a tool to help understand the relationship of the composition and structure of DOM released into the environment in terms of aromaticity. It is well known that aromaticity is an important indicator of the chemical characteristics of DOM and can be used to explain the role of DOM in environmental processes. Thus, identifying these compounds in terms of aromaticity after photodegradation will provide information about the fate, transport and mechanisms of the photolabile and recalcitrant compounds in the environment.

Spatial variation of dissolved organic matter composition and characteristics in an urbanized watershed

NASA Astrophysics Data System (ADS)

Hsieh, C.; Li, M.

2013-12-01

Dissolved organic matter (DOM) is a chemically complex mixture of organic polymers that plays an important role in river ecosystems and originates from various sources. Some DOMs are autochthonous originating through phytoplankton and microbial activity in situ. On the other hand, some DOMs are allochthonous which are transported to river from the surrounding watershed by natural or anthropogenic activities. The studies of DOM in river are usually conducted at the watershed scale; however, factors of local spatial scale affecting DOM composition also need to take into consideration for the study of DOM in an urbanized watershed. Through increasing urbanization, changes in a watershed occur not only in land use patterns but also in river channel characteristics. The objective of this study is to investigate effects of different river channel characteristics and patterns on changes in DOM source and composition. In this study, we chose three tributaries of Tamsui river in Taiwan according to its land use pattern and river channel characteristics. At each sub-basin, river water samples were sampled from three study sites. River water DOM was measured by using optical measurements of UV absorption and fluorescence spectroscopy. Water samples were also collected for laboratory analysis of different water quality parameters. From our study sites, they are from three sub-basins which are in the similar physical environments but with different river channel types: the highly channelized Keelung river, the less channelized Xindian river, and less channelized Dahan river with five human-made wetlands. From the upstream to the urbanized downstream, composition of DOM showed variation among different sampled sites. In all three sub-basins, the trends of 5-day biochemical oxygen demand (BOD5) and suspended solids (SS) are also different. The changes in DOM source and composition as well as different water quality parmaters occur at the local spatial-scale depended on their river channel characters in urbanized watersheds. Based on our result, it indicates river channel characters which can have effects on biogeochemical processes of DOM. This knowledge can help us in understanding biogeochemical processes controlled or manipulated by anthropogenic activities at different spatial scales, and help us to make an integrative river health management in a watershed.

The chemical composition and source identification of soil dissolved organic matter in riparian buffer zones from Chongming Island, China.

PubMed

Wang, Yulai; Yang, Changming; Li, Jianhua; Shen, Shuo

2014-09-01

Dissolved organic matter (DOM) that is derived from the soil of riparian buffer zones has a complex chemical composition, and it plays an important role in the transport and transformation of pollutants. To identify the source of DOM and to better understand its chemical and structural properties, we collected 33 soil samples from zones with fluctuating water levels along the major rivers on Chongming Island, evaluated the DOM contents in riparian soil, analyzed the chemical composition and functional groups and traced DOM origins by using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) combined with clustering analysis. All sampling sites were divided into four groups by principal component analysis (PCA) on the basis of the DOM molecules. The results showed that there was no significant difference in the DOM contents between every two groups; however, the DOM fractions differed significantly among the different site groups in the following order: Σ lipids and Σ proteins>Σ sugars and Σ fatty acids>Σ amino acids, Σ indoles and Σ alkaloids. DOM in the riparian buffer zones originated from riparian plants, domestic sewage and agricultural activities, and the hydrophobic and amphiphilic fractions accounting for over 60% of the identified molecules were the dominant fractions. Our study has confirmed the heterogeneous properties of DOM, and it is of vital importance to isolate and characterize the various DOM fractions at the molecular level for a better understanding of the behavior and roles of DOM in the natural environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Shift in the chemical composition of dissolved organic matter in the Congo River network

NASA Astrophysics Data System (ADS)

Lambert, Thibault; Bouillon, Steven; Darchambeau, François; Massicotte, Philippe; Borges, Alberto V.

2016-09-01

The processing of terrestrially derived dissolved organic matter (DOM) during downstream transport in fluvial networks is poorly understood. Here, we report a dataset of dissolved organic carbon (DOC) concentrations and DOM composition (stable carbon isotope ratios, absorption and fluorescence properties) acquired along a 1700 km transect in the middle reach of the Congo River basin. Samples were collected in the mainstem and its tributaries during high-water (HW) and falling-water (FW) periods. DOC concentrations and DOM composition along the mainstem were found to differ between the two periods because of a reduced lateral mixing between the central water masses of the Congo River and DOM-rich waters from tributaries and also likely because of a greater photodegradation during FW as water residence time (WRT) increased. Although the Cuvette Centrale wetland (one of the world's largest flooded forests) continuously releases highly aromatic DOM in streams and rivers of the Congo Basin, the downstream transport of DOM was found to result in an along-stream gradient from aromatic to aliphatic compounds. The characterization of DOM through parallel factor analysis (PARAFAC) suggests that this transition results from (1) the losses of aromatic compounds by photodegradation and (2) the production of aliphatic compounds by biological reworking of terrestrial DOM. Finally, this study highlights the critical importance of the river-floodplain connectivity in tropical rivers in controlling DOM biogeochemistry at a large spatial scale and suggests that the degree of DOM processing during downstream transport is a function of landscape characteristics and WRT.

Biochar amendment to soil changes dissolved organic matter content and composition.

PubMed

Smebye, Andreas; Alling, Vanja; Vogt, Rolf D; Gadmar, Tone C; Mulder, Jan; Cornelissen, Gerard; Hale, Sarah E

2016-01-01

Amendments of biochar, a product of pyrolysis of biomass, have been shown to increase fertility of acidic soils by enhancing soil properties such as pH, cation-exchange-capacity and water-holding-capacity. These parameters are important in the context of natural organic matter contained in soils, of which dissolved organic matter (DOM) is the mobile and most bioavailable fraction. The effect of biochar on the content and composition of DOM in soils has received little research attention. This study focuses on the effects of amendments of two different biochars to an acidic acrisol and a pH-neutral brown soil. A batch experiment showed that mixing biochar with the acrisols at a 10 wt.% dose increased the pH from 4.9 to 8.7, and this resulted in a 15-fold increase in the dissolved organic carbon concentration (from 4.5 to 69 mg L(-1)). The pH-increase followed the same trend as the release of DOM in the experiment, causing higher DOM solubility and desorption of DOM from mineral sites. The binding to biochar of several well-characterised reference DOM materials was also investigated and results showed a higher sorption of aliphatic DOM to biochar than aromatic DOM, with DOM-water partitioning coefficients (Kd-values) ranging from 0.2 to 590 L kg(-1). A size exclusion occurring in biochar's micropores, could result in a higher sorption of smaller aliphatic DOM molecules than larger aromatic ones. These findings indicate that biochar could increase the leaching of DOM from soil, as well as change the DOM composition towards molecules with a larger size and higher aromaticity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Continuous summer export of nitrogen-rich organic matter from the Greenland Ice Sheet inferred by ultrahigh resolution mass spectrometry.

PubMed

Lawson, Emily C; Bhatia, Maya P; Wadham, Jemma L; Kujawinski, Elizabeth B

2014-12-16

Runoff from glaciers and ice sheets has been acknowledged as a potential source of bioavailable dissolved organic matter (DOM) to downstream ecosystems. This source may become increasingly significant as glacial melt rates increase in response to future climate change. Recent work has identified significant concentrations of bioavailable carbon and iron in Greenland Ice Sheet (GrIS) runoff. The flux characteristics and export of N-rich DOM are poorly understood. Here, we employed electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to determine the elemental compositions of DOM molecules in supraglacial water and subglacial runoff from a large GrIS outlet glacier. We provide the first detailed temporal analysis of the molecular composition of DOM exported over a full melt season. We find that DOM pools in supraglacial and subglacial runoff are compositionally diverse and that N-rich material is continuously exported throughout the melt season, as the snowline retreats further inland. Identification of protein-like compounds and a high proportion of N-rich DOM, accounting for 27-41% of the DOM molecules identified by ESI FT-ICR MS, may suggest a microbial provenance and high bioavailability of glacially exported DOM to downstream microbial communities.

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.

Compositions and constituents of freshwater dissolved organic matter isolated by reverse osmosis.

PubMed

Zhang, Yulong; Huang, Wen; Ran, Yong; Mao, Jingdong

2014-08-15

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state (13)C nuclear magnetic resonance ((13)C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the (13)C NMR and δ(13)C analyses. Carbohydrates and lipids accounted for 25.0-41.5% and 30.2-46.3% of the identifiable DOM, followed by proteins (18.2-19.8%) and lignin (7.17-12.8%). The freshwater DOM contained much higher alkyl and aromatic C but lower alkoxyl and carboxyl C than marine DOM. The structural difference was not completely accounted for by using structure of high molecular weight (HMW) DOM, suggesting a size change involved in transformations of DOM during the transport from rivers to oceans. Copyright © 2014 Elsevier Ltd. All rights reserved.

Unraveling signatures of biogeochemical processes and the depositional setting in the molecular composition of pore water DOM across different marine environments

NASA Astrophysics Data System (ADS)

Schmidt, Frauke; Koch, Boris P.; Goldhammer, Tobias; Elvert, Marcus; Witt, Matthias; Lin, Yu-Shih; Wendt, Jenny; Zabel, Matthias; Heuer, Verena B.; Hinrichs, Kai-Uwe

2017-06-01

Dissolved organic matter (DOM) in marine sediment pore waters derives largely from decomposition of particulate organic matter and its composition is influenced by various biogeochemical and oceanographic processes in yet undetermined ways. Here, we determine the molecular inventory of pore water DOM in marine sediments of contrasting depositional regimes with ultrahigh-resolution mass spectrometry and complementary bulk chemical analyses in order to elucidate the factors that shape DOM composition. Our sample sets from the Mediterranean, Marmara and Black Seas covered different sediment depths, ages and a range of marine environments with different (i) organic matter sources, (ii) balances of organic matter production and preservation, and (iii) geochemical conditions in sediment and water column including anoxic, sulfidic and hypersaline conditions. Pore water DOM had a higher molecular formula richness than overlying water with up to 11,295 vs. 2114 different molecular formulas in the mass range of 299-600 Da and covered a broader range of element ratios (H/C = 0.35-2.19, O/C = 0.03-1.19 vs. H/C = 0.56-2.13, O/C = 0.15-1.14). Formula richness was independent of concentrations of DOC and TOC. Near-surface pore water DOM was more similar to water column DOM than to deep pore water DOM from the same core with respect to formula richness and the molecular composition, suggesting exchange at the sediment-water interface. The DOM composition in the deeper sediments was controlled by organic matter source, selective decomposition of specific DOM fractions and early diagenetic molecule transformations. Compounds in pelagic sediment pore waters were predominantly highly unsaturated and N-bearing formulas, whereas oxygen-rich CHO-formulas and aromatic compounds were more abundant in pore water DOM from terrigenous sediments. The increase of S-bearing molecular formulas in the water column and pore waters of the Black Sea and the Mediterranean Discovery Basin was consistent with elevated HS- concentrations reflecting the incorporation of sulfur into biomolecules during early diagenesis. Sulfurization resulted in an increased average molecular mass of DOM and higher formula richness (up to 5899 formulas per sample). In sediments from the methanogenic zone in the Black Sea, the DOM pool was distinctly more reduced than overlying sediments from the sulfate-reducing zone. Bottom and pore water DOM from the Discovery Basin contained the highest abundances of aliphatic compounds in the entire dataset; a large fraction of abundant N-bearing formulas possibly represented peptide and nucleotide formulas suggesting preservation of these molecules in the life inhibiting environment of the Discovery Basin. Our unique data set provides the basis for a comprehensive understanding of the molecular signatures in pore water DOM and the turnover of sedimentary organic matter in marine sediments.

Biochemical Composition of Dissolved Organic Matter Released During Experimental Diatom Blooms

NASA Technical Reports Server (NTRS)

Mannino, Antonio; Harvey, H. Rodger

2002-01-01

An axenic culture of Skeletonema costatum was grown to late-log phase to examine the molecular weight distribution and the biochemical composition of high molecular weight dissolved organic matter released in the absence of actively growing bacteria. A second culture was grown in a 5 m(exp 3) mesocosm and placed in darkness for a period of 51 days to examine the impact of phytoplankton bloom dynamics and microbial decomposition on dissolved (DOM) and particulate organic matter (POM) composition. DOM was separated using tangential-flow ultrafiltration into three nominal size fractions: LDOM (less than 1 kDa DOM), HDOM (1-30 kDa) and VHDOM (30 kDa-0.2 micron) and characterized. Both axenic and mesocosm diatom blooms released 28-33% of net primary production as dissolved organic carbon (DOC). In the axenic culture, HDOM and LDOM each comprised about half of the diatom-released DOC with less than l% as VHDOM. Diatoms from both experiments released carbohydrate-rich high molecular weight DOM. Much of the axenic diatom-released high molecular weight DOC could be chemically characterized (61% of HDOM and 78% of VHDOM) with carbohydrates as the primary component (45% of HDOM and 55% of VHDOM). Substantial amounts of hydrolyzable amino acids (16% of HDOM and 22% of VHDOM) and small amounts of lipids (less than 1%) were also released. Proportions of recognizable biochemical components in DOM produced in the mesocosm bloom were lower compared to the axenic culture. The presence of bacterial fatty acids and peptidoglycan-derived D-amino acids within high molecular weight fractions from the mesocosm bloom revealed that bacteria contributed a variety of macromolecules to DOM during the growth and decay of the diatom bloom. Release of significant amounts of DOC by diatoms demonstrates that DOM excretion is an important component of phytoplankton primary production. Similarities in high molecular weight DOM composition in marine waters and diatom cultures highlight the importance of phytoplankton to DOM composition in the ocean.

Cascading influence of inorganic nitrogen sources on DOM production, composition, lability and microbial community structure in the open ocean.

PubMed

Goldberg, S J; Nelson, C E; Viviani, D A; Shulse, C N; Church, M J

2017-09-01

Nitrogen frequently limits oceanic photosynthesis and the availability of inorganic nitrogen sources in the surface oceans is shifting with global change. We evaluated the potential for abrupt increases in inorganic N sources to induce cascading effects on dissolved organic matter (DOM) and microbial communities in the surface ocean. We collected water from 5 m depth in the central North Pacific and amended duplicate 20 liter polycarbonate carboys with nitrate or ammonium, tracking planktonic carbon fixation, DOM production, DOM composition and microbial community structure responses over 1 week relative to controls. Both nitrogen sources stimulated bulk phytoplankton, bacterial and DOM production and enriched Synechococcus and Flavobacteriaceae; ammonium enriched for oligotrophic Actinobacteria OM1 and Gammaproteobacteria KI89A clades while nitrate enriched Gammaproteobacteria SAR86, SAR92 and OM60 clades. DOM resulting from both N enrichments was more labile and stimulated growth of copiotrophic Gammaproteobacteria (Alteromonadaceae and Oceanospirillaceae) and Alphaproteobacteria (Rhodobacteraceae and Hyphomonadaceae) in weeklong dark incubations relative to controls. Our study illustrates how nitrogen pulses may have direct and cascading effects on DOM composition and microbial community dynamics in the open ocean. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Compositionally heterogeneous dissolved organic matter reflects changing flowpaths in a large ice sheet catchment over the course of the melt season at Leverett Glacier, southwest Greenland

NASA Astrophysics Data System (ADS)

Kellerman, A.; Hawkings, J.; Marshall, M.; Spencer, R.; Wadham, J.

2017-12-01

The Greenland Ice Sheet (GrIS) is losing mass at a remarkable rate. This loss of mass coincides with the export of dissolved organic matter (DOM) and other nutrients from the ice sheet and exerts a primary control on secondary production in downstream ecosystems. However, little is known about the source and composition of DOM exported from these dilute, yet immense, systems. Samples were collected from May 11, 2015 to July 29, 2015 from the outflow of Leverett Glacier, a large, land-terminating glacier of the southwest GrIS. Dissolved organic carbon (DOC) concentrations were measured and the optical properties of DOM were characterized using absorbance and fluorescence spectroscopy. At the beginning of the season, when discharge is <5 m3 sec-1, red-shifted fluorescence suggests terrestrial inputs from either overridden soils or proglacial inputs dominate the DOM pool. With the onset of melt, after an initial pulse in both DOC quantity and red-shifted fluorescence intensity, the DOC concentration and fluorescence intensity is diluted, with little change in DOM composition. The terrestrial signal is lost with the first outburst event in late June, and a single protein-like fluorophore is exhibited for three weeks. On July 10th, a fourth outburst event introduces a second protein-like fluorophore, indicative of production on the ice sheet, and this signature is maintained until the end of the July. These results suggest that subglaical drainage flowpaths and water source influence the exported DOC concentration and DOM composition over a summer melt season. As glacial outflow shifts from higher DOC concentrations early in the season to low DOC concentrations later in the summer, these results impact estimates of carbon export from glaciers. Furthermore, as composition is related to reactivity, the compositional changes observed may indicate shifts in the bioavailability of the DOM upon delivery to coastal systems, a result of changing DOM sources over the course of the season.

DOM composition and transformation in boreal forest soils: The effects of temperature and organic-horizon decomposition state

USGS Publications Warehouse

O’Donnell, Jonathan A.; Aiken, George R.; Butler, Kenna D.; Guillemette, Francois; Podgorski, David C.; Spencer, Robert G. M.

2016-01-01

The boreal region stores large amounts of organic carbon (C) in organic-soil horizons, which are vulnerable to destabilization via warming and disturbance. Decomposition of soil organic matter (SOM) contributes to the production and turnover of dissolved organic matter (DOM). While temperature is a primary control on rates of SOM and DOM cycling, little is known about temperature effects on DOM composition in soil leachate. Here we conducted a 30 day incubation to examine the effects of temperature (20 versus 5°C) and SOM decomposition state (moss versus fibric versus amorphous horizons) on DOM composition in organic soils of interior Alaska. We characterized DOM using bulk dissolved organic C (DOC) concentration, chemical fractionation, optical properties, and ultrahigh-resolution mass spectrometry. We observed an increase in DOC concentration and DOM aromaticity in the 20°C treatment compared to the 5°C treatment. Leachate from fibric horizons had higher DOC concentration than shallow moss or deep amorphous horizons. We also observed chemical shifts in DOM leachate over time, including increases in hydrophobic organic acids, polyphenols, and condensed aromatics and decreases in low-molecular weight hydrophilic compounds and aliphatics. We compared ultrahigh-resolution mass spectrometry and optical data and observed strong correlations between polyphenols, condensed aromatics, SUVA254, and humic-like fluorescence intensities. These findings suggest that biolabile DOM was preferentially mineralized, and the magnitude of this transformation was determined by kinetics (i.e., temperature) and substrate quality (i.e., soil horizon). With future warming, our findings indicate that organic soils may release higher concentrations of aromatic DOM to aquatic ecosystems.

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

USGS Publications Warehouse

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

2016-01-01

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

Properties of dissolved and total organic matter in throughfall, stemflow and forest floor leachate of Central European forests

NASA Astrophysics Data System (ADS)

Bischoff, S.; Schwarz, M. T.; Siemens, J.; Thieme, L.; Wilcke, W.; Michalzik, B.

2014-10-01

For the first time, we investigated the composition of dissolved organic matter (DOM) compared to total OM (TOM, consisting of DOM and particulate OM, POM) in throughfall, stemflow and forest floor leachate of beech and spruce forests using solid state 13C nuclear magnetic resonance spectroscopy. We hypothesized that the composition and properties of OM in forest ecosystem water samples differed between DOM and TOM and between the two tree species. Under beech, a contribution of phyllosphere-derived fresh POM was echoed in structural differences. Compared with DOM, TOM exhibited higher relative intensities for the alkyl C region, representing aliphatic C from less decomposed organic material, and lower relative intensities for lignin-derived and aromatic C of the aryl C region, resulting in lower aromaticity indices and reduced humification intensities. Since differences in the structural composition of DOM and TOM were less pronounced under spruce than under beech, we suspect a~tree species-related effect on the origin of OM composition and resulting properties (e.g. recalcitrance, allelopathic potential).

Biogeochemical and Optical Analysis of Coastal DOM for Satellite Retrieval of Terrigenous DOM in the U.S. Middle Atlantic Bight

NASA Technical Reports Server (NTRS)

Mannino, A.; Dyda, R. Y.; Hernes, P. J.; Hooker, Stan; Hyde, Kim; Novak, Mike

2012-01-01

Estuaries and coastal ocean waters experience a high degree of variability in the composition and concentration of particulate and dissolved organic matter (DOM) as a consequence of riverine/estuarine fluxes of terrigenous DOM, sediments, detritus and nutrients into coastal waters and associated phytoplankton blooms. Our approach integrates biogeochemical measurements (elemental content, molecular analyses), optical properties (absorption) and remote sensing to examine terrestrial DOM contributions into the U.S. Middle Atlantic Bight (MAB). We measured lignin phenol composition, DOC and CDOM absorption within the Chesapeake and Delaware Bay mouths, plumes and adjacent coastal ocean waters to derive empirical relationships between CDOM and biogeochemical measurements for satellite remote sensing application. Lignin ranged from 0.03 to 6.6 ug/L between estuarine and outer shelf waters. Our results demonstrate that satellite-derived CDOM is useful as a tracer of terrigenous DOM in the coastal ocean

Spatial pattern of dissolved organic matter (DOM) along a stream drainage in a forested, Piedmont catchment

NASA Astrophysics Data System (ADS)

Inamdar, S. P.; Singh, S.

2013-12-01

Understanding how dissolved organic matter (DOM) varies spatially in catchments and the processes and mechanisms that regulate this variation is critical for developing accurate and reliable models of DOM. We determined the concentrations and composition of DOM at multiple locations along a stream drainage network in a 79 ha forested, Piedmont, watershed in Maryland, USA. DOM concentrations and composition was compared for five stream locations during baseflow (drainage areas - 0.62, 3.5, 4.5, 12 and 79 ha) and three locations (3.5, 12, 79 ha) for storm flow. Sampling was conducted by manual grab samples and automated ISCO samplers. DOM composition was characterized using a suite of spectrofluorometric indices which included - HIX, a254, and FI. A site-specific PARAFAC model was also developed for DOM fluorescence to determine the humic-, fulvic-, and protein-like DOM constituents. Hydrologic flow paths during baseflow and stormflow were characterized for all stream locations using an end-member mixing model (EMMA). DOM varied notably across the sampled positions for baseflow and stormflow. During baseflow, mean DOC concentrations for the sampled locations ranged between 0.99-3.1 mg/L whereas for stormflow the range was 5.22-8.11 mg/L. Not surprisingly, DOM was more humic and aromatic during stormflow versus baseflow. The 3.5 ha stream drainage location that contained a large wetland yielded the highest DOC concentration as well as the most humic and aromatic DOM, during both, baseflow and stormflow. In contrast, a headwater stream location (0.62 ha) that received runoff from a groundwater seep registered the highest mean value for % protein-like DOM (30%) and the lowest index for aromaticity (mean a254 = 6.52) during baseflow. During stormflow, the mean % protein-like DOM was highest at the largest 79 ha drainage location (mean = 11.8%) and this site also registered the lowest mean value for a254 (46.3). Stream drainage locations that received a larger proportion of runoff along surficial flow paths produced a more aromatic and humic DOM with high DOC concentrations; whereas those with a greater proportion of groundwater contributions produced DOM with greater % of protein-like content. Overall, our observations suggest that occurrence of wetlands and the nature of hydrologic flow paths were the key determinants for the spatial pattern of DOM.

Effect of Diane-35, alone or in combination with orlistat or metformin in Chinese polycystic ovary syndrome patients.

PubMed

Ruan, Xiangyan; Song, Jinghua; Gu, Muqing; Wang, Lijuan; Wang, Husheng; Mueck, Alfred O

2018-06-01

To evaluate the effect of Diane-35, alone or in combination with orlistat or metformin, on androgen and body fat percentage parameters in Chinese overweight and obese polycystic ovary syndrome (PCOS) patients with insulin resistance. A total of 240 PCOS women were randomly allocated to receive Diane-35 alone (D group), Diane-35 plus orlistat (DO group), Diane-35 plus metformin (DM group), or Diane-35 plus orlistat plus metformin (DOM group). Serum TT, DHEA-S, androstenedione, SHBG, FT, FAI, body fat, and body fat percentage were assessed at baseline and after 12 weeks of treatment. Significant changes in serum TT, SHBG, and FAI were observed in all treatment groups compared with baseline. DHEA-S and androstenedione significantly decreased in the DO, DM, and DOM groups after treatment. FT only significantly decreased in the DOM group. Body fat and body fat percentage significantly decreased in the DO and DOM groups. Compared with the D group, DHEA-S significantly decreased in the DO, DM, and DOM groups (F = 4.081, p = 0.008); SHBG significantly increased in the DOM group (F = 3.019, p = 0.031); and FAI significantly decreased in the DO group (χ 2  = 12.578, p = 0.006). There were significant differences between groups in body fat percentage (χ 2  = 23.590, p < 0.001). Side-effects were less with orlistat than metformin. Diane-35 in combination with orlistat or metformin is more effective in reducing androgen than Diane-35 alone. Orlistat is more effective in reducing body fat percentage than metformin. In addition, orlistat has mild side-effects and is better tolerated compared with metformin.

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 variation in the fraction of non-chromophoric DOM. However, the relationship between HPOA content and UV absorbance was stronger and more consistent because the HPOA fraction contains a greater percentage of UV absorbing compounds than other fractions of the DOM. These results demonstrate that optical properties, such as UV absorbance, are excellent proxies for DOC and HPOA concentrations within a given system. For a limited set of samples, we observed that optical measurements were strongly correlated with lignin phenols, a biomarker indicative of higher plant sources of DOM, and with Hg, which interacts strongly with DOM. Optical measurements are relatively inexpensive to obtain, provide critical information related to DOM composition and reactivity, and can be measured in situ. When combined with discharge data, optical measurements allow estimation of both DOM flux and reactivity in streams and rivers. The link between the nature and reactivity of DOM and its optical properties can be exploited to provide powerful monitoring tools to assess the impacts of climate change and management practices on overall water quality, on DOM transport and transformation, and on the transport of other chemical constituents of interest.

Bioconcentration of perfluoroalkyl substances by Chironomus plumosus larvae in water with different types of dissolved organic matters.

PubMed

Wen, Wu; Xia, Xinghui; Chen, Xi; Wang, Haotian; Zhu, Baotong; Li, Husheng; Li, Yang

2016-06-01

The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L(-1). The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L(-1), body burdens of these PFASs increased by 7.5%-148.8% and 5.7%-37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Optical, Chemical, and Molecular Dissolved Organic Matter Succession Along a Boreal Soil-Stream-River Continuum

NASA Astrophysics Data System (ADS)

Hutchins, Ryan H. S.; Aukes, Pieter; Schiff, Sherry L.; Dittmar, Thorsten; Prairie, Yves T.; del Giorgio, Paul A.

2017-11-01

Soils export large amounts of organic matter to rivers, and there are still major uncertainties concerning the composition and reactivity of this material and its fate within the fluvial network. Here we reconstructed the pattern of movement and processing of dissolved organic matter (DOM) along a soil-stream-river continuum under summer baseflow conditions in a boreal region of Québec (Canada), using a combination of fluorescence spectra, size exclusion chromatography and ultrahigh resolution mass spectrometry. Our results show that there is a clear sequence of selective DOM degradation along the soil-stream-river continuum, which results in pronounced compositional shifts downstream. The soil-stream interface was a hot spot of DOM degradation, where biopolymers and low molecular weight (LMW) compounds were selectively removed. In contrast, processing in the stream channel was dominated by the degradation of humic-like aromatic DOM, likely driven by photolysis, with little further degradation of either biopolymers or LMW compounds. Overall, there was a high degree of coherence between the patterns observed in DOM chemical composition, optical properties, and molecular profiles, and none of these approaches pointed to measurable production of new DOM components, suggesting that the DOM pools removed during transit were likely mineralized to CO2. Our first order estimates suggest that rates of soil-derived DOM mineralization could potentially sustain over half of the measured CO2 emissions from this stream network, with mineralization of biopolymers and humic substances contributing roughly equally to these fluvial emissions.

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.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

PubMed

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

2014-06-15

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

Effects of iron on optical properties of dissolved organic matter.

PubMed

Poulin, Brett A; Ryan, Joseph N; Aiken, George R

2014-09-02

Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV-vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV-vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV-vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (E2:E3) and spectral slope ratios (SR) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation-emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

Effects of iron on optical properties of dissolved organic matter

USGS Publications Warehouse

Poulin, Brett; Ryan, Joseph N.; Aiken, George R.

2014-01-01

Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV–vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV–vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV–vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (E2:E3) and spectral slope ratios (SR) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation–emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

Spatial and temporal variations in DOM composition in ecosystems: The importance of long-term monitoring of optical properties

Treesearch

R. Jaffe; D. McKnight; N. Maie; R. Cory; W. H. McDowell; J.L. Campbell

2008-01-01

Source, transformation, and preservation mechanisms of dissolved organic matter (DOM) remain elemental questions in contemporary marine and aquatic sciences and represent a missing link in models of global elemental cycles. Although the chemical character of DOM is central to its fate in the global carbon cycle, DOM characterizations in long-term ecological research...

The river as a chemostat: fresh perspectives on dissolved organic matter flowing down the river continuum

USGS Publications Warehouse

Creed, Irena F.; McKnight, Diane M.; Pellerin, Brian; Green, Mark B.; Bergamaschi, Brian; Aiken, George R.; Burns, Douglas A.; Findlay, Stuart E G; Shanley, James B.; Striegl, Robert G.; Aulenbach, Brent T.; Clow, David W.; Laudon, Hjalmar; McGlynn, Brian L.; McGuire, Kevin J.; Smith, Richard A.; Stackpoole, Sarah M.

2015-01-01

A better understanding is needed of how hydrological and biogeochemical processes control dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) composition from headwaters downstream to large rivers. We examined a large DOM dataset from the National Water Information System of the US Geological Survey, which represents approximately 100 000 measurements of DOC concentration and DOM composition at many sites along rivers across the United States. Application of quantile regression revealed a tendency towards downstream spatial and temporal homogenization of DOC concentrations and a shift from dominance of aromatic DOM in headwaters to more aliphatic DOM downstream. The DOC concentration–discharge (C-Q) relationships at each site revealed a downstream tendency towards a slope of zero. We propose that despite complexities in river networks that have driven many revisions to the River Continuum Concept, rivers show a tendency towards chemostasis (C-Q slope of zero) because of a downstream shift from a dominance of hydrologic drivers that connect terrestrial DOM sources to streams in the headwaters towards a dominance of instream and near-stream biogeochemical processes that result in preferential losses of aromatic DOM and preferential gains of aliphatic DOM.

Origins and bioavailability of dissolved organic matter in groundwater

USGS Publications Warehouse

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

2015-01-01

Dissolved organic matter (DOM) in groundwater influences water quality and fuels microbial metabolism, but its origins, bioavailability and chemical composition are poorly understood. The origins and concentrations of dissolved organic carbon (DOC) and bioavailable DOM were monitored during a long-term (2-year) study of groundwater in a fractured-rock aquifer in the Carolina slate belt. Surface precipitation was significantly correlated with groundwater concentrations of DOC, bioavailable DOM and chromophoric DOM, indicating strong hydrological connections between surface and ground waters. The physicochemical and biological processes shaping the concentrations and compositions of DOM during its passage through the soil column to the saturated zone are conceptualized in the regional chromatography model. The model provides a framework for linking hydrology with the processes affecting the transformation, remineralization and microbial production of DOM during passage through the soil column. Lignin-derived phenols were relatively depleted in groundwater DOM indicating substantial removal in the unsaturated zone, and optical properties of chromophoric DOM indicated lower molecular weight DOM in groundwater relative to surface water. The prevalence of glycine, γ-aminobutyric acid, and d-enantiomers of amino acids indicated the DOM was highly diagenetically altered. Bioassay experiments were used to establish DOC-normalized yields of amino acids as molecular indicators of DOM bioavailability in groundwater. A relatively small fraction (8 ± 4 %) of DOC in groundwater was bioavailable. The relatively high yields of specific d-enantiomers of amino acids indicated a substantial fraction (15–34 %) of groundwater DOC was of bacterial origin.

Stream Dissolved Organic Matter Quantity and Quality Along a Wetland-Cropland Catchment Gradient

NASA Astrophysics Data System (ADS)

McDonough, O.; Hosen, J. D.; Lang, M. W.; Oesterling, R.; Palmer, M.

2012-12-01

Wetlands may be critical sources of dissolved organic matter (DOM) to stream networks. Yet, more than half of wetlands in the continental United States have been lost since European settlement, with the majority of loss attributed to agriculture. The degree to which agricultural loss of wetlands impacts stream DOM is largely unknown and may have important ecological implications. Using twenty headwater catchments on the Delmarva Peninsula (Maryland, USA), we investigated the seasonal influence of wetland and cropland coverage on downstream DOM quantity and quality. In addition to quantifying bulk downstream dissolved organic carbon (DOC) concentration, we used a suite of DOM UV-absorbance metrics and parallel factor analysis (PARAFAC) modeling of excitation-emission fluorescence spectra (EEMs) to characterize DOM composition. Percent bioavailable DOC (%BDOC) was measured during the Spring sampling using a 28-day incubation. Percent wetland coverage and % cropland within the watersheds were significantly negatively correlated (r = -0.93, p < 0.001). Results show that % wetland coverage was positively correlated with stream DOM concentration, molecular weight, aromaticity, humic-like fluorescence, and allochthonous origin. Conversely, increased wetland coverage was negatively correlated with stream DOM protein-like fluorescence. Percent BDOC decreased with DOM humic-like fluorescence and increased with protein-like fluorescence. We observed minimal seasonal interaction between % wetland coverage and DOM concentration and composition across Spring, Fall, and Winter sampling seasons. However, principal component analysis suggested more pronounced seasonal differences exist in stream DOM. This study highlights the influence of wetlands on downstream DOM in agriculturally impacted landscapes where loss of wetlands to cultivation may significantly alter stream DOM quantity and quality.

Molecular size-dependent abundance and composition of dissolved organic matter in river, lake and sea waters.

PubMed

Xu, Huacheng; Guo, Laodong

2017-06-15

Dissolved organic matter (DOM) is ubiquitous in natural waters. The ecological role and environmental fate of DOM are highly related to the chemical composition and size distribution. To evaluate size-dependent DOM quantity and quality, water samples were collected from river, lake, and coastal marine environments and size fractionated through a series of micro- and ultra-filtrations with different membranes having different pore-sizes/cutoffs, including 0.7, 0.4, and 0.2 μm and 100, 10, 3, and 1 kDa. Abundance of dissolved organic carbon, total carbohydrates, chromophoric and fluorescent components in the filtrates decreased consistently with decreasing filter/membrane cutoffs, but with a rapid decline when the filter cutoff reached 3 kDa, showing an evident size-dependent DOM abundance and composition. About 70% of carbohydrates and 90% of humic- and protein-like components were measured in the <3 kDa fraction in freshwater samples, but these percentages were higher in the seawater sample. Spectroscopic properties of DOM, such as specific ultraviolet absorbance, spectral slope, and biological and humification indices also varied significantly with membrane cutoffs. In addition, different ultrafiltration membranes with the same manufacture-rated cutoff also gave rise to different DOM retention efficiencies and thus different colloidal abundances and size spectra. Thus, the size-dependent DOM properties were related to both sample types and membranes used. Our results here provide not only baseline data for filter pore-size selection when exploring DOM ecological and environmental roles, but also new insights into better understanding the physical definition of DOM and its size continuum in quantity and quality in aquatic environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular fractionation of dissolved organic matter with metal salts.

PubMed

Riedel, Thomas; Biester, Harald; Dittmar, Thorsten

2012-04-17

Coagulation of dissolved organic matter (DOM) by hydrolyzing metals is an important environmental process with particular relevance, e.g., for the cycling of organic matter in metal-rich aquatic systems or the flocculation of organic matter in wastewater treatment plants. Often, a nonremovable fraction of DOM remains in solution even at low DOM/metal ratios. Because coagulation by metals results from interactions with functional groups, we hypothesize that noncoagulating fractions have a distinct molecular composition. To test the hypothesis, we analyzed peat-derived dissolved organic matter remaining in solution after mixing with salts of Ca, Al, and Fe using 15 T Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Addition of metals resulted in a net removal of DOM. Also a reduction of molecular diversity was observed, as the number of peaks from the ESI-FT-ICR-MS spectra decreased. At DOM/metal ratios of ∼9 Ca did not show any preference for distinct molecular fractions, while Fe and Al removed preferentially the most oxidized compounds (O/C ratio >0.4) of the peat leachate. Lowering DOM/metal ratios to ∼1 resulted in further removal of less oxidized as well as more aromatic compounds ("black carbon"). Molecular composition in the residual solution after coagulation was more saturated, less polar, and less oxidized compared to the original peat leachate and exhibited a surprising similarity with DOM of marine origin. By identifying more than 9200 molecular formulas we can show that structural properties (saturation and aromaticity) and oxygen content of individual DOM molecules play an important role in coagulation with metals. We conclude that polyvalent cations not only alter the net mobility but also the very molecular composition of DOM in aquatic environments.

Hydrological changes of DOM composition and biodegradability of rivers in temperate monsoon climates

NASA Astrophysics Data System (ADS)

Shin, Yera; Lee, Eun-Ju; Jeon, Young-Joon; Hur, Jin; Oh, Neung-Hwan

2016-09-01

The spatial and hydrological dynamics of dissolved organic matter (DOM) composition and biodegradability were investigated for the five largest rivers in the Republic of Korea (South Korea) during the years 2012-2013 using incubation experiments and spectroscopic measurements, which included parallel factor analysis (PARAFAC). The lower reaches of the five rivers were selected as windows showing the integrated effects of basin biogeochemistry of different land use under Asian monsoon climates, providing an insight on consistency of DOM dynamics across multiple sites which could be difficult to obtain from a study on an individual river. The mean dissolved organic carbon (DOC) concentrations of the five rivers were relatively low, ranging from 1.4 to 3.4 mg L-1, due to the high slope and low percentage of wetland cover in the basin. Terrestrial humic- and fulvic-like components were dominant in all the rivers except for one, where protein-like compounds were up to ∼80%. However, terrestrial components became dominant in all five of the rivers after high precipitation during the summer monsoon season, indicating the strong role of hydrology on riverine DOM compositions for the basins under Asian monsoon climates. Considering that 64% of South Korea is forested, our results suggest that the forests could be a large source of riverine DOM, elevating the DOM loads during monsoon rainfall. Although more DOM was degraded when DOM input increased, regardless of its sources, the percent biodegradability was reduced with increased proportions of terrestrially derived aromatic compounds. The shift in DOM quality towards higher percentages of aromatic terrestrial compounds may alter the balance of the carbon cycle of coastal ecosystems by changing microbial metabolic processes if climate extremes such as heavy storms and typhoons become more frequent due to climate change.

Spatiotemporal variations in the abundance and composition of bulk and chromophoric dissolved organic matter in seasonally hypoxia-influenced Green Bay, Lake Michigan, USA.

PubMed

DeVilbiss, Stephen E; Zhou, Zhengzhen; Klump, J Val; Guo, Laodong

2016-09-15

Green Bay, Lake Michigan, USA, is the largest freshwater estuary in the Laurentian Great Lakes and receives disproportional terrestrial inputs as a result of a high watershed to bay surface area ratio. While seasonal hypoxia and the formation of "dead zones" in Green Bay have received increasing attention, there are no systematic studies on the dynamics of dissolved organic matter (DOM) and its linkage to the development of hypoxia. During summer 2014, bulk dissolved organic carbon (DOC) analysis, UV-vis spectroscopy, and fluorescence excitation-emission matrices (EEMs) coupled with PARAFAC analysis were used to quantify the abundance, composition and source of DOM and their spatiotemporal variations in Green Bay, Lake Michigan. Concentrations of DOC ranged from 202 to 571μM-C (average=361±73μM-C) in June and from 279 to 610μM-C (average=349±64μM-C) in August. In both months, absorption coefficient at 254nm (a254) was strongly correlated to bulk DOC and was most abundant in the Fox River, attesting a dominant terrestrial input. Non-chromophoric DOC comprised, on average, ~32% of bulk DOC in June with higher terrestrial DOM and ~47% in August with higher aquagenic DOM, indicating that autochthonous and more degraded DOM is of lower optical activity. PARAFAC modeling on EEM data resulted in four major fluorescent DOM components, including two terrestrial humic-like, one aquagenic humic-like, and one protein-like component. Variations in the abundance of DOM components further supported changes in DOM sources. Mixing behavior of DOM components also indicated that while bulk DOM behaved quasi-conservatively, significant compositional changes occurred during transport from the Fox River to the open bay. Copyright © 2016 Elsevier B.V. All rights reserved.

Assessing the contribution of wetlands and subsided islands to dissolved organic matter and disinfection byproduct precursors in the Sacramento-San Joaquin River Delta: A geochemical approach

USGS Publications Warehouse

Kraus, T.E.C.; Bergamaschi, B.A.; Hernes, P.J.; Spencer, R.G.M.; Stepanauskas, R.; Kendall, C.; Losee, R.F.; Fujii, R.

2008-01-01

This study assesses how rivers, wetlands, island drains and open water habitats within the Sacramento-San Joaquin River Delta affect dissolved organic matter (DOM) content and composition, and disinfection byproduct (DBP) formation. Eleven sites representative of these habitats were sampled on six dates to encompass seasonal variability. Using a suite of qualitative analyses, including specific DBP formation potential, absorbance, fluorescence, lignin content and composition, C and N stable isotopic compositions, and structural groupings determined using CPMAS (cross polarization, magic angle spinning) 13C NMR, we applied a geochemical fingerprinting approach to characterize the DOM from different Delta habitats, and infer DOM and DBP precursor sources and estimate the relative contribution from different sources. Although river input was the predominant source of dissolved organic carbon (DOC), we observed that 13-49% of the DOC exported from the Delta originated from sources within the Delta, depending on season. Interaction with shallow wetlands and subsided islands significantly increased DOC and DBP precursor concentrations and affected DOM composition, while deep open water habitats had little discernable effect. Shallow wetlands contributed the greatest amounts of DOM and DBP precursors in the spring and summer, in contrast to island drains which appeared to be an important source during winter months. The DOM derived from wetlands and island drains had greater haloacetic acid precursor content relative to incoming river water, while two wetlands contributed DOM with greater propensity to form trihalomethanes. These results are pertinent to restoration of the Delta. Large scale introduction of shallow wetlands, a proposed restoration strategy, could alter existing DOC and DBP precursor concentrations, depending on their hydrologic connection to Delta channels. ?? 2008 Elsevier Ltd.

Seasonal Variation in Dissolved Organic Matter Composition and Photoreactivity within a Small Sub-arctic Stream.

NASA Astrophysics Data System (ADS)

Guerard, J.; Osborne, R.

2015-12-01

Dissolved organic matter (DOM) is a complex heterogeneous mixture, ubiquitous to all natural surface waters, uniquely composed of source inputs specific to spatial, temporal, and ecological circumstances. In arctic and sub-arctic regions, elucidating DOM composition and reactivity is complicated by seasonal variations. These include changes in productivity and source inputs to the water column, as well as winter overflow events that may contribute allochthonous organic material. DOM from a small boreal stream in a watershed of discontinuous permafrost in the Goldstream Valley of interior Alaska was isolated by solid-phase extraction (PPL) at multiple points during the year - late spring, late summer, and in the winter during an active overflow event. Compositional characteristics of each of the isolates were characterized by SPR-W5-WATERGATE 1H NMR spectroscopy, specific UV-Vis absorbance, and excitation emission matrix (EEM) fluorescence spectroscopy and compared against end-member reference DOM isolates. Kinetics of photobleaching experiments reveal the influence of compositional differences among the isolated DOMs on their chemical reactivity, and offer insight into potential differences in their source materials and ecological function throughout the year. Photobleaching studies were conducted using a variety of reactive species quenchers or sensitizers in order to assess susceptibility of oxidative transformation mechanisms on the different DOM isolates, which were then analyzed by 1H NMR, UV-Vis degradation kinetics, and parallel factor analysis (PARAFAC) of fluorescence EEMs. Better understanding of the seasonal variations of boreal DOM character and function on a molecular level is critical to assessing alterations in its ecological role and cycling in the face of current and future ecosystem perturbations in arctic and sub-arctic regions.

The quantity and quality of dissolved organic matter as supplementary carbon source impacts the pesticide-degrading activity of a triple-species bacterial biofilm.

PubMed

Horemans, Benjamin; Vandermaesen, Johanna; Breugelmans, Philip; Hofkens, Johan; Smolders, Erik; Springael, Dirk

2014-01-01

Effects of environmental dissolved organic matter (eDOM) that consists of various low concentration carbonic compounds on pollutant biodegradation by bacteria are poorly understood, especially when it concerns synergistic xenobiotic-degrading consortia where degradation depends on interspecies metabolic interactions. This study examines the impact of the quality and quantity of eDOM, supplied as secondary C-source, on the structure, composition and pesticide-degrading activity of a triple-species bacterial consortium in which the members synergistically degrade the phenylurea herbicide linuron, when grown as biofilms. Biofilms developing on 10 mg L⁻¹ linuron showed a steady-state linuron degradation efficiency of approximately 85 %. The three bacterial strains co-localized in the biofilms indicating syntrophic interactions. Subsequent feeding with eDOM or citrate in addition to linuron resulted into changes in linuron-degrading activity. A decrease in linuron-degrading activity was especially recorded in case of co-feeding with citrate and eDOM of high quality and was always associated with accumulation of the primary metabolite 3,4-dichloroaniline. Improvement of linuron degradation was especially observed with more recalcitrant eDOM. Addition of eDOM/citrate formulations altered biofilm architecture and species composition but without loss of any of the strains and of co-localization. Compositional shifts correlated with linuron degradation efficiencies. When the feed was restored to only linuron, the linuron-degrading activity rapidly changed to the level before the mixed-substrate feed. Meanwhile only minor changes in biofilm composition and structure were recorded, indicating that observed eDOM/citrate effects had been primarily due to repression/stimulation of linuron catabolic activity rather than to biofilm characteristics.

Variation of organic matter quantity and quality in streams at Critical Zone Observatory watersheds

USGS Publications Warehouse

Miller, Matthew P.; Boyer, Elizabeth W.; McKnight, Diane M.; Brown, Michael G.; Gabor, Rachel S.; Hunsaker, Carolyn T.; Iavorivska , Lidiia; Inamdar, Shreeram; Kaplan, Louis A.; Johnson, Dale W.; Lin, Henry; McDowell, William H.; Perdrial, Julia N.

2016-01-01

The quantity and chemical composition of dissolved organic matter (DOM) in surface waters influence ecosystem processes and anthropogenic use of freshwater. However, despite the importance of understanding spatial and temporal patterns in DOM, measures of DOM quality are not routinely included as part of large-scale ecosystem monitoring programs and variations in analytical procedures can introduce artifacts. In this study, we used consistent sampling and analytical methods to meet the objective of defining variability in DOM quantity and quality and other measures of water quality in streamflow issuing from small forested watersheds located within five Critical Zone Observatory sites representing contrasting environmental conditions. Results show distinct separations among sites as a function of water quality constituents. Relationships among rates of atmospheric deposition, water quality conditions, and stream DOM quantity and quality are consistent with the notion that areas with relatively high rates of atmospheric nitrogen and sulfur deposition and high concentrations of divalent cations result in selective transport of DOM derived from microbial sources, including in-stream microbial phototrophs. We suggest that the critical zone as a whole strongly influences the origin, composition, and fate of DOM in streams. This study highlights the value of consistent DOM characterization methods included as part of long-term monitoring programs for improving our understanding of interactions among ecosystem processes as controls on DOM biogeochemistry.

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.

Properties of dissolved and total organic matter in throughfall, stemflow and forest floor leachate of central European forests

NASA Astrophysics Data System (ADS)

Bischoff, S.; Schwarz, M. T.; Siemens, J.; Thieme, L.; Wilcke, W.; Michalzik, B.

2015-05-01

We present the first investigation of the composition of dissolved organic matter (DOM) compared to total organic matter (TOM, consisting of DOM, < 0.45 μm and particulate organic matter 0.45 μm < POM < 500 μm) in throughfall, stemflow and forest floor leachate of common beech (Fagus sylvatica L.) and Norway spruce (Picea abies (L.) H. Karst.) forests using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. We hypothesized that the composition and properties of organic matter (OM) in forest ecosystem water samples differ between DOM and TOM and between the two tree species. The 13C NMR results, derived from 21 samples, point to pronounced differences in the composition of DOM and TOM in throughfall solution at the beech sites, with TOM exhibiting higher relative intensities for the alkyl C region, which represents aliphatic C from less decomposed organic material compared to DOM. Furthermore, TOM shows lower intensities for lignin-derived and aromatic C of the aryl C region resulting in lower aromaticity indices and a diminished degree of humification. Across the ecosystem compartments, differences in the structural composition of DOM and TOM under beech lessened in the following order: throughfall > stemflow ≈ forest floor leachate. In contrast to the broadleaved sites, differences between DOM and TOM in throughfall solution under spruce were less pronounced and spectra were, overall, dominated by the alkyl C region, representing aliphatic C. Explanations of the reported results might be substantiated in differences in tree species-specific structural effects, leaching characteristics or differences in the microbial community of the tree species' phyllosphere and cortisphere. However, the fact that throughfall DOM under beech showed the highest intensities of recalcitrant aromatic and phenolic C among all samples analysed likely points to a high allelopathic potential of beech trees negatively affecting other organisms and hence ecosystem processes and functions.

Evaluating the distribution of terrestrial dissolved organic matter in a complex coastal ecosystem using fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Yamashita, Youhei; Boyer, Joseph N.; Jaffé, Rudolf

2013-09-01

The coastal zone of the Florida Keys features the only living coral reef in the continental United States and as such represents a unique regional environmental resource. Anthropogenic pressures combined with climate disturbances such as hurricanes can affect the biogeochemistry of the region and threaten the health of this unique ecosystem. As such, water quality monitoring has historically been implemented in the Florida Keys, and six spatially distinct zones have been identified. In these studies however, dissolved organic matter (DOM) has only been studied as a quantitative parameter, and DOM composition can be a valuable biogeochemical parameter in assessing environmental change in coastal regions. Here we report the first data of its kind on the application of optical properties of DOM, in particular excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC), throughout these six Florida Keys regions in an attempt to assess spatial differences in DOM sources. Our data suggests that while DOM in the Florida Keys can be influenced by distant terrestrial environments such as the Everglades, spatial differences in DOM distribution were also controlled in part by local surface runoff/fringe mangroves, contributions from seasgrass communities, as well as the reefs and waters from the Florida Current. Application of principal component analysis (PCA) of the relative abundance of EEM-PARAFAC components allowed for a clear distinction between the sources of DOM (allochthonous vs. autochthonous), between different autochthonous sources and/or the diagenetic status of DOM, and further clarified contribution of terrestrial DOM in zones where levels of DOM were low in abundance. The combination between EEM-PARAFAC and PCA proved to be ideally suited to discern DOM composition and source differences in coastal zones with complex hydrology and multiple DOM sources.

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 lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph; Dittmar, Thorsten; Kattner, Gerhard

2005-07-01

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

The effect of dissolved organic matter (DOM) on sodium transport and nitrogenous waste excretion of the freshwater cladoceran (Daphnia magna) at circumneutral and low pH.

PubMed

Al-Reasi, Hassan A; Yusuf, Usman; Smith, D Scott; Wood, Chris M

2013-11-01

Dissolved organic matter (DOM), a heterogeneous substance found in all natural waters, has many documented abiotic roles, but recently, several possible direct influences of DOM on organism physiology have been reported. However, most studies have been carried out with a limited number of natural DOM isolates or were restricted to the use of commercial or artificial humic substances. We therefore employed three previously characterized, chemically-distinct natural DOMs, as well as a commercially available humic acid (Aldrich, AHA), at circumneutral (7-8) and acidic pH (~5), to examine DOM effects on whole-body Na(+) concentration, unidirectional influx and efflux rates of Na(+), and ammonia and urea excretion rates in Daphnia magna. Whole-body Na(+) concentration, Na(+) influx, and Na(+) efflux rates were all unaffected regardless of pH, suggesting no influence of the various natural DOMs on active uptake and passive diffusion of Na(+) in this organism. Ammonia and urea excretion rates were both increased by low pH. Ammonia excretion rates were reduced at circumneutral pH by the most highly colored, allochthonous DOM, and at low pH by all three natural DOMs, as well as by the commercial AHA. Urea excretion rates were not influenced by the presence of the various DOMs in circumneutral solutions, but were attenuated by the presence of two allochthonous DOM sources (isolated from Bannister Lake and Luther Marsh) at acidic pH. The observed reductions may be attributed partially to the higher buffering capacities of natural DOM sources, as well as their ability to interact with biological membranes as estimated by a new measure calculated from their acid-base titration characteristics, the Proton Binding Index (PBI). © 2013.

Composition of dissolved organic matter (DOM) from periodically submerged soils in the Three Gorges Reservoir areas as determined by elemental and optical analysis, infrared spectroscopy, pyrolysis-GC-MS and thermally assisted hydrolysis and methylation.

PubMed

Jiang, Tao; Kaal, Joeri; Liang, Jian; Zhang, Yaoling; Wei, Shiqiang; Wang, Dingyong; Green, Nelson W

2017-12-15

Soil-derived dissolved organic matter (DOM) has a major influence in biogeochemical processes related to contaminant dynamics and greenhouse gas emissions, due to its reactivity and its bridging role between the soil and aquatic systems. Within the Three Gorges Reservoir (TGR, China) area, an extensive water-fluctuation zone periodically submerges the surrounding soils. Here we report a characterization study of soil-derived DOM across the TGR areas, using elemental and optical analysis, infrared spectroscopy (FTIR), pyrolysis-GC-MS (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS). The results showed that the soil DOM from the TGR area is a mixture of "allochthonous" (i.e., plant-derived/terrigenous) and "autochthonous" (i.e., microbial) origins. The terrigenous DOM is composed primarily of phenolic and aliphatic structures from lignin and aliphatic biopolymers (i.e. cutin, suberin), respectively. Multivariate statistics differentiated between two fractions of the microbial DOM, i.e. chitin-derived, perhaps from fungi and arthropods in soil, and protein-derived, partially sourced from algal or aquatic organisms. Molecular proxies of source and degradation state were in good agreement with optical parameters such as SUVA 254 , the fluorescence index (FI) and the humification index (HIX). The combined use of elemental analysis, fluorescence spectroscopy, and Py-GC-MS provides rigorous and detailed DOM characterization, whereas THM-GC-MS is useful for more precise but qualitative identification of the different phenolic (cinnamyl, p-hydroxyphenyl, guaiacyl, syringyl and tannin-derived) and aliphatic materials. With the multi-methodological approach used in this study, FTIR was the least informative, in part, because of the interference of inorganic matter in the soil DOM samples. The soil DOM from the TGR's water fluctuation zone exhibited considerable compositional diversity, mainly related to the balance between DOM source (microbial- or plant-derived), local vegetation and anthropogenic activities (e.g., agriculture). Finally, the relationship between DOM composition and its potential reactivity with substances of environmental concerns in the TGR area are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical compositions of dissolved organic matter from various sources as characterized by solid-state NMR

USDA-ARS?s Scientific Manuscript database

Dissolved organic matter (DOM) in surface waters plays an important role in biogeochemical and ecological processes. This study used solid-state NMR techniques to explore the molecular signatures of riverine DOM in relation to its point and nonpoint sources. DOM samples were isolated from (1) two st...

Molecular Characterization and Reactivity of Dissolved Organic Matter by High Resolution Nanospray Ionization Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS)

NASA Astrophysics Data System (ADS)

Sleighter, R. L.; Hatcher, S. A.; Hatcher, P. G.

2006-12-01

The ultrahigh resolving power of FTICR-MS allows for the intense characterization of dissolved organic matter (DOM). DOM is the largest reactive component of the global carbon cycle, and an improved understanding of its composition is necessary to determine the transport and eventual fate of pollutants. The seasonal and spatial variations in DOM composition are investigated by taking surface water samples from five different sampling sites, four times a year. Water sampling begins at the Dismal Swamp in North Carolina, continues north up the Elizabeth River to the Chesapeake Bay, and concludes approximately ten miles off the coast in the Atlantic Ocean. DOM was extracted from the water samples using C18 extraction disks and were prepared in 50:50 methanol:water. Ammonium hydroxide was added prior to nanospray in order to solubilize the DOM as well as to increase the ionization efficiency. The samples were continuously infused into the Apollo II ion source with an Advion TriVersa NanoMate system of a Bruker 12 Tesla Apex QE FTICR-MS with resolving powers exceeding 400,000. All samples were analyzed in negative ion mode and were externally and internally calibrated prior to data analysis. Our DOM mass spectra consist of a multitude of peaks spanning the range of 200-850 m/z. Complexity is apparent from the detection of up to 20 peaks per nominal mass at nearly every mass throughout that range. A molecular formula calculator generated molecular formula matches from which van Krevelen plots were constructed for characterization purposes. A wide range of molecules were observed each containing oxygen, sulfur and nitrogen functional groups. We utilize the van Krevelen diagram to assist in clustering the molecules according to their functional group compositions. To test the hypothesis that formation of adducts to DOM serve to protect peptides from bacterial degradation, microcosm experiments were performed with a small isotopically enriched peptide, GGGR. This peptide was predicted to covalently bond to DOM via a Michael addition reaction or Schiff base formation. Following the incubation of GGGR with DOM, adduct formation was examined by FTICR-MS. Covalent binding of GGGR to DOM is a process that may reduce the bioavailability and degradation of proteins in the environment and could potentially lead to their preservation on longer time scales. FTICR-MS is clearly a powerful technique used to examine the complex composition of DOM and allow for advancements in the areas of aquatic and analytical chemistry.

Molecular Hysteresis of Dissolved Organic Matter in the Connecticut River Watershed

NASA Astrophysics Data System (ADS)

Wagner, S.; Hoyle, J. B.; Matt, S.; Raymond, P. A.; Saiers, J. E.; Dittmar, T.; Stubbins, A.

2017-12-01

Rainfall-runoff processes have emerged as key controllers of the quantity and quality of terrestrial dissolved organic matter (DOM) exported from the landscape to inland waters. Hydrological events result in increased river discharge and a concomitant release of large amounts of DOM into fluvial networks. This study is part of a Macrosystems project which aims to test the Pulse-Shunt Concept: where rivers are converted from active to passive pipes during high discharge events ("pulse"), transporting labile, terrestrial DOM downstream ("shunt"), and relocating biogeochemical hotspots for DOM from the upper to the lower reaches of the watershed. The primary objective of our study was to track hysteretic changes in riverine DOM molecular composition over the course of a storm event. Samples were collected from nested watersheds in the Passumpsic River catchment, a tributary of the Connecticut River (USA). High resolution monitoring (via in-situ sondes) and high frequency collection of discreet samples (for FT-ICR/MS and other analyses) was necessary to capture short-term, hydrologically-driven variations in DOM concentration and composition. At the onset of the discharge event, we observed a unique DOM signature, enriched in aliphatic, and potentially biolabile, DOM. During peak discharge, and along the falling limb of the hydrograph, an aromatic, terrestrial-type DOM signature was more prevalent. These initial findings support the pulse-shunt hypothesis, providing evidence for the release of labile forms of DOM into rivers during the onset of a storm event, which apparently persists across low-to-high stream orders. Insights into the molecular hysteresis of fluvial DOM spotlights the impact of watershed hydrology on biogeochemical cycling in river networks.

Hydrologic Controls on In-Stream Optical Dissolved Organic Matter Characteristics in an Old-Growth Forest of the Oregon Cascades

NASA Astrophysics Data System (ADS)

Lajtha, K.; Lee, B. S.

2015-12-01

Dissolved organic matter (DOM) is a critical component of the carbon cycle linking terrestrial and aquatic ecosystems, yet DOM composition representative of DOM sources at headwater catchments in the western U.S is poorly understood. This study examined the effect of forest management history and hydrologic patterns on DOM chemistry at nine experimental watersheds located in the H.J. Andrews Long Term Ecological Research Experimental Forest of the Oregon Cascades. Stream water samples representing a three-week composite of each watershed were collected between May 2013 and February 2015 (32 events). DOM chemistry was characterized by examining UV and fluorescent properties of stream samples. Specific UV absorbance at 254 nm (SUVA254; Weishaar et al. 2003), generally indicative of aromaticity, showed the lowest value at the high elevation clear-cut site (watershed 6, 1,030 m) and the highest value at the low elevation clear-cut site (watershed 10, 680 m) throughout the study period. DOM fluorescent components, identified by this study using a multivariate statistical model, Parallel Factor Analysis (PARAFAC), did not differ significantly among experimental watersheds with varying forest management history. However, a protein-like DOM component exhibited temporal variations. Correlation analysis between the protein-like DOM and hydrologic patterns indicate that stream water during dry seasons come from protein-rich groundwater sources. This study shows UV and fluorescent spectroscopy DOM characterization is a viable finger printing method to detect DOM sources in pristine headwater streams at the western Cascades of Oregon where characterization of the stream water source with low DOC and DON concentrations is difficult.

Modeling rates of DOC degradation using DOM composition and hydroclimatic variables

NASA Astrophysics Data System (ADS)

Moody, C. S.; Worrall, F.

2017-05-01

The fluvial fluxes of dissolved organic carbon (DOC) from peatlands form an important part of that ecosystem's carbon cycle, contributing approximately 35% of the overall peatland carbon budget. The in-stream processes acting on the DOC, such as photodegradation and biodegradation, can lead to DOC loss and thus contribute CO2 to the atmosphere. The aim of this study was to understand what controls the rates of DOC degradation. Water samples from a headwater, peat-covered catchment, were collected over a 23 month period and analyzed for the DOC degradation rate and dissolved organic matter (DOM) composition in the context of hydroclimatic monitoring. Measures of DOM composition included 13C solid-state nuclear magnetic resonance spectroscopy, bomb calorimetry, and elemental analysis. Regression analysis showed that there was a significant role for the composition of the DOM in controlling degradation with degradation rates significantly increasing with the proportion of aldehyde and carboxylic acid functional groups but decreasing with the proportion of N-alkyl functional groups. The highest rates of DOC degradation occurred when aldehyde functionality was at its greatest and this occurred on the recession limb of storm hydrographs. Including this knowledge into models of fluvial carbon fate for an 818 km2 catchment gave an annual average DOC removal rate of 67% and 50% for total organic carbon, slightly lower than previously predicted. The compositional controls suggest that DOM is primarily being used as a ready energy source to the aquatic ecosystem rather than as a nutrient source.

Composition, dynamics, and fate of leached dissolved organic matter in terrestrial ecosystems: Results from a decomposition experiment

USGS Publications Warehouse

Cleveland, C.C.; Neff, J.C.; Townsend, A.R.; Hood, E.

2004-01-01

Fluxes of dissolved organic matter (DOM) are an important vector for the movement of carbon (C) and nutrients both within and between ecosystems. However, although DOM fluxes from throughfall and through litterfall can be large, little is known about the fate of DOM leached from plant canopies, or from the litter layer into the soil horizon. In this study, our objectives were to determine the importance of plant-litter leachate as a vehicle for DOM movement, and to track DOM decomposition [including dissolve organic carbon (DOC) and dissolved organic nitrogen (DON) fractions], as well as DOM chemical and isotopic dynamics, during a long-term laboratory incubation experiment using fresh leaves and litter from several ecosystem types. The water-extractable fraction of organic C was high for all five plant species, as was the biodegradable fraction; in most cases, more than 70% of the initial DOM was decomposed in the first 10 days of the experiment. The chemical composition of the DOM changed as decomposition proceeded, with humic (hydrophobic) fractions becoming relatively more abundant than nonhumic (hydrophilic) fractions over time. However, in spite of proportional changes in humic and nonhumic fractions over time, our data suggest that both fractions are readily decomposed in the absence of physicochemical reactions with soil surfaces. Our data also showed no changes in the ??13C signature of DOM during decomposition, suggesting that isotopic fractionation during DOM uptake is not a significant process. These results suggest that soil microorganisms preferentially decompose more labile organic molecules in the DOM pool, which also tend to be isotopically heavier than more recalcitrant DOM fractions. We believe that the interaction between DOM decomposition dynamics and soil sorption processes contribute to the ??13C enrichment of soil organic matter commonly observed with depth in soil profiles.

Tracking the behavior of different size fractions of dissolved organic matter in a full-scale advanced drinking water treatment plant.

PubMed

Quang, Viet Ly; Choi, Ilhwan; Hur, Jin

2015-11-01

In this study, five different dissolved organic matter (DOM) fractions, defined based on a size exclusion chromatography with simultaneous detection of organic carbon (OCD) and ultraviolet (UVD), were quantitatively tracked with a treatment train of coagulation/flocculation-sand filtration-ozonation-granular activated carbon (GAC) filtration in a full-scale advanced drinking water treatment plant (DWTP). Five DOM samples including raw water were taken after each treatment process in the DWTP every month over the period of three years. A higher abundance of biopolymer (BP) fraction was found in the raw water during spring and winter than in the other seasons, suggesting an influence of algal bloom and/or meltwater on DOM composition. The greater extent of removal was observed upon the coagulation/flocculation for high-molecular-weight fractions including BP and humic substances (HS) and aromatic moieties, while lower sized fractions were preferentially removed by the GAC filtration. Ozone treatment produced the fraction of low-molecular-weight neutrals probably resulting from the breakdown of double-bonded carbon structures by ozone oxidation. Coagulation/flocculation was the only process that revealed significant effects of influent DOM composition on the treatment efficiency, as revealed by a high correlation between the DOM removal rate and the relative abundance of HS for the raw water. Our study demonstrated that SEC-OCD-UVD was successful in monitoring size-based DOM composition for the advanced DWTP, providing an insight into optimizing the treatment options and the operational conditions for the removal of particular fractions within the bulk DOM.

Relationships between Molecular Composition and Optical Properties of Dissolved Organic Matter

NASA Astrophysics Data System (ADS)

Cooper, W. T.; Tfaily, M.; Osborne, D.; Paul, A.; Podgorski, D. C.; Corbett, J.; Chanton, J.

2009-12-01

Our focus is on the relationships between the optical properties of dissolved organic matter (DOM) and its molecular composition. For example, we demonstrated that changes in the absorption and fluorescence characteristics of DOM in outwelling from Brazilian mangrove forests correlated with decreases in highly unsaturated organic compounds as DOM was transported from mangrove porewaters to the continental shelf. In that work we combined ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) that provided detailed compositional information with absorption and Excitation/Emission Matrix (EEM) spectroscopy This presentation will highlight new results utilizing the combination of optical spectroscopy and FT-ICR mass spectrometry to illuminate the processes which control DOM cycling. Our focus will be on the contributions of the heteroatom components of DOM (i.e. organic sulfur and organic nitrogen) to its optical properties and how changes in optical properties correlate with important environmental processes like humification and bioavailability. Figure 1 below includes a narrow 0.20 Dalton window from a mass spectrum which demonstrates the ability of ultrahigh resolution mass spectrometry to resolve and identify nitrogen heteroatom compounds in DOM. Our study sites include the Glacial Lake Agassiz Peatlands (GLAP) in northern Minnesota and wetlands in the Caloosahatchee River basin in South Florida. Figure 1. Isolated 0.20 Da window of an ESI-FT-ICR mass spectrum of DOM from a GLAP bog. Labels identify N1 (d,e,f) and N3 classes of nitrogen heteroatoms. The 0.0031 Da mass spacing is used to confirm the N3 class.

[Characterizing composition and transformation of dissolved organic matter in subsurface wastewater infiltration system].

PubMed

Wang, Li-Jun; Liu, Yu-Zhong; Zhang, Lie-Yu; Xi, Bei-Dou; Xia, Xun-Feng; Liu, Ya-Ru

2013-08-01

In the present study, the soil column with radius of 30 cm and height of 200 cm was used to simulate a subsurface wastewater infiltration system. Under the hydraulic loading of 4 cm x d(-1), composition and transformation of dissolved organic matter (DOM) from different depths were analyzed in a subsurface wastewater infiltration system for treatment of septic tank effluent using three-dimensional excitation emission matrix fluorescence spectroscopy (3D-EEM) with regional integration analysis (FRI). The results indicate that: (1) from different depth, the composition of DOM was also different; influent with the depth of 0.5 m was mainly composed of protein-like substances, and that at other depths was mainly composed of humic- and fulvic-like substances. (2) DOM stability gradually increased and part of the nonbiodegradable organic matter can be removed during organic pollutants degradation process. (3) Not only the organic pollutants concentration was reduced effectively, but also the stability of the DOM improved in subsurface wastewater infiltration system.

Variation of organic matter quantity and quality in streams at Critical Zone Observatory watersheds

Treesearch

Matthew P. Miller; Elizabeth W. Boyer; Diane M. McKnight; Michael G. Brown; Rachel S. Gabor; Carolyn Hunsaker; Lidiia Iavorivska; Shreeram Inamdar; Dale W. Johnson; Louis A. Kaplan; Henry Lin; William H. McDowell; Julia N. Perdrial

2016-01-01

The quantity and chemical composition of dissolved organic matter (DOM) in surface waters influence ecosystem processes and anthropogenic use of freshwater. However, despite the importance of understanding spatial and temporal patterns in DOM, measures of DOM quality are not routinely included as part of large-scale ecosystem monitoring programs and variations in...

Short-term degradation of terrestrial DOM in the coastal ocean: Implications for nutrient subsidies and marine microbial community structure

NASA Astrophysics Data System (ADS)

Oliver, A. A.; Tank, S. E.; Kellogg, C.

2015-12-01

The export of riverine dissolved organic matter (DOM) to the coastal ocean provides an important link between terrestrial and aquatic ecosystems. The coastal temperate rainforests of British Columbia contain extensive freshwater networks that export significant amounts of water and DOM to the ocean, representing significant cross-system hydrologic and biogeochemical linkages. To better understand the importance of these linkages and implications for ecosystem structure and function, we used an experimental approach to investigate the role of microbial and photodegradation transformations of DOM exported from small coastal catchments to the marine environment. At two time periods (August 2014, March 2015), stream water from the outlets of two coastal watersheds was filtered (<0.2 μm), and treated with microbial inoculums from across a salinity gradient (i.e., freshwater, estuarine, and marine). Treatments were incubated in the ocean under light and dark conditions for 8 days. At 0, 3 and 8 days, samples were analyzed for DOC, TDN, DIN, and DON. Changes in DOM composition were determined with optical characterization techniques such as absorbance (SUVA, S, Sr) and fluorescence (EEM). Microbial community response was measured using cell counts and DNA/RNA amplicon sequencing to determine changes in bacterial abundance and community composition. General patterns indicated that microbial communities from the high salinity treatment (i.e. most marine) were the most effective at utilizing freshwater DOM, especially under light conditions. In some treatments, DOM appeared as a potential source of inorganic nitrogen with corresponding shifts in microbial community composition. Incubations using inoculum from low and mid salinity levels demonstrated smaller changes, indicating that DOM exported from these streams may not be extensively utilized until exposed to higher salinity environments further from stream outlets. These results suggest a role for terrestrial sourced-DOM as a subsidy for microbial communities within the near shore marine environment, and emphasize that changes in DOM exports due to land development or climate change may have implications for coastal food web processes and biogeochemical cycling.

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-altered terpenoids, such as sterols and hopanoids. Thermally-altered molecules, including black carbon, also appear to be important components of DOM, but their origins are unclear. We are rapidly acquiring novel information about the composition and molecular identity of DOM, and novel insights about the origins, transformations and fates this vast reservoir of DOM are emerging. This presentation will review and synthesize this information for comparison with non-living organic matter in other systems.

Diversity of bacterial communities and dissolved organic matter in a temperate estuary.

PubMed

Osterholz, Helena; Kirchman, David L; Niggemann, Jutta; Dittmar, Thorsten

2018-06-14

Relationships between bacterial community and dissolved organic matter (DOM) include microbial uptake, transformation and secretion, all of which influence DOM composition. In this study, we explore diversity and similarity metrics of dissolved organic molecules (Fourier-transform ion cyclotron resonance mass spectrometry) and bacterial communities (tag-sequencing of 16S rRNA genes) along the salinity gradient of the Delaware Estuary (USA). We found that even though mixing, discharge and seasonal changes explained most of the variation in DOM and bacterial communities, there was still a relationship, albeit weak, between the composition of DOM and bacterial communities in the estuary. Overall, many DOM molecular formulas (MFs) and bacterial operational taxonomic units (OTUs) reoccurred over years and seasons while the frequency of MF-OTU correlations varied. Diversity based on MFs and OTUs was significantly correlated, decreasing towards the open ocean. However, while the diversity of bacterial OTUs dropped markedly with low salinity, MF diversity decreased strongly only at high salinities. We hypothesize that the different turnover times of DOM and bacteria lead to different abundance distributions of OTUs and MFs. A significant portion of the detected DOM is of a more refractory nature with lifetimes largely exceeding the mixing time of the estuary, while bacterial community turnover times in the Delaware Estuary are estimated at several days.

Constraining Biomarkers of Dissolved Organic Matter Sourcing Using Microbial Incubations of Vascular Plant Leachates of the California landscape

NASA Astrophysics Data System (ADS)

Harfmann, J.; Hernes, P.; Chuang, C. Y.; Kaiser, K.; Spencer, R. G.; Guillemette, F.

2017-12-01

Source origin of dissolved organic matter (DOM) is crucial in determining reactivity, driving chemical and biological processing of carbon. DOM source biomarkers such as lignin (a vascular plant marker) and D-amino acids (bacterial markers) are well-established tools in tracing DOM origin and fate. The development of high-resolution mass spectrometry and optical studies has expanded our toolkit; yet despite these advances, our understanding of DOM sources and fate remains largely qualitative. Quantitative data on DOM pools and fluxes become increasingly necessary as we refine our comprehension of its composition. In this study, we aim to calibrate and quantify DOM source endmembers by performing microbial incubations of multiple vascular plant leachates, where total DOM is constrained by initial vascular plant input and microbial production. Derived endmembers may be applied to endmember mixing models to quantify DOM source contributions in aquatic systems.

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

USGS Publications Warehouse

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

2016-01-01

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

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

USGS Publications Warehouse

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

2016-01-01

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

The characteristics of dissolved organic matter (DOM) in storm sewer sediments and the binding interaction with Cu(II) in four typical regions in Beijing, China.

PubMed

Zhang, Ziyang; Li, Kun; Zhang, Xiaoran; Li, Haiyan

2017-07-01

In this work, dissolved organic matter (DOM) was extracted from storm sewer sediments collected in four typical regions (residential, campus, traffic and business regions) in Beijing, China. The basic characteristics of DOM were analyzed by UV-visible spectroscopy (UV-Vis), excitation-emission matrix Fluorescence Spectroscopy and Fourier Transform Infrared Spectroscopy. Furthermore, the complexation between DOM and Cu(II) were investigated. The results showed that there were large amount of aromatic structure in the DOM extracted from storm sewer sediments. The microbial activities had also made a contribution to the DOM in storm sewer sediments. The composition of DOM influenced the complexing capacity of Cu(II) greatly, which may be attributed to the protein-like and humic-like substances in storm sewer sediments. This study demonstrated valuable information on the structure present in the DOM of storm sewer sediments and provided new insight for exploring the relationship between DOM and co-existing heavy metals in storm sewer sediments.

[Study of the fluorescence characteristics of DOM from the Yangtze River and Jialing River around Chongqing's urban areas].

PubMed

Ji, Fang-ying; Li, Si; Zhou, Guang-ming; Yu, Dan-ni; Wang, Tu-jin; Cao, Lin; Tan, Xue-mei; Yang, Da-cheng; Zhou, Xiao-yi

2010-01-01

The fluorescence emission and excitation emission matrix (EEM) technologies were used to characterize the dissolved organic matter (DOM) in the water body of the Yangtze River and Jialing River around the Chongqing urban areas from April to August 2008. Concerning about the accidents of the Wenchuan's Earthquake in May and Tangjiashan Yansaihu's effects in June, and the high water period time in the summer in two months of July and August, from the EEM obtained from each sampling station and time, the composition, distribution and their changing features of the DOM in the two rivers were investigated as combined with the water samples' environmental parameters such as pH, DO, DOC with EEM's fingerprint features, f(450/500) etc; finally the bio-environment behavior effects of the three types of fluorescence peaks were elaborated, where humic-like, fulvic-like, and protein-like from the five sampling stations' EEMs during the five months were given detailed representation. From the experimental results obtained, the fluorescence peaks are mainly composed of two types of fluorophores: humic-like and protein-like in the two rivers around the Chongqing urban areas during the investigation in five months, the protein-like's peaks value in Jialing River is higher than the values in the Yangtze River, and all the fluorescence peaks in the two Rivers' water body decrease more or less after the two Rivers join in Chun Tan sampling station; the protein-like peak is notably higher after the "5 x 12" earthquake period time including May and June and high water period time, which mainly originated from terrestrial sources, but its intensities decreased observably while the water bodies of the two rivers joining together in the Chao Tianmen and Chun Tan's sampling station.

Global change-driven effects on dissolved organic matter composition: Implications for food webs of northern lakes.

PubMed

Creed, Irena F; Bergström, Ann-Kristin; Trick, Charles G; Grimm, Nancy B; Hessen, Dag O; Karlsson, Jan; Kidd, Karen A; Kritzberg, Emma; McKnight, Diane M; Freeman, Erika C; Senar, Oscar E; Andersson, Agneta; Ask, Jenny; Berggren, Martin; Cherif, Mehdi; Giesler, Reiner; Hotchkiss, Erin R; Kortelainen, Pirkko; Palta, Monica M; Vrede, Tobias; Weyhenmeyer, Gesa A

2018-03-15

Northern ecosystems are experiencing some of the most dramatic impacts of global change on Earth. Rising temperatures, hydrological intensification, changes in atmospheric acid deposition and associated acidification recovery, and changes in vegetative cover are resulting in fundamental changes in terrestrial-aquatic biogeochemical linkages. The effects of global change are readily observed in alterations in the supply of dissolved organic matter (DOM)-the messenger between terrestrial and lake ecosystems-with potentially profound effects on the structure and function of lakes. Northern terrestrial ecosystems contain substantial stores of organic matter and filter or funnel DOM, affecting the timing and magnitude of DOM delivery to surface waters. This terrestrial DOM is processed in streams, rivers, and lakes, ultimately shifting its composition, stoichiometry, and bioavailability. Here, we explore the potential consequences of these global change-driven effects for lake food webs at northern latitudes. Notably, we provide evidence that increased allochthonous DOM supply to lakes is overwhelming increased autochthonous DOM supply that potentially results from earlier ice-out and a longer growing season. Furthermore, we assess the potential implications of this shift for the nutritional quality of autotrophs in terms of their stoichiometry, fatty acid composition, toxin production, and methylmercury concentration, and therefore, contaminant transfer through the food web. We conclude that global change in northern regions leads not only to reduced primary productivity but also to nutritionally poorer lake food webs, with discernible consequences for the trophic web to fish and humans. © 2018 John Wiley & Sons Ltd.

Linkages between denitrification and dissolved organicmatter quality, Boulder Creek watershed, Colorado

USGS Publications Warehouse

Barnes, Rebecca T.; Smith, Richard L.; Aiken, George R.

2012-01-01

Dissolved organic matter (DOM) fuels the majority of in-stream microbial processes, including the removal of nitrate via denitrification. However, little is known about how the chemical composition of DOM influences denitrification rates. Water and sediment samples were collected across an ecosystem gradient, spanning the alpine to plains, in central Colorado to determine whether the chemical composition of DOM was related to denitrification rates. Laboratory bioassays measured denitrification potentials using the acetylene block technique and carbon mineralization via aerobic bioassays, while organic matter characteristics were evaluated using spectroscopic and fractionation methods. Denitrification potentials under ambient and elevated nitrate concentrations were strongly correlated with aerobic respiration rates and the percent mineralized carbon, suggesting that information about the aerobic metabolism of a system can provide valuable insight regarding the ability of the system to additionally reduce nitrate. Multiple linear regressions (MLR) revealed that under elevated nitrate concentrations denitrification potentials were positively related to the presence of protein-like fluorophores and negatively related to more aromatic and oxidized fractions of the DOM pool. Using MLR, the chemical composition of DOM, carbon, and nitrate concentrations explained 70% and 78% of the observed variability in denitrification potential under elevated and ambient nitrate conditions, respectively. Thus, it seems likely that DOM optical properties could help to improve predictions of nitrate removal in the environment. Finally, fluorescence measurements revealed that bacteria used both protein and humic-like organic molecules during denitrification providing further evidence that larger, more aromatic molecules are not necessarily recalcitrant in the environment.

Spatial Variations of DOM Compositions in the River with Multi-functional Weir

NASA Astrophysics Data System (ADS)

Yoon, S. M.; Choi, J. H.

2017-12-01

With the global trend to construct artificial impoundments over the last decades, there was a Large River Restoration Project conducted in South Korea from 2010 to 2011. The project included enlargement of river channel capacity and construction of multi-functional weirs, which can alter the hydrological flow of the river and cause spatial variations of water quality indicators, especially DOM (Dissolved Organic Matter) compositions. In order to analyze the spatial variations of organic matter, water samples were collected longitudinally (5 points upstream from the weir), horizontally (left, center, right at each point) and vertically (1m interval at each point). The specific UV-visible absorbance (SUVA) and fluorescence excitation-emission matrices (EEMs) have been used as rapid and non-destructive analytical methods for DOM compositions. In addition, parallel factor analysis (PARAFAC) has adopted for extracting a set of representative fluorescence components from EEMs. It was assumed that autochthonous DOM would be dominant near the weir due to the stagnation of hydrological flow. However, the results showed that the values of fluorescence index (FI) were 1.29-1.47, less than 2, indicating DOM of allochthonous origin dominated in the water near the weir. PARAFAC analysis also showed the peak at 450 nm of emission and < 250 nm of excitation which represented the humic substances group with terrestrial origins. There was no significant difference in the values of Biological index (BIX), however, values of humification index (HIX) spatially increased toward the weir. From the results of the water sample analysis, the river with multi-functional weir is influenced by the allochthonous DOM instead of autochthonous DOM and seems to accumulate humic substances near the weir.

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.

Dissolved organic matter composition of winter flow in the Yukon River basin: Implications of permafrost thaw and increased groundwater discharge

USGS Publications Warehouse

O'Donnell, Jonathan A.; Aiken, George R.; Walvoord, Michelle Ann; Butler, Kenna D.

2012-01-01

Groundwater discharge to rivers has increased in recent decades across the circumpolar region and has been attributed to thawing permafrost in arctic and subarctic watersheds. Permafrost-driven changes in groundwater discharge will alter the flux of dissolved organic carbon (DOC) in rivers, yet little is known about the chemical composition and reactivity of dissolved organic matter (DOM) of groundwater in permafrost settings. Here, we characterize DOM composition of winter flow in 60 rivers and streams of the Yukon River basin to evaluate the biogeochemical consequences of enhanced groundwater discharge associated with permafrost thaw. DOC concentration of winter flow averaged 3.9 ± 0.5 mg C L−1, yet was highly variable across basins (ranging from 20 mg C L−1). In comparison to the summer-autumn period, DOM composition of winter flow had lower aromaticity (as indicated by specific ultraviolet absorbance at 254 nm, or SUVA254), lower hydrophobic acid content, and a higher proportion of hydrophilic compounds (HPI). Fluorescence spectroscopy and parallel factor analysis indicated enrichment of protein-like fluorophores in some, but not all, winter flow samples. The ratio of DOC to dissolved organic nitrogen, an indicator of DOM biodegradability, was positively correlated with SUVA254 and negatively correlated with the percentage of protein-like compounds. Using a simple two-pool mixing model, we evaluate possible changes in DOM during the summer-autumn period across a range of conditions reflecting possible increases in groundwater discharge. Across three watersheds, we consistently observed decreases in DOC concentration and SUVA254 and increases in HPI with increasing groundwater discharge. Spatial patterns in DOM composition of winter flow appear to reflect differences in the relative contributions of groundwater from suprapermafrost and subpermafrost aquifers across watersheds. Our findings call for more explicit consideration of DOC loss and stabilization pathways associated with changing subsurface hydrology in watersheds underlain by thawing permafrost.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and EEM-PARAFAC components within the peat column. In particular the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate-depthmore » zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds (PAC) that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate-depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table and redox oscillation and porewater advection.« less

Comparison of the chemical composition of dissolved organic matter in three lakes in Minnesota

USGS Publications Warehouse

Cao, Xiaoyan; Aiken, George R.; Butler, Kenna D.; Mao, Jingdong; Schmidt-Rohr, Klaus

2018-01-01

New information on the chemical composition of dissolved organic matter (DOM) in three lakes in Minnesota has been gained from spectral editing and two-dimensional nuclear magnetic resonance (NMR) methods, indicating the effects of lake hydrological settings on DOM composition. Williams Lake (WL), Shingobee Lake (SL), and Manganika Lake (ML) had different source inputs, and the lake water residence time (WRT) of WL was markedly longer than that of SL and ML. The hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions combined comprised >50% of total DOM in these lakes, and contained carboxyl-rich alicyclic molecules (CRAM), aromatics, carbohydrates, and N-containing compounds. The previously understudied TPIA fractions contained fewer aromatics, more oxygen-rich CRAM, and more N-containing compounds compared to the corresponding HPOA. CRAM represented the predominant component in DOM from all lakes studied, and more so in WL than in SL and ML. Aromatics including lignin residues and phenols decreased in relative abundances from ML to SL and WL. Carbohydrates and N-containing compounds were minor components in both HPOA and TPIA and did not show large variations among the three lakes. The increased relative abundances of CRAM in DOM from ML, SL to WL suggested the selective preservation of CRAM with increased residence time.

Tracking Changes in Dissolved Organic Matter Patterns in Perennial Headwater Streams Throughout a Hydrologic Year Using In-situ Sensors and Optical Properties

NASA Astrophysics Data System (ADS)

Armstrong, A.; Epting, S.; Hosen, J. D.; Palmer, M.

2015-12-01

Dissolved organic matter (DOM) plays a central role in freshwater streams but key questions remain unanswered about temporal patterns in its quantity and composition. DOM in perennial streams in the temperate zone is a complex mixture reflecting a variety of sources such as leached plant material, organic matter from surrounding soils, and microbial processes in the streams themselves. Headwater perennial streams in the Tuckahoe Creek watershed of the Atlantic coastal plain (Maryland, USA) drain a mosaic of land cover types including row crops, forests, and both forested and marshy small depressional wetlands. Wetland-stream surface hydrologic connections generally occur between mid-fall and late spring, coinciding with peak wetland hydrologic expression (i.e. highest groundwater levels and surface inundation extent). When inundated, these wetlands contain high DOM concentrations, and surface connections may serve as conduits for downstream export. We hypothesized that changes in wetland-stream surface hydrologic connectivity would affect patterns of DOM concentration and composition in these streams. We deployed 6 sondes equipped with fluorescent DOM sensors in 4 perennial streams, 1 forested wetland, and the larger downstream channel draining all study sites for the 2015 water year. The 4 headwater streams drain areas containing forested wetlands and have documented temporary channel connections. Combined with baseflow and stormflow sampling, the sondes provided 15 minute estimates of dissolved organic carbon (DOC) concentrations. This resolution provided insights into patterns of DOC concentration across temporal scales from daily rhythms to seasonal changes, during both baseflow and storm conditions. Discrete measurements of absorbance and fluorescence provided information about DOM composition throughout the study. Together these measurements give a detailed record of DOM dynamics in multiple perennial headwater streams for an entire year. This information could inform future studies, such as investigations into stream network scale thresholds in DOM cycling, carbon cycling modelling for the study region, or understanding the impact of wetlands sometimes considered geographically isolated on downstream ecosystems.

Dissolved Organic Matter Composition and Export from U.S. Rivers

NASA Astrophysics Data System (ADS)

Aiken, G.; Butman, D. E.; Spencer, R. G.; Raymond, P.

2012-12-01

Dissolved organic matter (DOM) chemistry and flux are potentially useful indicators of watershed characteristics, climate influences on watershed hydrology and soils, and changes associated with water and land resource management. Organic source materials, watershed geochemistry, oxidative processes and hydrology strongly influence 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. 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 a multi-year study designed to assess the seasonal and spatial variability of DOM quantity and quality for 15 large North American river basins. Samples were collected from the mouths of the rivers using a sampling program designed to capture hydrologic and seasonal variability of DOM export. DOM concentrations and composition, based on DOM fractionation on XAD resins, chromophoric dissolved organic matter (CDOM) parameters (ultraviolet /visible absorption and fluorescence spectroscopy), specific compound analyses, and DO14C content varied greatly both between sites and seasonally within a given site. DOM in these rivers exhibited a wide range of concentration and carbon specific ultra-violet absorbance at 254 nm (SUVA254), an optical measurement that is an indicator of DOM aromatic carbon content. In almost all systems, CDOM optical parameters correlated strongly with DOC concentration and hydrophobic organic acid (HPOA) content (aquatic humic substances). In particular, SUVA254 was found to correlate strongly with the proportion of HPOA and Δ14C. Relationships between dissolved organic carbon (DOC) concentration and absorbance for individual rivers were quite variable due to differences in the fraction of non-chromophoric DOM. Notably, the relationship between UV absorption coefficients and DOC concentration for four rivers that drain arid regions and/or are heavily influenced by impoundments were statistically weak.although similar trends for these rivers were not observed for Δ14C. Basins with high discharge, high density of vegetation cover, and low population densities exported younger, more aromatic DOM. Conversely, old DOM was exported from low discharge watersheds draining arid regions and watersheds impacted by high population densities. While individual watershed characteristics control DOC concentrations, CDOM parameters and DO14C content, overall discharge dominated the flux of both CDOM and DO14C to coastal waters. The link between the nature and reactivity of DOM and its optical properties can be exploited to provide powerful monitoring tools to assess the impacts of climate change, land-use change, and management practices on overall water quality and on DOM transport and transformation.

Similarities in Photodegradation of Cyanobacteria-Derived and Marine Fluorescent Dissolved Organic Matter

NASA Astrophysics Data System (ADS)

Ianiri, H. L.; Timko, S.; Gonsior, M.

2016-02-01

Marine dissolved organic matter (DOM) is one of the largest reduced carbon reservoirs on Earth, yet we only have a limited understanding of its production, cycling, degradation, and overall structure. It was previously believed that a significant portion of refractory dissolved organic carbon (RDOC) in the ocean was derived from terrestrial sources, however recent studies indicated that the majority of marine DOM might be produced in situ by marine biota. Previous research has found that terrestrial and microbial DOM fluorescent signatures are similar, complicating the identification of the origins of marine fluorescent DOM (FDOM). However, photodegradation kinetics of terrestrial and microbial-derived DOM are expected to be different due to their assumed different chemical compositions. In this study we analyzed for the first time the photodegradation kinetics of microbial-derived DOM originating from different cyanobacteria strains. Cyanobacterial-derived DOM were exposed to simulated sunlight for a total of 20 hours while recording excitation emission matrix (EEM) fluorescence every twenty minutes to observe the photodegradation of this specific FDOM. Parallel Factor Analysis (PARAFAC) was applied to deconvolute the EEM matrices into six separate components. The photodegradation kinetics was then calculated for each component and compared with previously obtained photodegradation data of marine and terrestrial FDOM. This six component PARAFAC model was similar to those generated from open ocean data and global DOM data sets. The "humic-like" FDOM was also found in cyanobacteria FDOM and showed similar fluorescence intensities and percent fluorescence loss when compared to marine DOM. The degradation kinetics of the "humic-like" component of microbial-derived DOM was faster than that of terrestrial-derived DOM, and marine FDOM samples showed degradation kinetics more similar to microbial-derived FDOM. This indicates marine FDOM is more similar in chemical composition to microbial-derived FDOM than terrestrial-derived FDOM, supporting the hypothesis that the majority of marine FDOM is produced in situ.

Different effects of plant-derived dissolved organic matter (DOM) and urea on the priming of soil organic carbon.

PubMed

Qiu, Qingyan; Wu, Lanfang; Ouyang, Zhu; Li, Binbin; Xu, Yanyan

2016-03-01

Soil organic carbon (SOC) mineralization is important for the regulation of the global climate and soil fertility. Decomposition of SOC may be significantly affected by the supply of plant-derived labile carbon (C). To investigate the impact of plant-derived dissolved organic matter (DOM) and urea (N) additions on the decomposition of native SOC as well as to elucidate the underlying mechanisms of priming effects (PEs), a batch of incubation experiments was conducted for 250 days by application of (13)C-labeled plant-derived DOM and urea to soils. The direction of PE induced by the addition of DOM was different from the addition of N, i.e. it switched from negative to positive in DOM-amended soils, whereas in the N-treated soil it switched from positive to negative. Adding DOM alone was favorable for soil C sequestration (59 ± 5 mg C per kg soil), whereas adding N alone or together with DOM accelerated the decomposition of native SOC, causing net C losses (-62 ± 4 and -34 ± 31 mg C per kg soil, respectively). These findings indicate that N addition and its interaction with DOM are not favorable for soil C sequestration. Adding DOM alone increased the level of dissolved organic carbon (DOC), but it did not increase the level of soil mineral N. Changes in the ratio of microbial biomass carbon (MBC) to microbial biomass nitrogen (MBN) and microbial metabolic quotient (qCO2) after the addition of DOM and N suggest that a possible shift in the microbial community composition may occur in the present study. Adding DOM with or without N increased the activities of β-glucosidase and urease. Changes in the direction and magnitude of PE were closely related to changes in soil C and N availability. Soil C and N availability might influence the PE through affecting the microbial biomass and extracellular enzyme activity as well as causing a possible shift in the microbial community composition.

Molecular Insights on Dissolved Organic Matter Transformation by Supraglacial Microbial Communities.

PubMed

Antony, Runa; Willoughby, Amanda S; Grannas, Amanda M; Catanzano, Victoria; Sleighter, Rachel L; Thamban, Meloth; Hatcher, Patrick G; Nair, Shanta

2017-04-18

Snow overlays the majority of Antarctica and is an important repository of dissolved organic matter (DOM). DOM transformations by supraglacial microbes are not well understood. We use ultrahigh resolution mass spectrometry to elucidate molecular changes in snowpack DOM by in situ microbial processes (up to 55 days) in a coastal Antarctic site. Both autochthonous and allochthonous DOM is highly bioavailable and is transformed by resident microbial communities through parallel processes of degradation and synthesis. DOM thought to be of a more refractory nature, such as dissolved black carbon and carboxylic-rich alicyclic molecules, was also rapidly and extensively reworked. Microbially reworked DOM exhibits an increase in the number and magnitude of N-, S-, and P-containing formulas, is less oxygenated, and more aromatic when compared to the initial DOM. Shifts in the heteroatom composition suggest that microbial processes may be important in the cycling of not only C, but other elements such as N, S, and P. Microbial reworking also produces photoreactive compounds, with potential implications for DOM photochemistry. Refined measurements of supraglacial DOM and their cycling by microbes is critical for improving our understanding of supraglacial DOM cycling and the biogeochemical and ecological impacts of DOM export to downstream environments.

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

Differences in dissolved organic matter between reclaimed water source and drinking water source.

PubMed

Hu, Hong-Ying; Du, Ye; Wu, Qian-Yuan; Zhao, Xin; Tang, Xin; Chen, Zhuo

2016-05-01

Dissolved organic matter (DOM) significantly affects the quality of reclaimed water and drinking water. Reclaimed water potable reuse is an effective way to augment drinking water source and de facto reuse exists worldwide. Hence, when reclaimed water source (namely secondary effluent) is blended with drinking water source, understanding the difference in DOM between drinking water source (dDOM) and reclaimed water source (rDOM) is essential. In this study, composition, transformation, and potential risk of dDOM from drinking water source and rDOM from secondary effluent were compared. Generally, the DOC concentration of rDOM and dissolved organic nitrogen (DON) content in reclaimed water source were higher but rDOM exhibited a lower aromaticity. Besides, rDOM comprises a higher proportion of hydrophilic fractions and more low-molecular weight compounds, which are difficult to be removed during coagulation. Although dDOM exhibited higher specific disinfection byproducts formation potential (SDBPFP), rDOM formed more total disinfection byproducts (DBPs) during chlorination including halomethanes (THMs) and haloacetic acids (HAAs) due to high DOC concentration. Likewise, in consideration of DOC basis, rDOM contained more absolute assimilable organic carbon (AOC) despite showing a lower specific AOC (normalized AOC per unit of DOC). Besides, rDOM exhibited higher biotoxicity including genotoxicity and endocrine disruption. Therefore, rDOM presents a greater potential risk than dDOM does. Reclaimed water source needs to be treated carefully when it is blended with drinking water source. Copyright © 2015. Published by Elsevier B.V.

Spatial and Temporal Patterns of Dissolved Organic Matter Characteristics in the Upper Willamette River Basin, Oregon

NASA Astrophysics Data System (ADS)

Lee, B. S.; Lajtha, K.

2014-12-01

Dissolved organic matter (DOM) leaching through soil affects soil carbon sequestration and the carbon metabolism of receiving water bodies. Improving our understanding of the sources and fate of DOM at varying spatial and temporal patterns is crucial for land management decisions. However, little is known about how DOM sources change with land use types and seasonal flow patterns. In the Willamette River Basin (WRB), which is home to Oregon's major cities including Portland and Salem, forested headwaters transition to agricultural and urban land. The climate of WRB has a distinctive seasonal pattern with dry warm summers and wet winters driven by winter precipitation and snowmelt runoff between November and March. This study examined DOM fluorescence characteristic in stream water from 21 locations collected monthly and 16 locations collected seasonally to identify the sources and fate of DOM in the upper WRB in contrasting land uses. DOC and dissolved organic nitrogen concentrations increased as the flow rate increased during winter precipitation at all sites. This indicates that increased flow rate increased the connectivity between land and nearby water bodies. DOM fluorescent properties varied among land use types. During the first precipitation event after a long dry summer, a microbial DOM signature in agricultural areas increased along with nitrate concentrations. This may be because accumulated nutrients on land during the dry season flowed to nearby streams during the first rain event and promoted microbial growth in the streams. During the month of the highest flow rate in 2014, sampling sites near forest showed evidence of a greater terrestrial DOM signature compared to its signature during the dry season. This indicates fluorescent DOM characteristics in streams vary as the flow connectivity changes even within the same land type.

Design, fabrication, and testing of nanostructured carbons and composites

NASA Astrophysics Data System (ADS)

Wang, Zhiyong

Many applications, such as catalysis, sensing, separation and energy storage and conversion, will benefit from the miniaturization of materials to nanometer length scales. This dissertation details my study of nanocomposites based on three-dimensionally ordered macroporous (3DOM) carbons and zirconia, and three-dimensionally ordered macroporous/mesoporous (3DOM/m) carbons. The macropores of these materials were produced using colloidal crystal templates while the mesopores were generated using surfactant templates. These solids are composed of close-packed and three-dimensionally interconnected spherical macropores surrounded by nanoscale solid or mesoporous wall skeletons. This unique architecture offers large surface areas, pore volumes, and good access into the bulk via a macroporous network. 3DOM carbons have been demonstrated as promising electrode materials for lithium ion batteries and sensors, but their electrochemical performance still needs to be improved. As a model system for the modification of the electrode, 3DOM C/TiO2 was synthesized by fabricating a conformal coating of TiO2 nanoparticles on the macropore walls of 3DOM C. My research further extended the micro-structural design of monolithic carbon from 3DOM to 3DOM/m. 3DOM/m C monoliths with high surface areas, controllable mesopore sizes, and mesopore ordering, were synthesized by three methods. One of the methods is simpler and more environment benign than previously reported methods. The mesopores in 3DOM/m C-based electrode provide room to accommodate secondary phases, such as graphitic carbon, SnO2 and Si which can improve the conductivity or lithium capacity of the electrode. Owing to this advantage, 3DOM/m C/C and 3DOM/m C/SnO2 exhibited significantly improved rate performance, lithium capacity and cycleability, compared with 3DOM C. To meet the demands of nano-sized functional materials in applications such as nano-device fabrication and drug delivery, mesoporous carbon nanoparticles with cubic, spherical and tetrapod shapes were also synthesized. In addition, new methods were developed to assemble nanocomposites of bifunctional catalyst components. These materials were designed for the potential direct conversion of synthesis gas to clean liquid fuels. Coatings of zeolite and cobalt nanoparticles were fabricated on 3DOM promoted zirconia. The 3DOM zirconia-based nanocomposites were characterized by a wide variety of techniques to illustrate their morphologies, internal structures, chemical compositions, porosity, and crystallographic phases.

Dissolved Organic Matter in Groundwater: a Shadow of its Former Self

NASA Astrophysics Data System (ADS)

Chapelle, F.

2017-12-01

The occurrence and dynamics of dissolved organic matter (DOM) are fundamentally different between ground- and surface water systems. The most obvious difference is that primary production, an important source of DOM to many surface waters, it is wholly absent from groundwater systems. Because of that, the composition and bioavailability of DOM is functionally linked to its residence time within the subsurface. While sorption/desorption processes segregate chemical fractions of DOM in both ground- and surface water systems, their effects are magnified by the much higher sediment/water mass ratio characteristic of groundwater systems. These differences, which often act in concert with each other, explain many observed characteristics of DOM in groundwater systems including (1) the low and nearly uniform DOM concentrations (0.5-1.0 mg/L) characteristic of many aquifers, (2) the progressive loss of carbohydrate and amino acid DOM and the enrichment of aromatic DOM, with increasing aquifer residence time (3) the progressive loss of VIS/UV absorption capacity (color) of DOM with increasing aquifer residence time, (4) the negative correlation between dissolved oxygen concentrations and DOM bioavailability, and (5) the positive correlation between DOM bioavailability and the final products of anoxic redox processes. Thus, while the principal sources of DOM to many groundwater systems are surface-derived, the dynamics unique to subsurface environments tend to render that DOM a shadow of its former self.

Nematode feeding strategies and the fate of dissolved organic matter carbon in different deep-sea sedimentary environments

NASA Astrophysics Data System (ADS)

Pape, Ellen; van Oevelen, Dick; Moodley, Leon; Soetaert, Karline; Vanreusel, Ann

2013-10-01

Sediments sampled from the Galicia Bank seamount and the adjacent slope (northeast Atlantic), and from a western Mediterranean slope site, were injected onboard with 13C-enriched dissolved organic matter (DOM) to evaluate nematode feeding strategies and the fate of DOM carbon in different benthic environments. We hypothesized that nematode 13C label assimilation resulted from either direct DOM uptake or feeding on 13C labeled bacteria. Slope sediments were injected with glucose ("simple" DOM) or "complex" diatom-derived DOM to investigate the influence of DOM composition on carbon assimilation. The time-series (1, 7 and 14 days) experiment at the seamount site was the first study to reveal a higher 13C enrichment of nematodes than bacteria and sediments after 7 days. Although isotope dynamics indicated that both DOM and bacteria were plausible candidate food sources, the contribution to nematode secondary production and metabolic requirements (estimated from biomass-dependent respiration rates) was higher for bacteria than for DOM at all sites. The seamount nematode community showed higher carbon assimilation rates than the slope assemblages, which may reflect an adaptation to the food-poor environment. Our results suggested that the trophic importance of bacteria did not depend on the amount of labile sedimentary organic matter. Furthermore, there was a discrepancy between carbon assimilation rates observed in the experiments and the feeding type classification, based on buccal morphology. Sites with a similar feeding type composition (i.e. the northeast Atlantic sites) showed large differences in uptake, whilst the nematode assemblages at the two slope sites, which had a differing trophic structure, took up similar amounts of the DOM associated carbon. Our results did not indicate substantial differences in carbon processing related to the complexity of the DOM substrate. The quantity of processed carbon (5-42% of added DOM) was determined by the bacteria, and was primarily respired. The bulk of the added 13C-DOM was not ingested by the benthic biota under study, and a considerable fraction was possibly adsorbed onto the sediment grains.

Analysis and Characterization of Dissolved Organic Matter in Ice Cores as Indicators of Past Environmental Conditions Using High Resolution FTICR-MS

NASA Astrophysics Data System (ADS)

Boschi, V.; Grannas, A. M.; Willoughby, A. S.; Catanzano, V.; Hatcher, P.

2015-12-01

With rapid changes in global temperatures, research aimed at better understanding past climatic events in order to predict future trends is an area of growing importance. Carbonaceous gases stored in ice cores are known to correlate with temperature change and provide evidence of such events. However, more complex forms of carbon preserved in ice cores such as dissolved organic matter (DOM) can provide additional information relating to changes in environmental conditions over time. The examination of ice core samples presents unique challenges including detection of ultra-low concentrations of organic material and extremely limited sample amounts. In this study, solid phase extraction techniques combined with ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS) were utilized to successfully extract, concentrate and analyze the low concentrations of DOM in only 100 mL of ice core samples originating from various regions of Antarctica and Greenland. We characterize the DOM composition in each sample by evaluating elemental ratios, molecular formula distribution (CHO, CHON, CHOS and CHNOS) and compound class composition (lignin, tannin, lipid, condensed aromatic, protein and unsaturated hydrocarbon content). Upon characterization, we identified molecular trends in ice core DOM chemistry that correlated with past climatic events in addition to observing possible photochemical and microbial influences affecting DOM chemistry. Considering these samples range in age from 350-1175 years old, thus being formed during the Medieval Warm Period and Little Ice Age, we observed that DOM properties reflected anticipated changes in composition as influenced by warming and cooling events occurring during that time period.

Stormwater dissolved organic matter: influence of land cover and environmental factors.

PubMed

McElmurry, Shawn P; Long, David T; Voice, Thomas C

2014-01-01

Dissolved organic matter (DOM) plays a major role in defining biological systems and it influences the fate and transport of many pollutants. Despite the importance of DOM, understanding of how environmental and anthropogenic factors influence its composition and characteristics is limited. This study focuses on DOM exported as stormwater from suburban and urban sources. Runoff was collected before entering surface waters and DOM was characterized using specific ultraviolet absorbance at 280 nm (a proxy for aromaticity), molecular weight, polydispersity and the fraction of DOM removed from solution via hydrophobic and H-bonding mechanisms. General linear models (GLMs) incorporating land cover, precipitation, solar radiation and selected aqueous chemical measurements explained variations in DOM properties. Results show (1) molecular characteristics of DOM differ as a function of land cover, (2) DOM produced by forested land is significantly different from other landscapes, particularly urban and suburban areas, and (3) DOM from land cover that contains paved surfaces and sewers is more hydrophobic than from other types of land cover. GLMs incorporating environmental factors and land cover accounted for up to 86% of the variability observed in DOM characteristics. Significant variables (p < 0.05) included solar radiation, water temperature and water conductivity.

The composition and character of DOM from an upland peat catchment - sources, roles and fate

NASA Astrophysics Data System (ADS)

Worrall, F.; Moody, C.; Clay, G.; Boothroyd, I.; Burt, T. P.

2017-12-01

The fluvial fluxes of dissolved organic carbon (DOC) from peatlands form an important part of that ecosystem's carbon cycle, contributing approximately 35% of the overall peatland carbon budget. The source, role and fate of this component of the carbon cycle was explored for a peat covered catchment in the north east of England with dissolved organic matter (DOM) being sampled from both a first-order peat-hosted stream and soil water at two depths within the peat profile. All DOM samples were analysed within the context of analysing the particulate organic matter (POM) from the catchment; the peat profile; and biomass. All samples were analysed using: elemental analysis (C, H, N, O, P and S); bomb calorimetry; thermogravimetric analysis (TGA); 13C solid state NMR; and S isotopes. Furthermore, the degradation of fresh DOC was examined over periods of 70 hours every month for 23 months. The analysis has shown that: DOM is highly oxidised compared to all other organic in the ecosystem and DOM did not exist until [C]/[O] < 1.44. The DOM was dominantly the product of lignin breakdown and not the processing of proteins or carbohydrates, i.e. it was not an intermediate of oxidation to CO2. DOM could only be sourced from high in the peat profile at most above 41 cm depth. Thermodynamic inhibition shows that only DOM from the surface layers could be reactive in the catotelmic layers of the peat. There was a significant role for the composition of the DOM in controlling degradation with degradation rates significantly increasing with the proportion of aldehyde and carboxylic acid functional groups but decreasing with the proportion of N-alkyl functional groups. The study meant that is was possible to consider the behaviour of DOM in terms of its thermodynamic properties (DH, DS & DG) for both formation and reaction.

Effects of ocean acidification on marine dissolved organic matter are not detectable over the succession of phytoplankton blooms.

PubMed

Zark, Maren; Riebesell, Ulf; Dittmar, Thorsten

2015-10-01

Marine dissolved organic matter (DOM) is one of the largest active organic carbon reservoirs on Earth, and changes in its pool size or composition could have a major impact on the global carbon cycle. Ocean acidification is a potential driver for these changes because it influences marine primary production and heterotrophic respiration. We simulated ocean acidification as expected for a "business-as-usual" emission scenario in the year 2100 in an unprecedented long-term mesocosm study. The large-scale experiments (50 m(3) each) covered a full seasonal cycle of marine production in a Swedish Fjord. Five mesocosms were artificially enriched in CO2 to the partial pressure expected in the year 2100 (900 μatm), and five more served as controls (400 μatm). We applied ultrahigh-resolution mass spectrometry to monitor the succession of 7360 distinct DOM formulae over the course of the experiment. Plankton blooms had a clear effect on DOM concentration and molecular composition. This succession was reproducible across all 10 mesocosms, independent of CO2 treatment. In contrast to the temporal trend, there were no significant differences in DOM concentration and composition between present-day and year 2100 CO2 levels at any time point of the experiment. On the basis of our results, ocean acidification alone is unlikely to affect the seasonal accumulation of DOM in productive coastal environments.

Effects of ocean acidification on marine dissolved organic matter are not detectable over the succession of phytoplankton blooms

PubMed Central

Zark, Maren; Riebesell, Ulf; Dittmar, Thorsten

2015-01-01

Marine dissolved organic matter (DOM) is one of the largest active organic carbon reservoirs on Earth, and changes in its pool size or composition could have a major impact on the global carbon cycle. Ocean acidification is a potential driver for these changes because it influences marine primary production and heterotrophic respiration. We simulated ocean acidification as expected for a “business-as-usual” emission scenario in the year 2100 in an unprecedented long-term mesocosm study. The large-scale experiments (50 m3 each) covered a full seasonal cycle of marine production in a Swedish Fjord. Five mesocosms were artificially enriched in CO2 to the partial pressure expected in the year 2100 (900 μatm), and five more served as controls (400 μatm). We applied ultrahigh-resolution mass spectrometry to monitor the succession of 7360 distinct DOM formulae over the course of the experiment. Plankton blooms had a clear effect on DOM concentration and molecular composition. This succession was reproducible across all 10 mesocosms, independent of CO2 treatment. In contrast to the temporal trend, there were no significant differences in DOM concentration and composition between present-day and year 2100 CO2 levels at any time point of the experiment. On the basis of our results, ocean acidification alone is unlikely to affect the seasonal accumulation of DOM in productive coastal environments. PMID:26601292

Dissolved organic matter and estrogen interactions regulate estrogen removal in the aqueous environment: A review.

PubMed

Ma, Li; Yates, Scott R

2018-06-03

This review summarizes the characterization and quantification of interactions between dissolved organic matter (DOM) and estrogens as well as the effects of DOM on aquatic estrogen removal. DOM interacts with estrogens via binding or sorption mechanisms like π-π interaction and hydrogen bonding. The binding affinity is evaluated in terms of organic-carbon-normalized sorption coefficient (Log K OC ) which varies with types and composition of DOM. DOM has been suggested to be a more efficient sorbent compared with other matrices, such as suspended particulate matter, sediment and soil; likely associated with its large surface area and concentrated carbon content. As a photosensitizer, DOM enhanced estrogen photodegradation when the concentration of DOM was below a threshold value, and when above, the acceleration effect was not observed. DOM played a dual role in affecting biodegradation of estrogens depending on the recalcitrance of the DOM and the nutrition status of the degraders. DOM also acted as an electron shuttle (redox mediator) mediating the degradation of estrogens. DOM hindered enzyme-catalyzed removal of estrogens while enhanced their transformation during the simultaneous photo-enzymatic process. Membrane rejection of estrogens was pronounced for hydrophobic DOM with high aromaticity and phenolic moiety content. Elimination of estrogens via photolysis, biodegradation, enzymolysis and membrane rejection in the presence of DOM is initiated by sorption, accentuating the role of DOM as a mediator in regulating aquatic estrogen removal. Published by Elsevier B.V.

Spatial and seasonal variations in the composition of dissolved organic matter in a tropical catchment: the Lower Kinabatangan River, Sabah, Malaysia.

PubMed

Harun, Sahana; Baker, Andy; Bradley, Chris; Pinay, Gilles

2016-01-01

Dissolved organic matter (DOM) was characterised in water samples sampled in the Lower Kinabatangan River Catchment, Sabah, Malaysia between October 2009 and May 2010. This study aims at: (i) distinguishing between the quality of DOM in waters draining palm oil plantations (OP), secondary forests (SF) and coastal swamps (CS) and, (ii) identifying the seasonal variability of DOM quantity and quality. Surface waters were sampled during fieldwork campaigns that spanned the wet and dry seasons. DOM was characterised optically by using the fluorescence Excitation Emission Matrix (EEM), the absorption coefficient at 340 nm and the spectral slope coefficient (S). Parallel Factor Analysis (PARAFAC) was undertaken to assess the DOM composition from EEM spectra and five terrestrial derived components were identified: (C1, C2, C3, C4 and C5). Components C1 and C4 contributed the most to DOM fluorescence in all study areas during both the wet and dry seasons. The results suggest that component C4 could be a significant (and common) PARAFAC signal found in similar catchments. Peak M (C2 and C3) was dominant in all samples collected during wet and dry seasons, which could be anthropogenic in origin given the active land use change in the study area. In conclusion, there were significant seasonal and spatial variations in DOM which demonstrated the effects of land use cover and precipitation amounts in the Kinabatangan catchment.

Effects of dissolved organic matter (DOM) sources and nature of solid extraction sorbent on recoverable DOM composition: Implication into potential lability of different compound groups.

PubMed

Chen, Meilian; Kim, Sunghwan; Park, Jae-Eun; Kim, Hyun Sik; Hur, Jin

2016-07-01

Noting the source-dependent properties of dissolved organic matter (DOM), this study explored the recoverable compounds by solid phase extraction (SPE) of two common sorbents (C18 and PPL) eluted with methanol solvent for contrasting DOM sources via fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Fresh algae and leaf litter extracts DOM, one riverine DOM, and one upstream lacustrine DOM were selected for the comparison. C18 sorbent was generally found to extract more diverse molecular formula, relatively higher molecular weight, and more heteroatomic DOM compounds within the studied mass range than PPL sorbent except for the leaf litter extract. Even with the same sorbent, the main molecular features of the two end member DOM were distributed on different sides of the axes of a multivariate ordination, indicating the source-dependent characteristics of the recoverable compounds by the sorbents. In addition, further examination of the molecular formula uniquely present in the two end members and the upstream lake DOM suggested that proteinaceous, tannin-like, and heteroatomic DOM constituents might be potential compound groups which are labile and easily degraded during their mobilization into downstream watershed. This study provides new insights into the sorbent selectivity of DOM from diverse sources and potential lability of various compound groups.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Characterizing the release of different composition of dissolved organic matter in soil under acid rain leaching using three-dimensional excitation-emission matrix spectroscopy.

PubMed

Liu, Li; Song, Cunyi; Yan, Zengguang; Li, Fasheng

2009-09-01

Although excitation-emission matrix spectroscopy (EEMS) has been widely used to characterize dissolved organic matter (DOM), there has no report that EEMS has been used to study the effects of acid rain on DOM and its composition in soil. In this work, we employed three-dimensional EEMS to characterize the compositions of DOM leached by simulated acid rain from red soil. The red soil was subjected to leaching of simulated acid rain of different acidity, and the leached DOM presented five main peaks in its EEMS: peak-A, related to humic acid-like (HA-like) material, at Ex/Em of 310-330/395-420nm; peak-B, related to UV fulvic acid-like (FA-like) material, at Ex/Em of 230-280/400-435nm; peak-C and peak-D, both related to microbial byproduct-like material, at Ex/Em of 250-280/335-355nm and 260-280/290-320nm, respectively; and peak-E, related to simple aromatic proteins, at Ex/Em of 210-240/290-340nm. EEMS analysis results indicated that most DOM could be lost from red soil in the early phase of acid rain leaching. In addition to the effects of the pH of acid rain, the loss of DOM also depended on the properties of its compositions and the solubility of their complexes with aluminum. HA-like and microbial byproduct-like materials could be more easily released from red soil by acid rain at both higher pH (4.5 and 5.6) and lower pH (2.5 and 3) than that at middle pH (3.5). On the contrary, FA-like material lost in a similar manner under the action of different acid rains with pH ranging from 2.5 to 5.6.

[Absorption and fluorescence characteristics of dissolved organic matter (DOM) in rainwater and sources analysis in summer and winter season].

PubMed

Liang, Jian; Jiang, Tao; WeiI, Shi-Qiang; Lu, Song; Yan, Jin-Long; Wang, Qi-Lei; Gao, Jie

2015-03-01

This study aimed at evaluating the variability of the optical properties including UV-Vis and fluorescence characteristics of dissolved organic matter (DOM) from rainwater in summer and winter seasons. UV-Vis and fluorescence spectroscopy, together with Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and fire events map, were conducted to characterize DOM and investigate its sources and contributions. The results showed that as compared with aquatic and soil DOM, rainwater DOM showed similar spectral characteristics, suggesting DOM in precipitation was also an important contributor to DOM pool in terrestrial and aquatic systems. The concentrations of DOC in rainwater were 0.88-12.80 mg x L(-1), and the CDOM concentrations were 3.17-21.11 mg x L(-1). Differences of DOM samples between summer and winter were significant (P < 0.05). In comparison to summer, DOM samples in winter had lower molecular weight and aromaticity, and also lower humification. Input of DOM in winter was predominantly derived from local and short-distance distances, while non-special scattering sources were identified as the main contributors in summer. Although absorption and fluorescence spectroscopy could be used to identify DOM composition and sources, there were obvious differences in spectra and sources analysis between rainwater DOM and the others from other sources. Thus, the classic differentiation method by "allochthonous (terrigenous) and autochthonous (authigenic)" is possibly too simple and arbitrary for characterization of DOM in rainwater.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE PAGES

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; ...

2018-01-29

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Molecular Features of Dissolved Organic Matter Produced by Picophytoplankton

NASA Astrophysics Data System (ADS)

Ma, X.; Coleman, M.; Waldbauer, J.

2016-02-01

Compounds derived from picophytoplankton through exudation, grazing and viral lysis contribute a large proportion of labile DOM to the ocean. This labile DOM is rapidly turned over by and exchanged among microbial communities. However, identifying labile DOM compounds and tracking their sources and sinks in ocean ecosystems is complicated by the presence of non-labile DOM which has a significantly larger reservoir size and longer residence time. This study focuses on investigating labile DOM produced by single-strain cyanobacteria isolates via different modes of release and varied nutrient conditions. DOM compounds are analyzed by high-resolution mass spectrometry. Statistical comparison between intracellular and extracellular molecular data of Synechococcus WH7803 revealed noticeable differences in terms of compound number, size and structure. Incubation experiments using combined whole seawater and diluent of grazer-free or viral-free water at the BATS time-series station in Sargasso Sea yielded complimentary data to be synthesized with data from lab cultures. The compositional features of each type of DOM could serve as future proxies for different modes of DOM production in the oceans.

Extending the analytical window for water-soluble organic matter in sediments by aqueous Soxhlet extraction

NASA Astrophysics Data System (ADS)

Schmidt, Frauke; Koch, Boris P.; Witt, Matthias; Hinrichs, Kai-Uwe

2014-09-01

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 μm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Evaluation of passive samplers for the collection of dissolved organic matter in streams.

PubMed

Warner, Daniel L; Oviedo-Vargas, Diana; Royer, Todd V

2015-01-01

Traditional sampling methods for dissolved organic matter (DOM) in streams limit opportunities for long-term studies due to time and cost constraints. Passive DOM samplers were constructed following a design proposed previously which utilizes diethylaminoethyl (DEAE) cellulose as a sampling medium, and they were deployed throughout a temperate stream network in Indiana. Two deployments of the passive samplers were conducted, during which grab samples were frequently collected for comparison. Differences in DOM quality between sites and sampling methods were assessed using several common optical analyses. The analyses revealed significant differences in optical properties between sampling methods, with the passive samplers preferentially collecting terrestrial, humic-like DOM. We assert that the differences in DOM composition from each sampling method were caused by preferential binding of complex humic compounds to the DEAE cellulose in the passive samplers. Nonetheless, the passive samplers may provide a cost-effective, integrated sample of DOM in situations where the bulk DOM pool is composed mainly of terrestrial, humic-like compounds.

Fractionation and characterization of dissolved organic matter (DOM) in refinery wastewater by revised phase retention and ion-exchange adsorption solid phase extraction followed by ESI FT-ICR MS.

PubMed

Fang, Zhi; He, Chen; Li, Yongyong; Chung, Keng H; Xu, Chunming; Shi, Quan

2017-01-01

Although the progress of high resolution mass spectrometry in the past decade has enabled the molecular characterization of dissolved organic matter (DOM) in water as a whole, fractionation of DOM is necessary for a comprehensive characterization due to its super-complex nature. Here we proposed a method for the fractionation of DOM in a wastewater based on solubility and acidic-basic properties. Solid phase extraction (SPE) cartridges with reversed phase retention and ion-exchange adsorption capacities, namely MAX and MCX, were used in succession to fractionate a petroleum refinery wastewater into four fractions: hydrophobic acid (HOA), hydrophobic neutral (HON), hydrophobic base (HOB), and hydrophilic substance (HIS) fractions. According to the total organic carbon (TOC) analysis, 72.6% (in term of TOC) of DOM was extracted in hydrophobic fractions, in which HON was the most abundant. Hydrophobic extracts were characterized by negative and positive ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), respectively. Compounds with multiple oxygen atoms were predominant in the HOA, which were responded strongly in the negative ESI MS. Nitrogen containing compounds were the major detected species by positive ion ESI in all hydrophobic fractions. The molecular composition of the DOM were discussed based on the FT-ICR MS results. The fractionation provided salt free samples which enables the direct analysis of the fractions by ESI and a deep insight into the molecular composition of DOM in the wastewater. The method is potential for routine evaluation of DOM in industry wastewaters, as well as environmental water samples. Copyright © 2016. Published by Elsevier B.V.

Experimental insights into the importance of aquatic bacterial community composition to the degradation of dissolved organic matter

PubMed Central

Logue, Jürg B; Stedmon, Colin A; Kellerman, Anne M; Nielsen, Nikoline J; Andersson, Anders F; Laudon, Hjalmar; Lindström, Eva S; Kritzberg, Emma S

2016-01-01

Bacteria play a central role in the cycling of carbon, yet our understanding of the relationship between the taxonomic composition and the degradation of dissolved organic matter (DOM) is still poor. In this experimental study, we were able to demonstrate a direct link between community composition and ecosystem functioning in that differently structured aquatic bacterial communities differed in their degradation of terrestrially derived DOM. Although the same amount of carbon was processed, both the temporal pattern of degradation and the compounds degraded differed among communities. We, moreover, uncovered that low-molecular-weight carbon was available to all communities for utilisation, whereas the ability to degrade carbon of greater molecular weight was a trait less widely distributed. Finally, whereas the degradation of either low- or high-molecular-weight carbon was not restricted to a single phylogenetic clade, our results illustrate that bacterial taxa of similar phylogenetic classification differed substantially in their association with the degradation of DOM compounds. Applying techniques that capture the diversity and complexity of both bacterial communities and DOM, our study provides new insight into how the structure of bacterial communities may affect processes of biogeochemical significance. PMID:26296065

Depth-dependent variations of sedimentary dissolved organic matter composition in a eutrophic lake: Implications for lake restoration.

PubMed

Xu, Huacheng; Guo, Laodong; Jiang, Helong

2016-02-01

Dissolved organic matter (DOM) plays a significant role in regulating nutrients and carbon cycling and the reactivity of trace metals and other contaminants in the environment. However, the environmental/ecological role of sedimentary DOM is highly dependent on organic composition. In this study, fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis, two dimensional correlation spectroscopy (2D-COS), and ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) were applied to investigate the depth-dependent variations of sediment-leached DOM components in a eutrophic lake. Results of EEM-PARAFAC and 2D-COS showed that fluorescent humic-like component was preferentially degraded microbially over fulvic-like component at greater sediment depths, and the relative abundance of non-fluorescent components decreased with increasing depth, leaving the removal rate of carbohydrates > lignins. The predominant sedimentary DOM components derived from FT-ICR-MS were lipids (>50%), followed by lignins (∼15%) and proteins (∼15%). The relative abundance of carbohydrates, lignins, and condensed aromatics decreased significantly at greater depths, whereas that of lipids increased in general with depth. There existed a significant negative correlation between the short-range ordered (SRO) minerals and the total dissolved organic carbon concentration or the relative contents of lignins and condensed aromatics (p < 0.05), suggesting that SRO mineral sorption plays a significant role in controlling the composition heterogeneity and releasing of DOM in lake sediments. Higher metal binding potential observed for DOM at deeper sediment depth (e.g., 25-30 cm) supported the ecological safety of sediment dredging technique from the viewpoint of heavy metal de-toxicity. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

USGS Publications Warehouse

Kellerman, Anne M.; Guillemette, François; Podgorski, David C.; Aiken, George R.; Butler, Kenna D.; Spencer, Robert G. M.

2018-01-01

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ13C-dissolved organic carbon (DOC) and Δ14C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ14C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA254), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ13C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.

Assembly of Functional Porous Solids in Complex Hybrid Composites

DTIC Science & Technology

2004-03-19

synthesis … 30 7.1.2 Grafting … 34 7.2 Surface functionalization of 3DOM oxide supports with polyelectrolytes and nanoparticles of another oxide … 34...incorporating hydrothermally prepared rutile/anatase nanoparticles (᝿ nm) within the walls of 3DOM silica, varying the titania content from ca. 0.5-20 wt... nanoparticles showing the bright colors that can be obtained and varied through synthesis parameters. 5.7 Effects of 3DOM particle sizes on optical

Lability of High Molecular Weight Dissolved Organic Matter Polysaccharides Increases with Mild Acid or Base Treatment.

NASA Astrophysics Data System (ADS)

Pedler Sherwood, B.; Sosa, O.; Nelson, C. E.; Repeta, D.; DeLong, E.

2016-02-01

Approximately 662 Pg of dissolved organic carbon (DOC) has accumulated in the global ocean, yet the biological and chemical constraints on DOC turnover remain poorly understood. High molecular weight dissolved organic matter (HMWDOM) is largely comprised of semi-labile polysaccharides. These polysaccharides resist degradation even in the presence of nutrient amendments, suggesting unknown factors of polysaccharide composition affect microbial degradation. In a series of microcosm incubations conducted at station ALOHA in the North Pacific Subtropical Gyre, we tested the affect of mild base (KOH-DOM) and acid (HCl-DOM) treatments on polysaccharide lability. KOH-DOM, HCl-DOM, and untreated HMWDOM was added to seawater from the deep chlorophyll maximum and 200m. Microcosms amended with KOH-DOM and HCl-DOM yielded higher bacterial abundance and greater carbon drawdown relative to untreated HMWDOM and unamended controls. Microcosms amended with KOH-DOM and HCl-DOM also showed significant production of fluorescent DOM (fDOM), whereas untreated HMWDOM and unamended controls showed a net decrease in fDOM as measured by parallel factor analysis of DOM excitation-emission spectra. Metagenomic analyses revealed that microcosms amended with untreated HMWDOM and controls became dominated by Alteromonas genera ( 60% total sequence reads). In contrast, KOH-DOM and HCl-DOM amended microcosms yielded greater bacterial diversity; Alteromonas genera comprised 25% of sequence reads, with differences primarily accounted for by proportional increases in vibrio, roseobacter, rugeria and marinomonas clades. Transcriptomic analyses identified differential gene expression during growth on each DOM fraction. This study provides new insight into specific chemical moieties that may limit the bacterial degradation rate of semi-labile HMWDOM in the ocean.

Optical properties and bioavailability of dissolved organic matter along a flow-path continuum from soil pore waters to the Kolyma River mainstem, East Siberia

NASA Astrophysics Data System (ADS)

Frey, Karen E.; Sobczak, William V.; Mann, Paul J.; Holmes, Robert M.

2016-04-01

The Kolyma River in northeast Siberia is among the six largest Arctic rivers and drains a region underlain by vast deposits of Holocene-aged peat and Pleistocene-aged loess known as yedoma, most of which is currently stored in ice-rich permafrost throughout the region. These peat and yedoma deposits are important sources of dissolved organic matter (DOM) to inland waters that in turn play a significant role in the transport and ultimate remineralization of organic carbon to CO2 and CH4 along the terrestrial flow-path continuum. The turnover and fate of terrigenous DOM during offshore transport largely depends upon the composition and amount of carbon released to inland and coastal waters. Here, we measured the ultraviolet-visible optical properties of chromophoric DOM (CDOM) from a geographically extensive collection of waters spanning soil pore waters, streams, rivers, and the Kolyma River mainstem throughout a ˜ 250 km transect of the northern Kolyma River basin. During the period of study, CDOM absorption coefficients were found to be robust proxies for the concentration of DOM, whereas additional CDOM parameters such as spectral slopes (S) were found to be useful indicators of DOM quality along the flow path. In particular, the spectral slope ratio (SR) of CDOM demonstrated statistically significant differences between all four water types and tracked changes in the concentration of bioavailable DOC, suggesting that this parameter may be suitable for clearly discriminating shifts in organic matter characteristics among water types along the full flow-path continuum across this landscape. However, despite our observations of downstream shifts in DOM composition, we found a relatively constant proportion of DOC that was bioavailable ( ˜ 3-6 % of total DOC) regardless of relative water residence time along the flow path. This may be a consequence of two potential scenarios allowing for continual processing of organic material within the system, namely (a) aquatic microorganisms are acclimating to a downstream shift in DOM composition and/or (b) photodegradation is continually generating labile DOM for continued microbial processing of DOM along the flow-path continuum. Without such processes, we would otherwise expect to see a declining fraction of bioavailable DOC downstream with increasing residence time of water in the system. With ongoing and future permafrost degradation, peat and yedoma deposits throughout the northeast Siberian region will become more hydrologically active, providing greater amounts of DOM to fluvial networks and ultimately to the Arctic Ocean. The ability to rapidly and comprehensively monitor shifts in the quantity and quality of DOM across the landscape is therefore critical for understanding potential future feedbacks within the Arctic carbon cycle.

Spatially controlled carbon sponge for targeting internalized radioactive materials in human body.

PubMed

Hong, Jin-Yong; Oh, Wan-Kyu; Shin, Keun-Young; Kwon, Oh Seok; Son, Suim; Jang, Jyongsik

2012-07-01

Carbon sponge, an adsorbent with spatially controlled structure is demonstrated for targeting internalized radiocesium and other radionuclides in human body. Three dimensionally ordered macroporous (3DOM) carbons derived from inverse opal replicas of colloidal-crystal template exhibit large surface area and high porosity, resulting in highly efficient adsorbents for radionuclides. It is also possible to enhance binding affinity and selectivity to radionuclide targets by decoration of 3DOM carbon surfaces with Prussian blue (PB) nanoparticles, and synthesized PB nanoparticles reveal low toxicity toward macrophage cells with potential advantages over oral administration. It is noteworthy that the maximum (133)Cs adsorption capacity of PB-decorated 3DOM carbons is 40.07 mmol g(-1) which is ca. 30 and 200 times higher than that of commercialized medicine Radiogardase(®) and bulk PB, respectively. Further, adsorption kinetics study indicates that the PB-decorated 3DOM carbons have the homogenous surface for (133)Cs ion adsorption and all sites have equal adsorption energies in terms of ion exchange between the cyano groups of the PB-decorated 3DOM carbons and radionuclides. As a concept of the oral-administrable "carbon sponge", the PB-decorated 3DOM carbons offer useful implications in the separation science of radioactive materials and important insight for designing novel materials for treatment of patients or suspected internal contamination with radioactive materials. Copyright © 2012 Elsevier Ltd. All rights reserved.

Distribution, Source and Fate of Dissolved Organic Matter in Shelf Seas

NASA Astrophysics Data System (ADS)

Carr, N.; Mahaffey, C.; Hopkins, J.; Sharples, J.; Williams, R. G.; Davis, C. E.

2016-02-01

Dissolved organic matter (DOM) is a complex array of molecules containing carbon (DOC), nitrogen (DON) and phosphorous (DOP), and represents the largest pool of organic matter in the marine environment. DOM in the sea originates from a variety of sources, including allochthonous inputs of terrestrial DOM from land via rivers, and autochthonous inputs through in-situ biotic processes that include phytoplankton exudation, grazing and cell lysis. Marine DOM is a substrate for bacterial growth and can act as a source of nutrients for autotrophs. However, a large component of DOM is biologically refractory. This pool is carbon-rich and nutrient-poor, and can transport and store its compositional elements over large areas and on long time scales. The role of DOM in the shelf seas is currently unclear, despite these regions acting as conduits between the land and open ocean, and also being highly productive ecosystems. Using samples collected across the Northwest European Shelf Sea, we studied the distribution, source, seasonality and potential fate of DOM using a combination of analytical tools, including analysis of amino acids, DOM absorbance spectra and excitation emission matrices, in conjunction with parallel factor analysis (PARAFAC). Strong cross shelf and seasonal gradients in DOM source and lability were found. We observed a strong seasonally dependent significant correlation between salinity and terrestrial DOM in the bottom mixed layer, an enrichment of DOM at the shelf edge in winter and a three-fold increase in fresh marine DOM coinciding with the timing of a spring bloom. Together, our findings illustrate the dynamic nature of DOM in shelf seas over a seasonal cycle and, highlight the potential for DOM to play a key role in the carbon cycle in these regions.

Contrasting effects of photochemical and microbial degradation on Cu(II) binding with fluorescent DOM from different origins.

PubMed

Xu, Huacheng; Guan, Dong-Xing; Zou, Li; Lin, Hui; Guo, Laodong

2018-08-01

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV-Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Tree species related functional properties of dissolved and total organic matter in throughfall, stemflow and forest floor solutions

NASA Astrophysics Data System (ADS)

Michalzik, Beate; Bischoff, Sebastian; Schwarz, Martin; Siemens, Jan; Thieme, Lisa; Wilcke, Wolfgang

2016-04-01

The amount and chemical nature of water-bound organic matter is a prerequisite for advancing our understanding of the C and nutrient cycling and associated ecosystem processes. While many investigations have addressed the nature and dynamics of DOM in terrestrial ecosystems, only a few have investigated the dynamics and composition of water-bound total OM (TOM) including the particulate organic matter fraction (POM; 0.45 μm < POM < 500 μm). Since water-bound element and nutrient concentrations are conventionally measured after 0.45 μm-filtration, the exclusion of the POM fraction results in misleading inferences and budgeting gaps of nutrient and energy fluxes in terrestrial ecosystems. Furthermore, tree species differ in leaf composition (e.g. nutrient, polyphenols content) and leaf litter quality, which in turn affect a variety of ecosystem processes. Nevertheless, the composition and amount of DOM and TOM derived from living plant material via throughfall (TF), stemflow (SF) and its compositional fate traversing the forest floor (FF) are insufficiently understood. In particular we asked: How do tree species and forest types affect the amount of dissolved and particulate C and N in TF and FF solutions and thus the input into the mineral soil? Do functional properties (e.g. aromaticity) of DOM and TOM differ in TF, SF and FF solutions collected in beech and spruce stands and among different beech stands across Germany? To monitor (mineral) soil input fluxes of DOM and POM in different spruce and beech forests, we fortnightly sampled TF and FF solution over three years (2010-2012) in the "Hainich-Dün-Exploratory", Thuringia, Central Germany, which forms part of the DFG SPP 1374 "Exploratories for Large-scale and Long-term Functional Biodiversity Research". To characterize chemical properties of DOM and TOM, we applied solid-state 13C NMR spectroscopy to TF, SF and FF solutions from three European beech regions across Germany and from Norway spruce sites of the Hainich-Dün-Exploratory. Fluxes of POC and PN were highly variable between years and added significantly to the annual budgets of DOC and DN in TF and FF solutions especially in beech forests. The non-consideration of these particle-bound element fluxes remarkable underestimates the TOC input to the soil by 30 to 40% and those of TN by 10 to 20%. We therefore emphasize the imperative to include POC and PN fluxes into C and N budgeting of forest ecosystems. 13C NMR spectroscopy revealed remarkable tree-species related differences in the composition of DOM and TOM. Compared to DOM, TOM generally showed higher intensities for the alkyl C region and lower ones for lignin-derived and aromatic C of the aryl C region resulting in lower aromaticity indices and a diminished degree of humification. Differences in the structural composition of DOM and TOM under beech lessened in the order: throughfall > stemflow > forest floor leachate. Compared to spruce, TF DOM under beech concordantly showed the highest intensities of aromatic and phenolic C and lowest ones of alkyl-C. Phenolic compounds are known for their allelopathic potential successfully impairing competing plants and hence altering ecosystem structure and functions - mechanisms being still imperfectly understood.

Molecular characterization of dissolved organic matter during the Arctic spring melt period

NASA Astrophysics Data System (ADS)

Gueguen, C.; Mangal, V.; Shi, Y. X.

2016-02-01

The application of high resolution electrospray ionization mass spectrometry has advanced our understanding of dissolved organic matter (DOM) at molecular level. The arctic spring melt period has been largely undersampled owing to logistical and safety issues, yet this period is extremely important to the overall flux of DOM and related contaminants including metals from high latitude rivers. In this study, we present high resolution molecular composition of 35 DOM samples collected in the Churchill River (Manitoba) during the 2015 spring melt period. As spring melt progresses, a significant change in the two most dominant carbon pools, protein and lignin, was observed. For example, the relative abundance of proteins detected in the river DOM samples increased from 19 to 44% during the spring flush, likely reflecting a change in DOM source. Similar patterns were found using fluorescence spectroscopy.

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.

Bacterial community structure and dissolved organic matter in repeatedly flooded subsurface karst water pools.

PubMed

Shabarova, Tanja; Villiger, Jörg; Morenkov, Oleg; Niggemann, Jutta; Dittmar, Thorsten; Pernthaler, Jakob

2014-07-01

Bacterial diversity, community assembly, and the composition of the dissolved organic matter (DOM) were studied in three temporary subsurface karst pools with different flooding regimes. We tested the hypothesis that microorganisms introduced to the pools during floods faced environmental filtering toward a 'typical' karst water community, and we investigated whether DOM composition was related to floodings and the residence time of water in stagnant pools. As predicted, longer water residence consistently led to a decline of bacterial diversity. The microbial assemblages in the influx water harbored more 'exotic' lineages with large distances to known genotypes, yet these initial communities already appeared to be shaped by selective processes. β-Proteobacterial operational taxonomic units (OTUs) closely related to microbes from subsurface or surface aquatic environments were mainly responsible for the clustering of samples according to water residence time in the pools. By contrast, several Cytophagaceae and Flavobacteriaceae OTUs were related to different floodings, which were also the main determinants of DOM composition. A subset of compounds distinguishable by molecular mass and O/C content were characteristic for individual floods. Moreover, there was a transformation of DOM in stagnant pools toward smaller and more aromatic compounds, potentially also reflecting microbial utilization. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Evaluating Changes in the Molecular Composition and Optical Properties of Pacific Ocean Dissolved Organic Matter (DOM) caused by Borodeuteride Reduction

NASA Astrophysics Data System (ADS)

Bianca, M.; Blough, N. V.; Del Vecchio, R.; Cartisano, C. M.; Schmitt-Kopplin, P.; Gonsior, M.

2016-02-01

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) is a powerful tool to obtain detailed molecular information for complex DOM and was combined in this study with optical measurements to determine the molecular fingerprint of Pacific Ocean DOM before and after borodeuteride reduction. Selective chemical reductions, using sodium borodeuteride, has been previously demonstrated to produce unique mass markers of ketone and aldehyde-containing species in ultrahigh resolution mass spectrometry. These functional groups have also been proposed to be responsible for chromophoric dissolved organic matter (CDOM) long wavelength optical properties through charge transfer interactions and their chemical reduction has shown to irreversibly alter the CDOM optical properties. ESI-FT-ICR MS coupled with borodeuteride reduction was thus applied to reference material, Suwannee River Fulvic Acid (SRFA), and CDOM extracts collected from Station ALOHA, in the North Pacific Ocean during December 2014. Results showed distinct differences between samples collected at different depths, indicating that the combination of FT-ICR-MS with borodeuteride reduction is a useful analytical tool to further understand marine DOM molecular composition. When this method is combined with optical measurements, specific insights into the CDOM composition can also be obtained.

Microbial degradation of terrigenous dissolved organic matter and potential consequences for carbon cycling in brown-water streams.

PubMed

Fasching, Christina; Behounek, Barbara; Singer, Gabriel A; Battin, Tom J

2014-05-15

Streams receive substantial terrestrial deliveries of dissolved organic matter (DOM). The chromophoric (CDOM) fraction of terrestrial deliveries confers the brown colour to streamwater, often understood as browning, and plays a central role in aquatic photochemistry and is generally considered resistant to microbial metabolism. To assess the relevance of terrigenous DOM for carbon fluxes mediated by stream microorganisms, we determined the bioavailable fraction of DOM and microbial carbon use efficiency (CUE), and related these measures to partial pressure of CO2 in headwater streams spanning across a browning gradient. Fluorescence and absorbance analyses revealed high molecular weight and aromaticity, and elevated contributions from humic-like components to characterize terrestrial CDOM. We found that microorganisms metabolized this material at the cost of low CUE and shifted its composition (from fluorescence and absorbance) towards less aromatic and low-molecular weight compounds. Respiration (from CUE) was related to CO2 supersaturation in streams and this relationship was modulated by DOM composition. Our findings imply that terrigenous DOM is respired by microorganisms rather than incorporated into their biomass, and that this channelizes terrigenous carbon to the pool of CO2 potentially outgassing from streams into the atmosphere. This finding may gain relevance as major terrigenous carbon stores become mobilized and browning progresses.

Microbial degradation of terrigenous dissolved organic matter and potential consequences for carbon cycling in brown-water streams

PubMed Central

Fasching, Christina; Behounek, Barbara; Singer, Gabriel A.; Battin, Tom J.

2014-01-01

Streams receive substantial terrestrial deliveries of dissolved organic matter (DOM). The chromophoric (CDOM) fraction of terrestrial deliveries confers the brown colour to streamwater, often understood as browning, and plays a central role in aquatic photochemistry and is generally considered resistant to microbial metabolism. To assess the relevance of terrigenous DOM for carbon fluxes mediated by stream microorganisms, we determined the bioavailable fraction of DOM and microbial carbon use efficiency (CUE), and related these measures to partial pressure of CO2 in headwater streams spanning across a browning gradient. Fluorescence and absorbance analyses revealed high molecular weight and aromaticity, and elevated contributions from humic-like components to characterize terrestrial CDOM. We found that microorganisms metabolized this material at the cost of low CUE and shifted its composition (from fluorescence and absorbance) towards less aromatic and low-molecular weight compounds. Respiration (from CUE) was related to CO2 supersaturation in streams and this relationship was modulated by DOM composition. Our findings imply that terrigenous DOM is respired by microorganisms rather than incorporated into their biomass, and that this channelizes terrigenous carbon to the pool of CO2 potentially outgassing from streams into the atmosphere. This finding may gain relevance as major terrigenous carbon stores become mobilized and browning progresses. PMID:24828296

Three-dimensionally ordered macroporous Li2FeSiO4/C composite as a high performance cathode for advanced lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Zhengping; Liu, Jiatu; Ji, Ran; Zeng, Xiaohui; Yang, Shuanglei; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

2016-10-01

Li2MSiO4 (M = Mn, Fe, Co, Ni, et al.) has received great attention because of the theoretical possibility to reversibly deintercalate two Li+ ions from the structure. However, the silicates still suffer from low electronic conductivity, sluggish lithium ion diffusion and structural instability upon deep cycling. In order to solve these problems, a "hard-soft" templating method has been developed to synthesize three-dimensionally ordered macroporous (3DOM) Li2FeSiO4/C composites. The 3DOM Li2FeSiO4/C composites show a high reversible capacity (239 mAh g-1) with ∼1.50 lithium ion insertion/extraction, a capacity retention of nearly 100% after 420 cycles and excellent rate capability. The enhanced electrochemical performance is ascribed to the interconnected carbon framework that improves the electronic conductivity and the 3DOM structure that offers short Li ion diffusion pathways and restrains volumetric changes.

Importance of allochthonous and autochthonous dissolved organic matter in Fe(II) oxidation: A case study in Shizugawa Bay watershed, Japan.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro

2017-08-01

Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1  s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transformations of the chemical compositions of high molecular weight DOM along a salinity transect: Using two dimensional correlation spectroscopy and principal component analysis approaches

NASA Astrophysics Data System (ADS)

Abdulla, Hussain A. N.; Minor, Elizabeth C.; Dias, Robert F.; Hatcher, Patrick G.

2013-10-01

In a study of chemical transformations of estuarine high-molecular-weight (HMW, >1000 Da) dissolved organic matter (DOM) collected over a period of two years along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA, δ13C values, N/C ratios, and principal component analysis (PCA) of the solid-state 13C NMR (nuclear magnetic resonance) spectra of HMW-DOM show an abrupt change in both its sources and chemical structural composition occurring around salinity 20. HMW-DOM in the lower salinity region had lighter isotopic values, higher aromatic and lower carbohydrate contents relative to that in the higher salinity region. These changes around a salinity of 20 are possibly due to introduction of a significant amount of new carbon (autotrophic DOM) to the transect. PC-1 loadings plot shows that spatially differing DOM components are similar to previously reported 13C NMR spectra of heteropolysaccharides (HPS) and carboxyl-rich alicyclic molecules (CRAM). Applying two dimensional correlation spectroscopy techniques to 1H NMR spectra from the same samples reveals increases in the contribution of N-acetyl amino sugars, 6-deoxy sugars, and sulfated polysaccharides to HPS components along the salinity transect, which suggests a transition from plant derived carbohydrates to marine produced carbohydrates within the HMW-DOM pool. In contrast to what has been suggested previously, our combined results from 13C NMR, 1H NMR, and FTIR indicate that CRAM consists of at least two different classes of compounds (aliphatic polycarboxyl compounds and lignin-like compounds).

Elemental composition and optical properties reveal changes in dissolved organic matter along a permafrost thaw chronosequence in a subarctic peatland

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hodgkins, Suzanne B.; Tfaily, Malak M.; Podgorski, David C.

2016-08-01

The fate of carbon stored in permafrost-zone peatlands represents a significant uncertainty in global climate modeling. Given that the breakdown of dissolved organic matter (DOM) is often a major pathway for decomposition in peatlands, knowledge of DOM reactivity under different permafrost regimes is critical for determining future climate feedbacks. To explore the effects of permafrost thaw and resultant plant succession on DOM reactivity, we used a combination of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), UV/Vis absorbance, and excitation-emission matrix spectroscopy (EEMS) to examine the DOM elemental composition and optical properties of 27 pore water samples gathered frommore » various sites along a permafrost thaw sequence in Stordalen Mire, a thawing subarctic peatland in northern Sweden. The presence of dense Sphagnum moss, a feature that is dominant in the intermediate thaw stages, appeared to be the main driver of variation in DOM elemental composition and optical properties at Stordalen. Specifically, DOM from sites with Sphagnum had greater aromaticity, higher average molecular weights, and greater O/C, consistent with a higher abundance of phenolic compounds that likely inhibit decomposition. These compounds are released by Sphagnum and may accumulate due to inhibition of phenol oxidase activity by the acidic pH at these sites. In contrast, sites without Sphagnum, specifically fully-thawed rich fens, had more saturated, more reduced compounds, which were high in N and S. Optical properties at rich fens were indicated the presence of microbially-derived DOM, consistent with the higher decomposition rates previously measured at these sites. These results indicate that Sphagnum acts as an inhibitor of rapid decomposition and CH4 release in thawing subarctic peatlands, consistent with lower rates of CO2 and CH4 production previously observed at these sites. However, this inhibitory effect may disappear if Sphagnumdominated bogs transition to more waterlogged rich fens that contain very little to no living Sphagnum. Release of this inhibition allows for higher levels of microbial activity and potentially greater CH4 release, as has been observed in these fen sites.« less

Elemental composition and optical properties reveal changes in dissolved organic matter along a permafrost thaw chronosequence in a subarctic peatland

NASA Astrophysics Data System (ADS)

Hodgkins, Suzanne B.; Tfaily, Malak M.; Podgorski, David C.; McCalley, Carmody K.; Saleska, Scott R.; Crill, Patrick M.; Rich, Virginia I.; Chanton, Jeffrey P.; Cooper, William T.

2016-08-01

The fate of carbon stored in permafrost-zone peatlands represents a significant uncertainty in global climate modeling. Given that the breakdown of dissolved organic matter (DOM) is often a major pathway for decomposition in peatlands, knowledge of DOM reactivity under different permafrost regimes is critical for determining future climate feedbacks. To explore the effects of permafrost thaw and resultant plant succession on DOM reactivity, we used a combination of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), UV/Vis absorbance, and excitation-emission matrix spectroscopy (EEMS) to examine the DOM elemental composition and optical properties of 27 pore water samples gathered from various sites along a permafrost thaw sequence in Stordalen Mire, a thawing subarctic peatland in northern Sweden. The presence of dense Sphagnum moss, a feature that is dominant in the intermediate thaw stages, appeared to be the main driver of variation in DOM elemental composition and optical properties at Stordalen. Specifically, DOM from sites with Sphagnum had greater aromaticity, higher average molecular weights, and greater O/C, consistent with a higher abundance of phenolic compounds that likely inhibit decomposition. These compounds are released by Sphagnum and may accumulate due to inhibition of phenol oxidase activity by the acidic pH at these sites. In contrast, sites without Sphagnum, specifically fully-thawed rich fens, had more saturated, more reduced compounds, which were high in N and S. Optical properties at rich fens indicated the presence of microbially-derived DOM, consistent with the higher decomposition rates previously measured at these sites. These results indicate that Sphagnum acts as an inhibitor of rapid decomposition and CH4 release in thawing subarctic peatlands, consistent with lower rates of CO2 and CH4 production previously observed at these sites. However, this inhibitory effect may disappear if Sphagnum-dominated bogs transition to more waterlogged rich fens that contain very little to no living Sphagnum. Release of this inhibition allows for higher levels of microbial activity and potentially greater CH4 release, as has been observed in these fen sites.

Organic Sulfur Associated with Aquatic Humic Substances

NASA Astrophysics Data System (ADS)

Aiken, G.; Vairavamurthy, M. A.; Ravichandran, M.

2003-12-01

This study examines the speciation and reactivity of organic sulfur associated with dissolved organic matter isolated from a variety of freshwater environments and the Pacific Ocean. The isolates, which included aquatic humic substances, were obtained using XAD resins and exhibited a wide range of elemental compositions, aromatic carbon contents, and molecular weights. Organic sulfur contents for the samples ranged from 0.4% to 1.9% of the atomic composition and were strongly dependent on the redox chemistry of the environments whence the samples originated, especially with regard to potential interactions with sulfide in sulfate reducing environments. The speciation of the sulfur associated with these samples was investigated using X-ray adsorption near edge spectroscopy (XANES). The samples, all obtained from oxic environments, contained reduced sulfur moieties. Reduced sulfur content (thiophene, organic sulfides and thiols) ranged from 22-70%. In general, humic acid fractions were found to have the largest percentage of reduced sulfur, followed by the fulvic acid and hydrophobic acid fractions. Hydrophilic fractions of the DOC contained a large percentage of oxidized organic sulfur (sulfonate and sulfate moieties). To assess the significance of reduced S content on interactions with soft metals, an environmentally significant process, the binding strength and binding capacity of Hg with organic matter isolated from the Florida Everglades were determined using equilibrium dialysis ligand exchange. Based on elemental analyses and XANES, the DOM sample from the Everglades used in our binding experiments had a reduced-S content of approximately 1.0%. Very strong interactions (KDOM' = 1023.2+/-0.5 L kg-1) were observed at Hg/DOM ratios below approximately 1 μ g Hg per mg DOM. Only a small fraction (approximately 2%) of the reduced-S groups were involved with the strongest interactions between Hg and DOM, suggesting that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios ranging from 0.01 to 10 ng of Hg/mg of DOM) is controlled by a small fraction of DOM molecules containing reactive sulfur functional groups.

Seasonal Changes in Estuarine Dissolved Organic Matter Due to Variations in Discharge, Flushing Times and Wind-driven Mixing Events

NASA Astrophysics Data System (ADS)

Dixon, Jennifer Louise

Estuaries are highly productive habitats that transport and transform organic matter (OM), experience large changes in ionic composition and act as a transition zone between terrestrial and marine environments (Paerl et al. 1998; Markager et al. 2011; Osburn et al. 2012). OM source and matrix effects (such as salinity and pH) influence the chemical structure of DOM in estuaries and therefore affect its bioavailability, photo-reactivity, and its overall fate in these systems (Jaffe et al. 2004; Boyd et al. 2010; Pace et al. 2012; Osburn et al. 2012; Cawley et al. 2013). Within estuaries, dissolved organic matter (DOM) is a heterogeneous mixture of aromatic and aliphatic compounds, and its composition in aquatic systems varies spatially and temporally with source (Bauer and Bianchi 2011). However, the main source of DOM in estuaries, rivers and other aquatic systems, originates from vascular plant detritus, soil humus, older fossil (i.e., petrogenic) organic carbon, black carbon, marine OM and in situ production (Hedges 2002; Houghton 2007; Bauer and Bianchi 2011). Chromophoric dissolved organic matter (CDOM), the light absorbing fraction of DOM, can be characterized using optical methods such as absorption and fluorescence spectroscopy (e.g. Coble, 1996; Stedmon and Markager, 2003). By analyzing the spatial and temporal variability of DOM and CDOM within estuaries, information pertaining to OM source and fate across the freshwater-marine continuum can be obtained. These methods offer an inexpensive, non-destructive means for obtaining sensitive measurements of a diverse group of organic compounds. By using this technology to analyze the spatial and temporal variability of CDOM within estuaries, information pertaining to OM source and fate across the freshwater-marine continuum can be obtained (Fellman et al. 2011; Osburn et al. 2012; Murphy et al. 2014). Chemical biomarkers are also routinely used to identify DOM sources in coastal waters. Examples are carbon stable isotopes (Bauer, 2002) and lignin (e.g., Benner and Opsahl, 2001; Harvey and Mannino, 2001). Marine DOM derived from phytoplankton typically has carbon stable isotope (delta13C) values that range from --20 to --22‰, while terrestrial DOM derived from C3 land plants typically have delta13C values that range from --26 to --28‰ (Bauer, 2002). Lignin is an important component of vascular plants, thus making it a unique geochemical biomarker, which can be used to trace the fate of terrestrial DOM in coastal seawater (e.g., Hernes and Benner, 2003; Walker et al. 2009; Osburn and Stedmon, 2011). Further, the ratios of the different phenolic compounds derived from the oxidation of lignin can be used to distinguish between plant sources (e.g. angiosperm vs. gymnosperm, or woody vs. non-woody tissue) and the extent of exposure to degradation (Hedges et al. 1988). The highly productive, eutrophic waters of the Neuse River Estuary (NRE), in eastern North Carolina, USA, serve as a transition zone for terrigenous DOM between the head of the Neuse River and Pamlico Sound. Previous studies have determined that the NRE is dominated by inputs from riverine discharge, yet very clear shifts in DOM quality are apparent as discharge varied (Paerl et al. 1998; Osburn et al. 2012). Furthermore, flushing times within the NRE will aid in determining whether DOM is primarily autochthonous or allochthonous and if it is processed internally or transported downstream to the Pamlico Sound (Paerl et al. 1998; Mari et al. 2007, Peierls et al. 2012). Therefore, the main sources of DOM and its composition can change throughout an estuary depending on the hydrodynamic conditions. For example, increases in flushing time may allow for the accumulation of autochthonous DOM because of (1) planktonic communities within the water column having more time to utilize nutrients within the system, resulting in phytoplankton blooms and (2) lower inputs of allochthonous OM from the NRE's watershed (Dixon et al. accepted). Therefore, the main sources of DOM and its composition can change throughout an estuary depending on the hydrodynamic conditions.

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

USGS Publications Warehouse

Henneberry, Yumiko K.; Kraus, Tamara E.C.; Nico, Peter S.; Horwath, William R.

2012-01-01

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Extraneous dissolved organic matter enhanced adsorption of dibutyl phthalate in soils: Insights from kinetics and isotherms.

PubMed

Wu, Wei; Sheng, Hongjie; Gu, Chenggang; Song, Yang; Willbold, Sabine; Qiao, Yan; Liu, Guangxia; Zhao, Wei; Wang, Yu; Jiang, Xin; Wang, Fang

2018-08-01

The widespread use of plastic film, especially in agricultural practices, has resulted in phthalic acid esters (PAEs) pollution, which poses risks for greenhouse soils. Application of composted manure is a common agricultural practice that adds extraneous dissolved organic matter (DOM) to the soil, however, the effect of extraneous DOM on the behavior of PAEs in agricultural soil is not clear. Dibutyl phthalate (DBP) was used as a model compound to investigate the effect and mechanism of extraneous DOM on the adsorption kinetics and isotherms of PAEs in two types of soils, through batch experiments and characterization of extraneous DOM and soils using fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The equilibrium adsorption amount of DBP in black soil was higher than in red soil regardless of the presence of extraneous DOM, due to the higher organic matter content of black soil. Hydrophobic partition played a dominant role in the DBP adsorption process of soils with and without extraneous DOM. The addition of DOM enhanced the adsorption capacity of DBP through partition in the two soils, especially at high DBP concentrations. Additions of a lower concentration of DOM better enhanced the adsorption effect than the higher concentrated DOM, due to an increase in water solubility of DBP resulted from excessive extraneous DOM in aqueous phase. Differences in mineral composition of soils led to diverse adsorption mechanisms of DBP as affected by additions of extraneous DOM. The FTIR spectra indicated that the intra-molecular and intermolecular hydrogen bond interactions of carboxylic acids, aromatic CC and CO in amides were involved in DBP adsorption in soils. Therefore, addition of DOM may increase adsorption of DBP in soils and thus influence its bioavailability and transformation in soils. Copyright © 2018 Elsevier B.V. All rights reserved.

The effect of freezing and drying on leaching of DOM from above ground vascular plant material from the Alaskan Arctic

NASA Astrophysics Data System (ADS)

Khosh, M. S.; McClelland, J. W.

2014-12-01

Our understanding of the seasonal dynamics of fluvial dissolved organic matter (DOM) concentrations and fluxes in Arctic catchments has increased substantially during recent years, especially during the spring, which historically has been an under-sampled time period. While a number of studies have observed peaks in both DOM concentrations and fluxes during the spring snowmelt, our knowledge of the mechanisms that control these observations are still lacking. During the initial snowmelt period, frozen ground and the snow matrix act to constrain melt-water to the soil surface. We hypothesize that restriction of flow during this time facilitates leaching of DOM from senescent above ground vegetation and detritus contributing to the high DOM concentrations observed during the spring melt. This study focuses on the effect of freezing and drying on the leaching of dissolved organic carbon and nitrogen (DOC and DON) from above ground vascular plant material. Specifically, we examined the treatment effects of freezing, drying, and freeze-drying on three genera of common Alaskan Arctic vascular plants; Eriophorum (spp.), Carex (spp.), and Salix (spp.). Frozen and freeze-dried plant material released more DOC over the experimental 96 hour leaching period compared to plant material that was only dried. Qualitatively, these patterns were similar among the different plant types, while quantitatively Salix leached more DOC than either Eriophorum or Carex in all treatments. Similar patterns were also seen for DON between the different treatments and among the different plant types. Compositionally, DOM that was leached from frozen and freeze-dried material had higher C:N ratios than material that was only dried. Comparatively, DOM leached from Salix had much higher C:N ratios than either Eriophorum or Carex. During the first 24 hours of leaching, C:N ratios tended to increase followed by a subsequent leveling or decrease, suggesting that the composition of leached DOM varied during the 96 hour time period. Our findings suggest that the seasonal timing of freezing and drying conditions experienced by senesced plant material during the late summer, fall, and winter may impact DOM leaching dynamics on that same plant material the following spring during snowmelt.

Influence of dissolved organic matter concentration and composition on the removal efficiency of perfluoroalkyl substances (PFASs) during drinking water treatment.

PubMed

Kothawala, Dolly N; Köhler, Stephan J; Östlund, Anna; Wiberg, Karin; Ahrens, Lutz

2017-09-15

Drinking water treatment plants (DWTPs) are constantly adapting to a host of emerging threats including the removal of micro-pollutants like perfluoroalkyl substances (PFASs), while concurrently considering how background levels of dissolved organic matter (DOM) influences their removal efficiency. Two adsorbents, namely anion exchange (AE) and granulated active carbon (GAC) have shown particular promise for PFAS removal, yet the influence of background levels of DOM remains poorly explored. Here we considered how the removal efficiency of 13 PFASs are influenced by two contrasting types of DOM at four concentrations, using both AE (Purolite A-600 ® ) and GAC (Filtrasorb 400 ® ). We placed emphasis on the pre-equilibrium conditions to gain better mechanistic insight into the dynamics between DOM, PFASs and adsorbents. We found AE to be very effective at removing both PFASs and DOM, while largely remaining resistant to even high levels of background DOM (8 mg carbon L -1 ) and surprisingly found that smaller PFASs were removed slightly more efficiently than longer chained counterparts, In contrast, PFAS removal efficiency with GAC was highly variable with PFAS chain length, often improving in the presence of DOM, but with variable response based on the type of DOM and PFAS chain length. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optical properties and molecular diversity of dissolved organic matter in the Bering Strait and Chukchi Sea

NASA Astrophysics Data System (ADS)

Gonsior, Michael; Luek, Jenna; Schmitt-Kopplin, Philippe; Grebmeier, Jacqueline M.; Cooper, Lee W.

2017-10-01

Changes in the molecular composition of dissolved organic matter (DOM) and its light absorbing chromophoric component (CDOM) are of particular interest in the Arctic region because of climate change effects that lead to warmer sea surface temperatures and longer exposure to sunlight. We used continuous UV-vis (UV-vis) spectroscopy, excitation emission matrix fluorescence and ultrahigh resolution mass spectrometry during a transect from the Aleutian Islands in the Bering Sea to the Chukchi Sea ice edge through Bering Strait to determine the variability of DOM and CDOM. These data were combined with discrete sampling for stable oxygen isotopes of seawater, in order to evaluate the contributions of melted sea ice versus runoff to the DOM and CDOM components. This study demonstrated that high geographical resolution of optical properties in conjunction with stable oxygen ratios and non-targeted ultrahigh resolution mass spectrometry was able to distinguish between different DOM sources in the Arctic, including identification of labile DOM sources in Bering Strait associated with high algal blooms and sampling locations influenced by terrestrially-derived DOM, such as the terrestrial DOM signal originating from Arctic rivers and dirty/anchor sea ice. Results of this study also revealed the overall variability and chemodiversity of Arctic DOM present in the Bering and Chukchi Seas.

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

USGS Publications Warehouse

Hansen, Angela; Kraus, Tamara; Pellerin, Brian; Fleck, Jacob; Downing, Bryan D.; Bergamaschi, Brian

2016-01-01

Advances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. We measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials overlapped at the end of the 111-day lab experiment, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material even after degradation, with 17 optical properties determined by discriminant analysis to be significant (p<0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring the source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

The Molecular Composition of Dissolved Organic Matter in Forest Soils as a Function of pH and Temperature

PubMed Central

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2015-01-01

We examined the molecular composition of forest soil water during three different seasons at three different sites, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). We examined oxic soils and tested the hypothesis that pH and season correlate with the molecular composition of dissolved organic matter (DOM). We used molecular formulae and their relative intensity from ESI-FT-ICR-MS for statistical analysis. Applying unconstrained and constrained ordination methods, we observed that pH, dissolved organic carbon (DOC) concentration and season were the main factors correlating with DOM molecular composition. This result is consistent with a previous study where pH was a main driver of the molecular differences between DOM from oxic rivers and anoxic bog systems in the Yenisei River catchment. At a higher pH, the molecular formulae had a lower degree of unsaturation and oxygenation, lower molecular size and a higher abundance of nitrogen-containing compounds. These characteristics suggest a higher abundance of tannin connected to lower pH that possibly inhibited biological decomposition. Higher biological activity at a higher pH might also be related to the higher abundance of nitrogen-containing compounds. Comparing the seasons, we observed a decrease in unsaturation, molecular diversity and the number of nitrogen-containing compounds in the course of the year from March to November. Temperature possibly inhibited biological degradation during winter, which could cause the accumulation of a more diverse compound spectrum until the temperature increased again. Our findings suggest that the molecular composition of DOM in soil pore waters is dynamic and a function of ecosystem activity, pH and temperature. PMID:25793306

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota

NASA Astrophysics Data System (ADS)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; Kostka, Joel E.; Hanson, Paul; Chanton, Jeffrey P.

2018-02-01

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone ( 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.

Tracking changes in the optical properties and molecular composition of dissolved organic matter during drinking water production.

PubMed

Lavonen, E E; Kothawala, D N; Tranvik, L J; Gonsior, M; Schmitt-Kopplin, P; Köhler, S J

2015-11-15

Absorbance, 3D fluorescence and ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were used to explain patterns in the removal of chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) at the molecular level during drinking water production at four large drinking water treatment plants in Sweden. When dissolved organic carbon (DOC) removal was low, shifts in the dissolved organic matter (DOM) composition could not be detected with commonly used DOC-normalized parameters (e.g. specific UV254 absorbance - SUVA), but was clearly observed by using differential absorbance and fluorescence or ESI-FT-ICR-MS. In addition, we took a novel approach by identifying how optical parameters were correlated to the elemental composition of DOM by using rank correlation to connect optical properties to chemical formulas assigned to mass peaks from FT-ICR-MS analyses. Coagulation treatment selectively removed FDOM at longer emission wavelengths (450-600 nm), which significantly correlated with chemical formulas containing oxidized carbon (average carbon oxidation state ≥ 0), low hydrogen to carbon ratios (H/C: average ± SD = 0.83 ± 0.13), and abundant oxygen-containing functional groups (O/C = 0.62 ± 0.10). Slow sand filtration was less efficient in removing DOM, yet selectively targeted FDOM at shorter emission wavelengths (between 300 and 450 nm), which commonly represents algal rather than terrestrial sources. This shorter wavelength FDOM correlated with chemical formulas containing reduced carbon (average carbon oxidation state ≤ 0), with relatively few carbon-carbon double bonds (H/C = 1.32 ± 0.16) and less oxygen per carbon (O/C = 0.43 ± 0.10) than those removed during coagulation. By coupling optical approaches with FT-ICR-MS to characterize DOM, we were for the first time able to confirm the molecular composition of absorbing and fluorescing DOM selectively targeted during drinking water treatment. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

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.

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.

Variation in the Humification Degree of Dissolved Organic Matter from Cattle Manure during Composting as Analyzed by Ultraviolet-Visible and Fluorescence Spectroscopy.

PubMed

Chen, Yukun; Jiang, Zhao; Zhang, Xiuyuan; Cao, Bo; Yang, Fan; Wang, Ziyi; Zhang, Ying

2017-11-01

This study investigated the degree of humification of dissolved organic matter (DOM) during different periods of cattle manure composting using ultraviolet-visible (UV-vis) and fluorescence spectroscopy (emission, synchronous scan, and excitation-emission matrix) and determined which method is more suitable for analysis of the humification degree of DOM. Two composting piles were prepared by mixing manure and corn straw. One pile (Pile A [PA]) contained inoculated exogenous composite agents at a ratio of 2% (v/v), and a pile without the addition of inoculants (PNA) served as the control treatment. The results showed that ultraviolet integrated absorption intensities in the range of 226 to 400 nm and 260 to 280 nm and specific ultraviolet absorbances at 254 and 280 nm of both PA and PNA gradually increased with composting time. Based on the fluorescence regional integration analysis and parallel factor analysis, the humic-like substances became the main components of the DOM after composting. Our study demonstrated that the humification degree of DOM was enhanced during composting and that the inoculation composite agent was beneficial for the humification of DOM at the mesophilic and thermophilic phases of the composting process. Moreover, the results of correlation analysis and principal component analysis demonstrated that the fluorescence spectral parameters evaluated the humification degree of DOM during the whole cattle manure composting process better than the UV-vis spectral parameters. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

Application of fluorescence spectroscopy for dissolved organic matter characterization in constructed wetlands

NASA Astrophysics Data System (ADS)

Sardana, A.; Aziz, T. N.; Cottrell, B. A.

2017-12-01

In this presentation we will discuss our ongoing work to characterize the photochemical behavior of dissolved organic matter (DOM) from wastewater treated in constructed wetlands. We have used a suite of spectroscopic and chromatographic techniques to characterize the DOM and to quantify the potential production of reactive oxygenated species (ROS). In the present study, DOM was fractionated based on its hydrophobicity and both the natural water isolates and fractionated DOM were characterized using SUVA254, spectral slope ratios, excitation emission matrix fluorescence spectroscopy (EEMs) and proton nuclear magnetic resonance (1H NMR). Photodegradation of wetland DOM and the formation of the hydroxyl radical (*OH), singlet oxygen (1O2), and the triplet-excited state (3DOM*) was also determined to assess the reactivity of DOM. EEM spectra exhibited the four main fluorescence peaks that are characteristic of DOM: peak A humic-like DOM, Peak C (fulvic or chromophoric DOM), Peak M (marine-like DOM), and peak T (tryptophan or protein-like absorbance). Two additional observed peaks with shorter emission wavelengths (A' Ex/Em = 243/278 nm and T' Ex/Em = 272/319 nm) were attributed to the microbial DOM in wastewater effluent. The spectral slope ratios decreased from 1.46 at the wetland inlet to 0.89 at the wetland outlet. The protein-like Peak T fluorescence decreased from 50% at the wetland inlet to 6.7% at the Wetland 2 outlet. A negative correlation between the percent fluorescence of Peak T and Peaks A, C and M confirmed the transition from the spectrum of pure wastewater with a primarily protein-like signature to a spectrum characteristic of terrestrially derived DOM. This transition coincided with enhanced formation rates and steady state concentrations of photochemically produced reactive intermediates (PPRIs). Size Exclusion Chromatography demonstrated that the influent wastewater had a lower molecular weight as compared to downstream wetland locations. Fractionation of DOM based on hydrophobicity followed by 1H NMR analysis indicated an increase in the complexity and composition of wetland effluent DOM. This presentation will summarize these findings and present results from our new microcosm constructed wetlands built to develop insights into DOM production and photochemical characteristics.

Using dissolved organic matter age and composition to detect permafrost thaw in boreal watersheds of interior Alaska

NASA Astrophysics Data System (ADS)

O'Donnell, Jonathan A.; Aiken, George R.; Walvoord, Michelle A.; Raymond, Peter A.; Butler, Kenna D.; Dornblaser, Mark M.; Heckman, Katherine

2014-11-01

Recent warming at high latitudes has accelerated permafrost thaw, which can modify soil carbon dynamics and watershed hydrology. The flux and composition of dissolved organic matter (DOM) from soils to rivers are sensitive to permafrost configuration and its impact on subsurface hydrology and groundwater discharge. Here, we evaluate the utility of DOM composition and age as a tool for detecting permafrost thaw in three rivers (Beaver, Birch, and Hess Creeks) within the discontinuous permafrost zone of interior Alaska. We observed strong temporal controls on Δ14C content of hydrophobic acid isolates (Δ14C-HPOA) across all rivers, with the most enriched values occurring during spring snowmelt (75 ± 8‰) and most depleted during winter flow (-21 ± 8‰). Radiocarbon ages of winter flow samples ranged from 35 to 445 yr BP, closely tracking estimated median base flow travel times for this region (335 years). During spring snowmelt, young DOM was composed of highly aromatic, high molecular-weight compounds, whereas older DOM of winter flow had lower aromaticity and molecular weight. We observed a significant correlation between Δ14C-HPOA and UV absorbance coefficient at 254 nm (α254) across all study rivers. Using α254 as an optical indicator for Δ14C-HPOA, we also observed a long-term decline in α254 during maximum annual thaw depth over the last decade at the Hess Creek study site. These findings suggest a shift in watershed hydrology associated with increasing active layer thickness. Further development of DOM optical indicators may serve as a novel and inexpensive tool for detecting permafrost degradation in northern watersheds.

Using dissolved organic matter age and composition to detect permafrost thaw in boreal watersheds of interior Alaska

USGS Publications Warehouse

O'Donnell, Jonathan A.; Aiken, George R.; Walvoord, Michelle Ann; Raymond, Peter A.; Butler, Kenna D.; Dornblaser, Mark M.; Heckman, Katherine

2014-01-01

Recent warming at high latitudes has accelerated permafrost thaw, which can modify soil carbon dynamics and watershed hydrology. The flux and composition of dissolved organic matter (DOM) from soils to rivers are sensitive to permafrost configuration and its impact on subsurface hydrology and groundwater discharge. Here, we evaluate the utility of DOM composition and age as a tool for detecting permafrost thaw in three rivers (Beaver, Birch, and Hess Creeks) within the discontinuous permafrost zone of interior Alaska. We observed strong temporal controls on Δ14C content of hydrophobic acid isolates (Δ14C-HPOA) across all rivers, with the most enriched values occurring during spring snowmelt (75 ± 8‰) and most depleted during winter flow (−21 ± 8‰). Radiocarbon ages of winter flow samples ranged from 35 to 445 yr BP, closely tracking estimated median base flow travel times for this region (335 years). During spring snowmelt, young DOM was composed of highly aromatic, high molecular-weight compounds, whereas older DOM of winter flow had lower aromaticity and molecular weight. We observed a significant correlation between Δ14C-HPOA and UV absorbance coefficient at 254 nm (α254) across all study rivers. Usingα254 as an optical indicator for Δ14C-HPOA, we also observed a long-term decline in α254 during maximum annual thaw depth over the last decade at the Hess Creek study site. These findings suggest a shift in watershed hydrology associated with increasing active layer thickness. Further development of DOM optical indicators may serve as a novel and inexpensive tool for detecting permafrost degradation in northern watersheds.

Characterization of spectral responses of dissolved organic matter (DOM) for atrazine binding during the sorption process onto black soil.

PubMed

Wang, Yifan; Zhang, Xinyuan; Zhang, Xing; Meng, Qingjuan; Gao, Fengjie; Zhang, Ying

2017-08-01

This study was aim to investigate the interaction between soil-derived dissolved organic matter (DOM) and atrazine as a kind of pesticides during the sorption process onto black soil. According to the experimental data, the adsorption capacity of Soil + DOM, Soil and DOM were 41.80, 31.45 and 9.35 mg kg -1 , separately, which indicated that DOM significantly enhanced the adsorption efficiency of atrazine by soil. Data implied that the pseudo-second-order kinetic equation could well explain the adsorption process. The adsorption isotherms (R 2  > 0.99) had a satisfactory fit in both Langmuir and Freundlich models. Three-dimensional excitation-emission matrix (3D-EEM), synchronous fluorescence, two-dimensional correlation spectroscopy (2D-COS) and Fourier transform infrared spectroscopy (FT-IR) were selected to analyze the interaction between DOM and atrazine. 3D-EEM showed that humic acid-like substances were the main component of DOM. The fluorescence of DOM samples were gradually quenched with the increased of atrazine concentrations. Synchronous fluorescence spectra showed that static fluorescence quenching was the main quenching process. 2D-COS indicated that the order of the spectral changes were as following: 336 nm > 282 nm. Furthermore, the fluorescence quenching of humic-like fraction occurred earlier than that of protein-like fraction under atrazine surroundings. FT-IR spectra indicated that main compositions of soil DOM include proteins, polysaccharides and humic substances. The findings of this study are significant to reveal DOM played an important role in the environmental fate of pesticides during sorption process onto black soil and also provide more useful information for understanding the interaction between DOM and pesticides by using spectral responses. Copyright © 2017. Published by Elsevier Ltd.

The Effects of Biodegradation and Photodegradation on DOM Optical Properties: Controlled Laboratory Study Using Plant, Soil and Algal Leachates

NASA Astrophysics Data System (ADS)

Hansen, A. M.; Kraus, T. E. C.; Pellerin, B. A.; Fleck, J.

2014-12-01

Many studies use optical properties to infer dissolved organic matter (DOM) composition and origin; however, there are few controlled studies which examine the effects of environmental processing on different DOM sources. Our goal was to better understand the roles DOM plays in wetland environments of the Sacramento-San Joaquin Delta. Therefore, five endmember sources of DOM from this region were selected for use in this study: peat soil (euic, thermic Typic Medisaprists); three aquatic macrophytes (white rice (Oryza sativa); tule (Schoenoplectus acutus); cattail (Typha spp.)); and one diatom (Thalassiosira weissflogii). We measured DOM concentrations (mg C/L) and optical properties (absorbance and fluorescence) of these sources following biological and photochemical degradation over a three month period. DOM concentration decreased by over 90% in plant and algal leachates following 3 months of biodegradation, while photoexposure had negligible effects. The fluorescence index (FI), humic index (HI), specific UV absorbance at 254 nm (SUVA), and carbon-normalized fluorescence of Peaks C and A increased with biodegradation, whereas Peak T decreased. Photoexposure resulted in a decrease of the FI, HI and SUVA values. Our results emphasize the need to better understand how environmental processing affects DOM properties in aquatic environments; the frequently opposing effects of biodegradation and photodegradation, which occur simultaneously in nature, make it challenging to decipher the original DOM source without considering multiple parameters. This dataset can help us better identify which optical properties, either individual or in combination, can provide insight into how biogeochemical processes affect DOM in aquatic environments.

Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils

NASA Astrophysics Data System (ADS)

Sauerwein, Meike; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

2010-05-01

Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils Meike Sauerwein1, Alexander Hanke2, Klaus Kaiser3, Karsten Kalbitz2 1) Dept. of Soil Ecology, Bayreuth Centre of Ecology and Environmental Research (BayCEER), University of Bayreuth, 95440 Bayreuth, Germany, meike.sauerwein@gmail.com 2) Institute of ecosystem dynamics and biodiversity, University of Amsterdam, 1018 WV, Netherlands, a.hanke@uva.nl, k.kalbitz@uva.nl 3) Soil Sciences, Martin Luther University Halle, 06099 Halle, Germany, klaus.kaiser@landw.uni-halle.de Current knowledge on dissolved organic matter (DOM) in soils is based mainly on observations and experiments in aerobic environments. Adsorption to soil minerals is an important mechanism of DOM retention and stabilization against microbial decay under oxic conditions. Under anoxic conditions where hydrous iron oxides, the potential main adsorbents of DOM, possibly dissolve, the importance of adsorption seems questionable. Therefore, we studied the adsorption of DOM to selected soil minerals and to mineral soils under oxic and anoxic conditions. In detail, we tested the following hypotheses: 1. Minerals and soils adsorb less DOM under anoxic conditions than under oxic ones. 2. The reduced adsorption under anoxic conditions is result of the smaller adsorption to hydrous Fe oxides whereas adsorption to clay minerals and Al hydroxides is not sensitive to changes in redox conditions 3. DOM adsorption will increase with the number of redox cycles, thus time of soil formation, due to increasing contents of poorly crystalline Fe oxides. This will, however, cause a stronger sensitivity to redox changes as poor crystalline Fe oxides are more reactive. 4. Aromatic compounds, being preferentially adsorbed under oxic conditions, will be less strongly adsorbed under anoxic conditions. We chose paddy soils as models because their periodically and regular exposure to changing redox cycles, with anoxic conditions during the rice growing period and oxic conditions during harvest and growth of other crops. Soils of a unique chronosequence of paddy soils (50, 300, 700 and 2000 years) in China were studied in direct comparison to non-paddy soils of the same age. In additions, selected soil minerals (goethite, ferrihydrite, amorphous Al hydroxide, hydrobiotite, nontronite and ripodolite), differing in their response to changes in redox conditions, were studied in order to indentify those mineral constituents responsible for redox-induced changes in DOM adsorption to the test soils. The DOM for the adsorption was extracted from composted rice straw as a surrogate for DOM percolating in paddy soils. Batch adsorption experiments were carried out with DOM pre-incubated to give oxic and anoxic conditions and maintaining these redox conditions during the whole procedure. The redox potential resulting from anoxic pre-incubation was about 100 mV, thus in the range of Fe reduction. Besides of dissolved organic carbon (DOC), we determined changes in the composition of DOM by the specific UV absorbance. We also analyzed main cations, anions and redox-sensitive elements to give a comprehensive picture of the effects of changing redox conditions on the dynamics of organic C, N, P, S, Fe and Al. First results indicated indeed less adsorption of DOM to Fe oxides under anoxic than under oxic conditions, with a more pronounced effect for ferrihydrite than for goethite. Maximum adsorption of DOM was more than 50% larger under oxic than under anoxic conditions. The effect was less pronounced but still detectable for clay minerals such as hydrobiotite, nontronite, and ripodolite. The specific UV absorbance of DOM contact with minerals was 20-50% stronger under anoxic than under oxic conditions. These changes in DOM composition indicated that preferential adsorption of aromatic compounds might be limited to aerated soils. We conclude that adsorption, although less strong than under oxic conditions, is an important mechanism of DOM retention also under anoxic conditions. Decreasing amounts of adsorbed DOM and changes in its composition might result in a less effective sorptive stabilization against microbial decay under anoxic than under oxic conditions.

Abundance and Bulk Composition of DOM in the Lower Mississippi and Pearl Rivers (USA)

NASA Astrophysics Data System (ADS)

Duan, S.; Bianchi, T. S.; Shiller, A. M.; Dria, K.; Hatcher, P. G.

2005-05-01

Here we report on temporal changes in the composition of dissolved organic carbon (DOC) and nitrogen (DON) collected in the tidal freshwater region of the lower Mississippi and Pearl Rivers (MR and PR) (USA). Bulk stable carbon isotopes and 13C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight (< 0.2 µm > 1 kDa) dissolved organic matter (HMW DOM). Monthly water samples were collected at one station in each river from August 2001 to July 2003. Surveys of spatial variability (225 km downstream in the MR and from Jackson to Stennis Space Center in the PR) in total DOC and DON were also conducted in both rivers in June 2003. Higher total DOC (336 to 1156 uM), DON (9.3 to 59.5 uM), % HMW DOM (25 to 47 %), ultraviolet (UV) absorption (0.13 to 0.70 /m), and more depleted delta-15N (0.76 to 2.16 per mil) delta-13C (-25.1 to -28.0 permil) were observed in the PR than in the lower MR (223 to 380 uM, 6.1 to 13.4 uM, 16 to 38 %, 0.08 to 0.17 /m, 0.76 to 2.16 permil, -25.7 to -27.1 permil, respectively). 13C-NMR spectra revealed that alkyl and carbohydrate carbons were dominant in HMW DOC in both rivers. However, a significantly lower percentage of aromatic C (13.2 to 16.6 %) and higher carboxyl C (17.1 to 25.8 %) were observed in the lower MR than in the PR (16.9 to 21.3 % and 12.3 to 20.9 %). Total DOC, DON, HMW DOM, and percent aromaticity of HMW DOM were higher in the PR during local flooding events, and lower during low discharge, indicating a coupling between local carbon inputs (soil and wetlands) and regional precipitation events in the PR. Conversely, seasonal variability of total DOC, DON, and HMW DOM in the lower MR was controlled by spatial variability of an integrative signal from watershed inputs and in-situ production from upriver sources, resulting in a more phytoplankton-derived 13C-NMR signature of HMW DOM. Spatially, very little change occurred in total DOC (259 to 282 uM) and DON (8.85 to 13.3 uM) in the downstream survey of the lower MR, compared to decreases of 24 % and 50 % in DOC and DON, respectively, in the PR. Once again local inputs are more important in the PR compared to the MR and likely account for higher variability. Recent lab incubation experiments also suggest that photochemical oxidation, coupled with bacterial degradation of DOM, accounts for significant alteration of DOM in these lower floodplain rivers.

The biogeochemical fingerprint of urbanization: increasing carbon quality in Maine headwater streams

NASA Astrophysics Data System (ADS)

Parr, T.; Cronan, C.; Ohno, T.; Simon, K. S.

2012-12-01

Conversion of land cover to urban use is an accelerating global phenomenon. Physical landscape change manifests as the replacement of forests, grasslands, and wetlands with buildings, novel vegetation, and infrastructure. This physical change also brings with it a change in the human management of the landscape for aesthetic and practical purposes (i.e. road salt applications). Although urbanization's effects on inorganic nutrients have been well studied, far less is known about the interactive influences of urbanization and urban landscape management practices on dissolved organic matter (DOM), a key energy source essential to ecosystem function. We examined the seasonal abundance and composition of DOM, nutrients, and common cations in 116 small streams along a gradient of urbanization (0-60% total watershed imperviousness, TWI), in Maine, USA. Dissolved organic carbon concentration ranged from 0.5 to 20 ppm with no clear relationship to watershed urbanization. In contrast, DOM composition, quantified with specific ultra violet absorbance at 254 nm (SUVA_{254}), fluorescence indices, and parallel factor analysis (PARAFAC), changed considerably with increasing urbanization. SUVA_{254} indicated a shift from higher molecular weight humic compounds (SUVA_{254}>4) toward lower molecular weight compounds (SUVA_{254}<2.5) with increasing urbanization. Fluorescence indices (Fluorescence Index, Humification Index, and α:β) indicated DOM source shifted from allochthonous sources (e.g. plant and soil carbon) toward autochthonously derived compounds (e.g. derivatives of in-stream algal and microbial production). Humic acid-like compounds decreased from 40% to 10% of the fluorescent DOM pool, while fluorescence of more labile compounds increased from 10 to 25% with increasing urbanization. Laboratory bioassays of DOM degradation rates showed that increasing urbanization doubled the bioavailability of DOM. Ratios of DOC:DON declined from 20-50 at TWI<8% to <20 above 8% TWI. Changes in the DOM pool were unrelated to inorganic nutrient concentrations, but were related to base cation concentrations. Concentrations of base cations (Ca^{2+}, Mg^{2+}, K^+, Na^+) increased 3-100 fold with increasing impervious cover. The stoichiometric relationships among Na^+, Cl^- and other base cations suggest road salt application may mobilize base cations into streams draining urbanized watersheds. There was a strong negative relationship between humic-like DOM components and Ca^{2+} (R^2=0.3-0.5, p<0.01) across streams. Bottle incubations of ^1+ and ^{2+} base cation salts over a natural range (0 - 6 mM) showed that ^{2+} cations (esp. Ca^{2+}) preferentially flocculated the humic fraction of DOM (R^2=0.6-0.9, p<0.01). These results indicate that the carbon composition change observed with urbanization in Maine may be controlled by multiple concurrent processes linked to the creation and maintenance of urban landscapes. Our data suggest that a key biogeochemical consequence of urbanization may be an increase in abundance of labile carbon which may have important consequences for ecosystem function in urban systems. This process may be driven by a combination of altered landscape C sources reducing terrestrial C inputs, enhancement of in-stream C production, and base cation enrichment that removing terrestrial C from the aquatic DOM pool in urban landscapes.

Microbial Community Response to Terrestrially Derived Dissolved Organic Matter in the Coastal Arctic.

PubMed

Sipler, Rachel E; Kellogg, Colleen T E; Connelly, Tara L; Roberts, Quinn N; Yager, Patricia L; Bronk, Deborah A

2017-01-01

Warming at nearly twice the global rate, higher than average air temperatures are the new 'normal' for Arctic ecosystems. This rise in temperature has triggered hydrological and geochemical changes that increasingly release carbon-rich water into the coastal ocean via increased riverine discharge, coastal erosion, and the thawing of the semi-permanent permafrost ubiquitous in the region. To determine the biogeochemical impacts of terrestrially derived dissolved organic matter (tDOM) on marine ecosystems we compared the nutrient stocks and bacterial communities present under ice-covered and ice-free conditions, assessed the lability of Arctic tDOM to coastal microbial communities from the Chukchi Sea, and identified bacterial taxa that respond to rapid increases in tDOM. Once thought to be predominantly refractory, we found that ∼7% of dissolved organic carbon and ∼38% of dissolved organic nitrogen from tDOM was bioavailable to receiving marine microbial communities on short 4 - 6 day time scales. The addition of tDOM shifted bacterial community structure toward more copiotrophic taxa and away from more oligotrophic taxa. Although no single order was found to respond universally (positively or negatively) to the tDOM addition, this study identified 20 indicator species as possible sentinels for increased tDOM. These data suggest the true ecological impact of tDOM will be widespread across many bacterial taxa and that shifts in coastal microbial community composition should be anticipated.

Seasonal changes in the chemical quality and biodegradability of dissolved organic matter exported from soils to streams in coastal temperate rainforest watersheds

Treesearch

Jason B. Fellman; Eran Hood; David V. D' Amore; Richard T. Edwards; Dan White

2009-01-01

The composition and biodegradability of streamwater dissolved organic matter (DOM) varies with source material and degree of transformation. We combined PARAFAC modeling of fluorescence excitation-emission spectroscopy and biodegradable dissolved organic carbon (BDOC) incubations to investigate seasonal changes in the lability of DOM along a soil-stream continuum in...

Design, fabrication, and testing of three-dimensionally ordered macroporous materials for pseudomorphic transformation and power storage

NASA Astrophysics Data System (ADS)

Lytle, Justin Conrad

This dissertation details my study of three-dimensionally ordered macroporous (3DOM) materials, which were prepared using polymer latex colloidal crystal templates. These solids are composed of close-packed and three-dimensionally interconnected spherical macropores surrounded by nanoscale solid wall skeletons. This unique architecture offers relatively large surface areas that are accessible by interconnected macropores, making these materials important for innovative catalysis, sensing, and separations applications. In addition, the three-dimensionally alternating dielectric structure can establish photonic stop bands that control the flow of light analogously to the restraint of electronic conduction by electronic bandgaps. Many potential applications would benefit from reducing device feature sizes from the bulk into the nanoscale regime. However, some compositions are more easily prepared as nanostructured materials than others. Therefore, it would be immensely important to develop synthetic methods of transforming solids that are more easily formed with nanoarchitectural features into compositions that are not. Pseudomorphic transformation reactions may be one solution to this problem, since they are capable of altering chemical composition while maintaining shape and structural morphology. Several compositions of inverse opal and nanostructured preforms were investigated in this work to study the effects of vapor-phase and solution-phase conversion reactions on materials with feature sizes ranging from a few nm to tens of mum. 3DOM SiO2 and WO3, nanostructured Ni, and colloidal silica sphere performs were studied to investigate the effects of preform chemistries, feature sizes and shapes, processing temperatures, and reagent ratios on overall pseudomorphic structural retention. Power storage and fuel cell devices based on nanostructured electrodes are a major example of how reducing device component feature sizes can greatly benefit applications. Bulk electrode geometries have diffusion-limited kinetics and relatively low energy and power densities. Nanostructured electrodes offer extremely short ion diffusion pathlengths and relatively numerous reaction sites. 3DOM SnO2 thin films, 3DOM Li4Ti 5O12 powders, and 3DOM carbon monoliths have been fabricated and characterized in this work as Li-ion anode materials, with 3DOM carbon exhibiting an enormous rate capability beyond similarly prepared, but non-templated, bulk carbon. Furthermore, a novel battery design that is three-dimensionally interpenetrated on the nanoscale was prepared and evaluated in this research.

Chemical characterization of dissolved organic matter in an alpine stream from thawing and collapsing permafrost to Qinghai Lake

NASA Astrophysics Data System (ADS)

Wang, Y.; Xu, Y.

2016-12-01

The Tibetan Plateau is the world's largest and highest plateau, approximately two thirds of which is covered by permafrost. Due to recent climate warming, large organic carbon stored in the permafrost is thawing and becomes available for transport to aquatic ecosystems (i.e., stream and lake) as dissolved organic matter (DOM) and fine particulate organic matter (POM). These DOM and POM are not only important food sources for the aquatic food web, but also a significant feedback if remineralized during transport. In this work, we collected water samples along a stream from the headwater in the Permafrost region to the downstream in the Qinghai Lake. The concentration and composition of DOM were determined using high temperature combustion analysis, UV- Vis absorption spectroscopy and fluorescence spectroscopy. The concentration of dissolved organic carbon decreased sharply from 13.87 mg/L to 4.32 mg/L from collapsing permafrost area (3850 m a.s.l.) to the foot of the mountain (3200 m a.s.l.), and then fluctuated in a narrow range between 3.00 mg/L and 4.50 mg/L. The DOM with high humic-like fluorescence, specific UV absorbance (SUVA254), and low spectral slope ratio (S275-295) and fluorescence index (FI) was observed in the headwater, which was distinct difference from that at the middle and downstream area where the DOM are less aromatic and low molecular weight. Meanwhile, the freshness index (β/α) increased slightly in mid and down-stream. This increasing trend for FI and β/α indicated a contribution of recently in situ produced DOM by aquatic bacteria and algae in the stream. We speculate that the biological process is an important way to cause the chemical change of DOM composition and concentration, and therefore the thawing and transport of permafrost carbon may play a key role in sustaining the alpine stream ecosystem.

Long Term Effect of Land Reclamation from Lake on Chemical Composition of Soil Organic Matter and Its Mineralization

PubMed Central

He, Dongmei; Ruan, Honghua

2014-01-01

Since the late 1950s, land reclamation from lakes has been a common human disturbance to ecosystems in China. It has greatly diminished the lake area, and altered natural ecological succession. However, little is known about its impact on the carbon (C) cycle. We conducted an experiment to examine the variations of chemical properties of dissolved organic matter (DOM) and C mineralization under four land uses, i.e. coniferous forest (CF), evergreen broadleaf forest (EBF), bamboo forest (BF) and cropland (CL) in a reclaimed land area from Taihu Lake. Soils and lake sediments (LS) were incubated for 360 days in the laboratory and the CO2 evolution from each soil during the incubation was fit to a double exponential model. The DOM was analyzed at the beginning and end of the incubation using UV and fluorescence spectroscopy to understand the relationships between DOM chemistry and C mineralization. The C mineralization in our study was influenced by the land use with different vegetation and management. The greatest cumulative CO2-C emission was observed in BF soil at 0–10 cm depth. The active C pool in EBF at 10–25 cm had longer (62 days) mean residence time (MRT). LS showed the highest cumulative CO2-C and shortest MRT comparing with the terrestrial soils. The carbohydrates in DOM were positively correlated with CO2-C evolution and negatively correlated to phenols in the forest soils. Cropland was consistently an outlier in relationships between DOM chemistry and CO2-evolution, highlighting the unique effects that this land use on soil C cycling, which may be attributed the tillage practices. Our results suggest that C mineralization is closely related to the chemical composition of DOM and sensitive to its variation. Conversion of an aquatic ecosystem into a terrestrial ecosystem may alter the chemical structure of DOM, and then influences soil C mineralization. PMID:24905998

Small scale variability of transport and composition of dissolved organic matter in the subsoil

NASA Astrophysics Data System (ADS)

Leinemann, T.; Mikutta, R.; Kalbitz, K.; Guggenberger, G.

2016-12-01

Dissolved organic matter (DOM) is the most mobile fraction of carbon in the soil and connects the carbon-rich topsoil with the subsoil where translocated OM may get stabilized. The water flux in soil is highly heterogeneous, both temporarily and spatially. We, therefore, hypothesize that at high flow velocities, DOM can bypass possible mineral binding sites and microorganisms, thus leading to less degraded DOM under high flow velocities. To address this question, we investigated water and DOM fluxes in situ using segmented suction plates (4 x 4 segments on 24 x 24 cm) installed into three soil observatories at three depths (10 cm, 50 cm, and 150 cm) in a Dystric Cambisol under Beech (Fagus sylvatica) near Hannover, Germany. To follow the transport of carbon from the litter layer through the soil, an in situ 13C-labelling experiment has been conducted in January 2015. Concentration of dissolved organic carbon (DOC) and DOM composition was analyzed using high temperature combustion and photometric methods. The amount of transported DOC decreased by ca. 80 % from 10 to 50 cm depth and by 40 % from 50 to 150 cm depth. Different flow patterns existed at the centimeter scale, which were stable over time for individual suction plate segments. The specific UV280 nm absorbance of DOM decreased with increasing soil depth. This indicates a selective loss of aromatic compounds. The influence of different flow regimes on the DOM quality became apparent in the subsoil samples (>50 cm depth) showing a correlation of increasing UV280 nm absorbance with increasing water flux. The 13C-labelling experiment showed that after 10 month just 0.3 % of the DOC in 150 cm depth was derived from fresh litter. The transport of leaf litter carbon seemed to be controlled by the flow regime as the DO13C ratio and the water flux correlated positively. This can be an indication for the importance of preferential flow on carbon transport to the subsoil.

Changes in Dissolved Organic Matter Composition and Disinfection Byproduct Precursors in Advanced Drinking Water Treatment Processes.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2018-03-20

Molecular changes in dissolved organic matter (DOM) from treatment processes at two drinking water treatment plants in Japan were investigated using unknown screening analysis by Orbitrap mass spectrometry. DOM formulas with carbon, hydrogen and oxygen (CHO-DOM) were the most abundant class in water samples, and over half of them were commonly found at both plants. Among the treatment processes, ozonation induced the most drastic changes to DOM. Mass peak intensities of less saturated CHO-DOM (positive (oxygen subtracted double bond equivalent per carbon (DBE-O)/C)) decreased by ozonation, while more saturated oxidation byproducts (negative (DBE-O)/C) increased and new oxidation byproducts (OBPs) were detected. By Kendrick mass analysis, ozone reactions preferred less saturated CHO-DOM in the same alkylation families and produced more saturated alkylation families of OBPs. Following ozonation, biological activated carbon filtration effectively removed <300 Da CHO-DOM, including OBPs. Following chlorination, over 50 chlorinated formulas of disinfection byproducts (DBPs) were found in chlorinated water samples where at least half were unknown. Putative precursors of these DBPs were determined based on electrophilic substitutions and addition reactions. Ozonation demonstrated better decomposition of addition reaction-type precursors than electrophilic substitution-type precursors; over half of both precursor types decreased during biological activated carbon filtration.

Land-based salmon aquacultures change the quality and bacterial degradation of riverine dissolved organic matter

PubMed Central

Kamjunke, Norbert; Nimptsch, Jorge; Harir, Mourad; Herzsprung, Peter; Schmitt-Kopplin, Philippe; Neu, Thomas R.; Graeber, Daniel; Osorio, Sebastian; Valenzuela, Jose; Carlos Reyes, Juan; Woelfl, Stefan; Hertkorn, Norbert

2017-01-01

Aquacultures are of great economic importance worldwide but pollute pristine headwater streams, lakes, and estuaries. However, there are no in-depth studies of the consequences of aquacultures on dissolved organic matter (DOM) composition and structure. We performed a detailed molecular level characterization of aquaculture DOM quality and its bacterial degradation using four salmon aquacultures in Chile. Fluorescence measurements, ultrahigh-resolution mass spectrometry, and nuclear magnetic resonance spectroscopy of the DOM revealed specific and extensive molecular alterations caused by aquacultures. Aquacultures released large quantities of readily bioavailable metabolites (primarily carbohydrates and peptides/proteins, and lipids), causing the organic matter downstream of all the investigated aquacultures to deviate strongly from the highly processed, polydisperse and molecularly heterogeneous DOM found in pristine rivers. However, the upstream individual catchment DOM signatures remained distinguishable at the downstream sites. The benthic algal biovolume decreased and the bacterial biovolume and production increased downstream of the aquacultures, shifting stream ecosystems to a more heterotrophic state and thus impairing the ecosystem health. The bacterial DOM degradation rates explain the attenuation of aquaculture DOM within the subsequent stream reaches. This knowledge may aid the development of improved waste processing facilities and may help to define emission thresholds to protect sensitive stream ecosystems. PMID:28256613

Land-based salmon aquacultures change the quality and bacterial degradation of riverine dissolved organic matter

NASA Astrophysics Data System (ADS)

Kamjunke, Norbert; Nimptsch, Jorge; Harir, Mourad; Herzsprung, Peter; Schmitt-Kopplin, Philippe; Neu, Thomas R.; Graeber, Daniel; Osorio, Sebastian; Valenzuela, Jose; Carlos Reyes, Juan; Woelfl, Stefan; Hertkorn, Norbert

2017-03-01

Aquacultures are of great economic importance worldwide but pollute pristine headwater streams, lakes, and estuaries. However, there are no in-depth studies of the consequences of aquacultures on dissolved organic matter (DOM) composition and structure. We performed a detailed molecular level characterization of aquaculture DOM quality and its bacterial degradation using four salmon aquacultures in Chile. Fluorescence measurements, ultrahigh-resolution mass spectrometry, and nuclear magnetic resonance spectroscopy of the DOM revealed specific and extensive molecular alterations caused by aquacultures. Aquacultures released large quantities of readily bioavailable metabolites (primarily carbohydrates and peptides/proteins, and lipids), causing the organic matter downstream of all the investigated aquacultures to deviate strongly from the highly processed, polydisperse and molecularly heterogeneous DOM found in pristine rivers. However, the upstream individual catchment DOM signatures remained distinguishable at the downstream sites. The benthic algal biovolume decreased and the bacterial biovolume and production increased downstream of the aquacultures, shifting stream ecosystems to a more heterotrophic state and thus impairing the ecosystem health. The bacterial DOM degradation rates explain the attenuation of aquaculture DOM within the subsequent stream reaches. This knowledge may aid the development of improved waste processing facilities and may help to define emission thresholds to protect sensitive stream ecosystems.

Lignin Contribution to the Global Carbon Pool: Investigating the Abiotic Modification of Lignin by Reactive Oxygen Species

NASA Astrophysics Data System (ADS)

Waggoner, Derek Charles

Evidence suggests that reactive oxygen species (ROS), largely generated through photochemical processes, are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. The main focus of the studies within this dissertation aim to more thoroughly characterize the alterations to lignin, used as an analog for terrestrial DOM, resulting from reactions with ROS. To investigate the possibility that the alteration of lignin, through reactions involving ROS, could lead to the production of compounds not recognized as having terrestrial origin, lignin-derived DOM was prepared from a sample of Atlantic white cedar (Chamaecyparis thyoides) and used for a number of studies. Lignin-derived DOM was independently exposed to hydroxyl radical (•OH) generated by Fenton reaction, singlet oxygen (1O2) produced using the photosensitizer Rose Bengal, and superoxide (O2-•) via stable potassium superoxide solution, under controlled laboratory conditions to accentuate how each ROS is responsible for the alteration of lignin. Advanced analytical techniques including high performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR), and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), were employed to characterize alteration to lignin taking place following various ROS treatments. Results of these studies have shown distinct differences in the types of new compounds observed from exposure to each ROS as well as ROS reactivity. The alteration of lignin to compounds not typically associated with terrestrial DOM has been demonstrated upon exposure to ROS. It is also suggested that ROS could selectively react with different fractions of lignin like compounds based largely on oxygen content. Additionally, results indicate that partially oxidized lignin could react further with ROS to generate compounds resembling condensed aromatic-like compounds, previously believed to be primarily pyrogenic in origin, as well as alicyclic compounds commonly observed in marine DOM.

Chemical Composition of Microbe-Derived Dissolved Organic Matter in Cryoconite in Tibetan Plateau Glaciers: Insights from Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Analysis.

PubMed

Feng, Lin; Xu, Jianzhong; Kang, Shichang; Li, Xiaofei; Li, Yang; Jiang, Bin; Shi, Quan

2016-12-20

Cryoconite in mountain glaciers plays important roles in glacial ablation and biogeochemical cycles. In this study, the composition and sources of dissolved organic matter (DOM) in cryoconite from the ablation regions of two Tibetan Plateau glaciers were determined using electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence spectrometry. A marked absorbance between 300 and 350 nm in the DOM absorption spectra was observed which was consistent with microbe-derived mycosporine-like amino acids. Fluorescence excitation-emission matrices showed that DOM had intense signals at protein-like substance peaks and weak signals at humic-like substance peaks. The high-resolution mass spectra of FT-ICR-MS showed cryoconite DOM from both glaciers contained diverse lignins, lipids, proteins, and unsaturated hydrocarbons. The lipids and proteins were consistent with material from microbial sources, and the lignins and unsaturated hydrocarbons were probably from vascular plant material supplied in atmospheric aerosols and debris from around the glaciers. Almost one-third of the identified DOM molecules had low C/N ratios (≤20), indicating their high bioavailability. Using a conservative cryoconite distribution on Chinese mountain glacier surfaces (6%) and an average debris mass per square meter of cryoconite (292 ± 196 g m -2 ), we found that the amount of DOC produced in cryoconite on Chinese glaciers as much as 0.23 ± 0.1 Gg per cryoconite formation process. This dissolved organic carbon may absorb solar radiation, accelerate glacial melting, and be an important source of bioavailable DOM to proglacial and downstream aquatic ecosystems.

Variability in the bulk composition and abundance of dissolved organic matter in the lower Mississippi and Pearl rivers

NASA Astrophysics Data System (ADS)

Duan, Shuiwang; Bianchi, Thomas S.; Shiller, Alan M.; Dria, Karl; Hatcher, Patrick G.; Carman, Kevin R.

2007-06-01

In this study, we examined the temporal and spatial variability of dissolved organic matter (DOM) abundance and composition in the lower Mississippi and Pearl rivers and effects of human and natural influences. In particular, we looked at bulk C/N ratio, stable isotopes (δ15N and δ13C) and 13C nuclear magnetic resonance (NMR) spectrometry of high molecular weight (HMW; 0.2 μm to 1 kDa) DOM. Monthly water samples were collected at one station in each river from August 2001 to 2003. Surveys of spatial variability of total dissolved organic carbon (DOC) and nitrogen (DON) were also conducted in June 2003, from 390 km downstream in the Mississippi River and from Jackson to Stennis Space Center in the Pearl River. Higher DOC (336-1170 μM), C/N ratio,% aromaticity, and more depleted δ15N (0.76-2.1‰) were observed in the Pearl than in the lower Mississippi River (223-380 μM, 4.7-11.5‰, respectively). DOC, C/N ratio, δ13C, δ15N, and % aromaticity of Pearl River HMW DOM were correlated with water discharge, which indicated a coupling between local soil inputs and regional precipitation events. Conversely, seasonal variability in the lower Mississippi River was more controlled by spatial variability of a larger integrative signal from the watershed as well as in situ DOM processing. Spatially, very little change occurred in total DOC in the downstream survey of the lower Mississippi River, compared to a decrease of 24% in the Pearl River. Differences in DOM between these two rivers were reflective of the Mississippi River having more extensive river processing of terrestrial DOM, more phytoplankton inputs, and greater anthropogenic perturbation than the Pearl River.

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.

The response of water quality variation in Poyang Lake (Jiangxi, People's Republic of China) to hydrological changes using historical data and DOM fluorescence.

PubMed

Yao, Xin; Wang, Shengrui; Ni, Zhaokui; Jiao, Lixin

2015-02-01

Poyang Lake is a unique wetland system that has evolved in response to natural seasonal fluctuations in water levels. To better characterize the response of water quality to hydrological variation, historical data were analyzed in combination with dissolved organic matter (DOM) fluorescence samplings conducted in situ. Historical data showed that long-term changes in water quality are mainly controlled by the sewage inputs to Poyang Lake. Monthly changes in water quality recorded during 2008 and 2012 suggest that water level may be the most important factor for water quality during a hydrological year. DOM fluorescence samples were identified as three humic-like components (C1, C2, and C3) and a protein-like component (C4). These obvious compositional changes in DOM fluorescence were considered to be related to the hydrodynamic differences controlled by water regimen. Principal component analysis (PCA) showed higher C1 and C2 signals during a normal season than the wet season, whereas C3 was lower, and C4 was higher in the dry season than in the wet or normal seasons. From the open lake to the Yangtze River mouth, increased C3 component carried by backflows of the Yangtze River to the lake resulted in these unique variations of PCA factor 2 scores during September. These obvious compositional changes in DOM fluorescence were considered to be related to the hydrodynamic differences controlled by water regimen. DOM fluorescence could be a proxy for capturing rapid changes in water quality and thereby provide an early warning signal for the quality of water supply.

Interactive effects of solar radiation and dissolved organic matter on bacterial activity and community structure

PubMed Central

Pérez, María Teresa; Sommaruga, Ruben

2007-01-01

We studied the interactive effects of dissolved organic matter (DOM) and solar radiation on the activity and community structure of bacteria from an alpine lake. Activity was assessed both at the community level as leucine incorporation rates and at the single-cell level by microautoradiography. Fluorescent in situ hybridization and signal amplification by catalysed reporter deposition (CARD-FISH) was used to track changes in the bacterial community composition. Bacteria-free filtrates of different DOM sources (lake, algae or soil) were incubated either in the dark or exposed to solar radiation. Afterwards, the natural bacterial assemblage was inoculated and the cultures incubated in the dark for 24–48 h. Bacterial activity was enhanced in the first 24 h in the soil and algal DOM amendments kept in the dark. After 48 h, the enhancement effect was greatly reduced. The initial bacterial community was dominated by Betaproteobacteria followed by Actinobacteria. The relative abundance (expressed as a percentage of DAPI-stained cells) of Betaproteobacteria increased first in dark incubated DOM amendments, but after 48 h no significant differences were detected among treatments. In contrast, the relative abundance of Actinobacteria increased in pre-irradiated DOM treatments. Although Betaproteobacteria dominated at the end of the experiment, the relative abundance of their R-BT subgroup differed among treatments. Changes in bacterial community activity were significantly correlated with those of the relative abundance and activity of Betaproteobacteria, whereas the contribution of Actinobacteria to the bulk activity was very modest. Our results indicate a negative effect of DOM photoalteration on the bulk bacterial activity. The magnitude of this effect was time-dependent and related to rapid changes in the bacterial assemblage composition. PMID:17686018

Interactive effects of solar radiation and dissolved organic matter on bacterial activity and community structure.

PubMed

Pérez, María Teresa; Sommaruga, Ruben

2007-09-01

We studied the interactive effects of dissolved organic matter (DOM) and solar radiation on the activity and community structure of bacteria from an alpine lake. Activity was assessed both at the community level as leucine incorporation rates and at the single-cell level by microautoradiography. Fluorescent in situ hybridization and signal amplification by catalysed reporter deposition (CARD-FISH) was used to track changes in the bacterial community composition. Bacteria-free filtrates of different DOM sources (lake, algae or soil) were incubated either in the dark or exposed to solar radiation. Afterwards, the natural bacterial assemblage was inoculated and the cultures incubated in the dark for 24-48 h. Bacterial activity was enhanced in the first 24 h in the soil and algal DOM amendments kept in the dark. After 48 h, the enhancement effect was greatly reduced. The initial bacterial community was dominated by Betaproteobacteria followed by Actinobacteria. The relative abundance (expressed as a percentage of DAPI-stained cells) of Betaproteobacteria increased first in dark incubated DOM amendments, but after 48 h no significant differences were detected among treatments. In contrast, the relative abundance of Actinobacteria increased in pre-irradiated DOM treatments. Although Betaproteobacteria dominated at the end of the experiment, the relative abundance of their R-BT subgroup differed among treatments. Changes in bacterial community activity were significantly correlated with those of the relative abundance and activity of Betaproteobacteria, whereas the contribution of Actinobacteria to the bulk activity was very modest. Our results indicate a negative effect of DOM photoalteration on the bulk bacterial activity. The magnitude of this effect was time-dependent and related to rapid changes in the bacterial assemblage composition.

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

NASA Astrophysics Data System (ADS)

Rahikainen, Mika; Hoikkala, Laura; Soinne, Helena

2013-04-01

Bayesian belief nets (BBN) are capable of developing holistic understanding of the origin, transportation, and effects of dissolved organic matter (DOM) in ecosystems. The role of riverine DOM, transporting carbon and macronutrients N and P into lakes and coastal areas, has been largely neglected in research about processes influencing aquatic ecosystem functions although dissolved organic matter provides a significant nutrient source for primary producers in aquatic environments. This neglect has also contributed to the environmental policies which are focused in the control of inorganic N and P load. It is of great social and economic interest to gain improved knowledge of whether the currently applied policy instruments act in synchrony in mitigating eutrophication caused by N and P versus DOM load. DOM is a complex mixture of compounds that are poorly characterized. DOM export is strongly regulated by land use (urban, forest, agricultural land, peat land), in addition to soil type and soil organic carbon concentration. Furthermore, the composition of DOM varies according to its origin. The fate and effects of DOM loads in the fresh water and coastal environments depend, for example, on their biodegradability. Degradation kinetics again depends on the interactions between composition of the DOM pool and the receiving environment. Impact studies of dissolved organic matter pose a complicated environmental impact assessment challenge for science. There exists strategic uncertainty in the science about the causal dependencies and about the quality of knowledge related to DOM. There is a clear need for systematization in the approach as uncertainty is typically high about many key processes. A cross-sectorial, integrative analysis will aid in focusing on the most relevant issues. A holistic and unambiguous analysis will provide support for policy-decisions and management by indicating which outcome is more probable than another. The task requires coupling complex models of different environmental compartments (soil chemistry, agricultural management practices, aquatic processes, costs and benefits for society) with explicit treatment of uncertainty. In order to achieve policy relevance, these models have to be integrated into resource management. We use a Bayesian belief net to describe the probabilistic dependencies among the driving forces, processes, and impacts relevant to dissolved organic matter in boreal waterways.

Reactivity and mobilization of permafrost-derived organic matter along the Lena River Delta - Laptev Sea transition

NASA Astrophysics Data System (ADS)

Koch, Boris P.; Dubinenkov, Ivan; Flerus, Ruth; Schmitt-Kopplin, Philippe; Kattner, Gerhard

2015-04-01

The impact of global warming on organic carbon budgets in permafrost systems are not well constrained. Changes in organic carbon fluxes caused by permafrost thaw depend on microbial activity, coastal erosion, mobilization of organic matter by increased porewater fluxes, and the inherent chemical stability of organic matter in permafrost soils. Here we aim at the identification and molecular characterization of active and inactive dissolved organic matter (DOM) components within the river-ocean transition. We studied four transects in the coastal Laptev Sea characterized by steep physico-chemical gradients. Molecular information on solid-phase extracted DOM was derived from ultrahigh resolution mass spectrometry. Changes of the chemical composition with salinity were used as a measure for DOM reactivity. Although changes of dissolved organic carbon (DOC) in the estuary suggested conservative mixing, only 27% of the identified molecular formulas behaved conservatively, 32% were moderately affected, and 41% were actively involved in estuarine processes. The molecular complexity in the DOM samples increased with growing marine influence and the average elemental composition (i.e. relative contribution of organic nitrogen and oxygen compounds) changed significantly with increasing salinity. These chemical changes were consistent with the results of a 20-day microbial incubation experiment, during which more than half of the permafrost-derived DOC was mineralized. We conclude that, although the DOC gradient in the estuary suggests conservative behavior, terrestrial DOM is substantially affected by estuarine processes which in turn also impact organic carbon budgets in the Lena Delta.

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.

Linking of EEM spectra with FTICRMS data via van Krevelen diagrams and rank correlation

NASA Astrophysics Data System (ADS)

Herzsprung, Peter; von Tümpling, Wolf; Hertkorn, Norbert; Harir, Mourad; Bravidor, Jenny; Büttner, Olaf; Friese, Kurt; Schmitt-Kopplin, Philippe

2014-05-01

DOM plays an important role in both natural and engineered water systems. Due to its sensitivity and non-destruction of samples EEM is widespread used for comprehension of CDOM. EEM provides sensitive bulk optical parameters with low structural resolution concerning DOM quality even when spectra are modelled by PARAFAC or EEM is coupled to chromatography. Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) is a high-resolution analytical tool to determine the elemental compositions of thousands of DOM components directly out of mixtures. Lacking the ability for identification of distinct chemical substances (isomers), the elemental compositions can nevertheless be allocated to biogeochemical pools by means of van Krevelen diagrams. The spearman rank correlation was applied to link the EEM intensities (humic like fluorescence) with exact molecular formulas and their corresponding relative mass peak abundances. The initiative for this study to find out what is humic like fluorescence was the environmental problem of increasing levels of organic carbon in fresh waters as a great challenge for processing and commercial supply of drinking water. In the southern Saxony region, Germany, raw drinking water is mainly received from reservoirs situated in the ore mountains (Erzgebirge). Most of these reservoirs are affected by high concentrations of humic substances detected by the drinking water administration via measurement of the dissolved organic carbon (DOC) and the spectral absorption coefficient at 254 nm (SAC254). To get a better insight into the DOM composition, the seasonal variability of DOM quality was determined using EEM and FTICRMS and coupling these two methods in the catchment area of the reservoir Muldenberg. Thereby, humic-like fluorescence could be allocated to the pool of oxygen-rich and relatively unsaturated components with stoichiometries similar to those of tannic acids [1]. [1] Herzsprung, P., von Tümpling, W., Hertkorn, N., Harir, M., Büttner, O., Bravidor, J., Friese, K., Schmitt-Kopplin, P. Variations of DOM quality in inflows of a drinking water reservoir: Linking of van Krevelen diagrams with EEMF spectra by rank correlation. Environ. Sci. Technol. 46, 5511-5518 (2012).

Dissolved organic matter composition and biodegradability in a permafrost-dominated watershed network in central Siberia

NASA Astrophysics Data System (ADS)

Coble, A. A.; Rodriguez-Cardona, B.; Wymore, A.; Prokishkin, A. S.; Kolosov, R.; McDowell, W. H.

2016-12-01

Thawing permafrost soils can mobilize large quantities of dissolved organic matter (DOM) from soils to headwater streams, and DOM may undergo rapid transformations in streams and rivers in transit to the Arctic Ocean. With climate change an increased frequency of fire is also expected, which will further alter the DOM entering streams, and may contribute to changes in its biodegradability. Elucidating how DOM composition varies across a fire gradient within a river network underlain by continuous permafrost will therefore improve our understanding of the impact of climate change on Arctic ecosystems and its role in the global carbon cycle. To determine DOM composition we measured optical properties via excitation-emission matrices (EEMs) and subsequent parallel factor analysis across a spatially extensive collection of sites in central Siberia. Within a subset of streams in the Nizhnyaya Tunguska watershed network, we also measured biodegradable dissolved organic carbon (BDOC) incubated at in situ temperatures over a 7 day period during spring freshet on two dates in early June. Despite clear changes in optical properties of DOM and background DOC concentration along the fire gradient (range: 3 to >100 y since burn) BDOC did not vary systematically with years since fire for either incubation date. In the first incubation conducted near peak flow BDOC ranged from negligible to 7.6% (BDOC concentration = negligible to 1.4 mg C L-1) within a 7 day period. In the second incubation conducted 5 days later BDOC was negligible across all sites (as both a percentage and a concentration). Our results suggest that DOC exported from permafrost soils in the central Siberian plateau is relatively unreactive at in situ temperatures over 7 day time scales, which contrasts with previous studies conducted in watersheds underlain with Yedoma outcrops where biodegradability comprises a large fraction of DOC. Our preliminary results suggest that melting of permafrost soils in central Siberia may export large quantities of C to the Arctic Ocean that are not rapidly degraded in streams and rivers.

The genesis and exodus of vascular plant DOM from an oak woodland landscape

NASA Astrophysics Data System (ADS)

Hernes, Peter J.; Spencer, Robert G. M.; Dyda, Rachael Y.; O'Geen, Anthony T.; Dahlgren, Randy A.

2017-02-01

Evaluating the collective impact of small source inputs to larger rivers is a constant challenge in riverine biogeochemistry. In this study, we investigated the generation of dissolved organic matter (DOM) in a small oak woodland catchment in the foothills of northern California, the subsequent transformation in lignin biomarkers and chromophoric DOM (CDOM) parameters during transport through the landscape to an exporting stream, and finally the overall compositional impact on the larger receiving stream and river. Our study included a natural leaching experiment in which precipitation passing through oak, pine, and grass litter and duff samples was collected after each of a series of storms. Also included were soil trench samples to capture subsurface flow, stream samples along with point-source reservoir inputs, and samples of canopy throughfall, stemflow, and gopher hole (bypass) flow. The litter/duff leaching study demonstrated changing DOM fractionation patterns throughout the season, as evidenced by changing lignin compositions in the leachates with each successive storm. This adds a necessary seasonal component to interpreting lignin compositions in streams, as the source signatures are constantly changing. Released DOM from leaching was modified extensively during transit through the subsurface to the stream, with preferential increases in aromaticity as evidenced by increases in carbon-normalized absorbance at 254 nm, yet preferential decreases in lignin phenols, as evidence by carbon-normalized lignin yields in the headwater stream that was less than half that of the litter/duff leachates. Our extensive number of lignin measurements for source materials reveals a much more complex perspective on using lignin as a source indicator, as many riverine values for syringyl:vanillyl and cinnamyl:vanillyl ratios that have previously been interpreted as degraded lignin signatures are also possible as unmodified source signatures. Finally, this study demonstrated that the impact of numerous small headwater streams can significantly overprint the DOM signatures of much larger rivers over relatively short distances spanning several to tens of kilometers. This finding in particular challenges the assumption that river studies can be adequately conducted by focusing only on the main tributaries.

Three-dimensional ordered macroporous MnO2/carbon nanocomposites as high-performance electrodes for asymmetric supercapacitors.

PubMed

Yang, Chunzhen; Zhou, Ming; Xu, Qian

2013-12-07

MnO2/carbon composites with ultrathin MnO2 nanofibers (diameter of 5-10 nm) uniformly deposited on three dimensional ordered macroporous (3DOM) carbon frameworks were fabricated via a self-limiting redox process. The MnO2 nanofibers provide a large surface area for charge storage, whereas the 3DOM carbon serves as a desirable supporting material providing rapid ion and electron transport through the composite electrodes. Cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) were used to characterize the capacitive performance of these composites. Optimization of the composition results in a composite with 57 wt% MnO2 content, which gives both a high specific capacitance (234 F g(-1) at a discharge current of 0.1 A g(-1)) and good rate capability (52% retention of the capacitance at 5 A g(-1)). An asymmetric supercapacitor was fabricated by assembling the optimized MnO2/carbon composite as the positive electrode and 3DOM carbon as the negative electrode. The asymmetric supercapacitor exhibits superior electrochemical performances, which can be reversibly charged and discharged at a maximum cell voltage of 2.0 V in 1.0 M Na2SO4 aqueous electrolyte, delivering both high energy density (30.2 W h kg(-1)) and power density (14.5 kW kg(-1)). Additionally, the asymmetric supercapacitor exhibits an excellent cycle life, with 95% capacitance retained after 1000 cycles.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially-mediated DOM turnover in the upwelling region off Peru

NASA Astrophysics Data System (ADS)

Galgani, L.; Engel, A.

2015-12-01

The coastal upwelling system off Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. During the Meteor (M91) cruise to the Peruvian upwelling system in 2012, we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples at 38 stations determining DOC concentration, amino acid composition, marine gels, CDOM and bacterial and phytoplankton abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. We identified five fluorescent components of the CDOM pool, of which two had excitation/emission characteristics of protein-like fluorophores and were highly enriched in the SML. CDOM composition and changes in spectral slope properties suggested a local microbial release of HMW DOM directly in the SML as a response to light exposure in this extreme environment. Our results suggest that microbial and photochemical processes play an important role for the production, alteration and loss of optically active substances in the SML.

Microbial Community Structure and Activity Linked to Contrasting Biogeochemical Gradients in Bog and Fen Environments of the Glacial Lake Agassiz Peatland

PubMed Central

Lin, X.; Green, S.; Tfaily, M. M.; Prakash, O.; Konstantinidis, K. T.; Corbett, J. E.; Chanton, J. P.; Cooper, W. T.

2012-01-01

The abundances, compositions, and activities of microbial communities were investigated at bog and fen sites in the Glacial Lake Agassiz Peatland of northwestern Minnesota. These sites contrast in the reactivity of dissolved organic matter (DOM) and the presence or absence of groundwater inputs. Microbial community composition was characterized using pyrosequencing and clone library construction of phylogenetic marker genes. Microbial distribution patterns were linked to pH, concentrations of dissolved organic carbon and nitrogen, C/N ratios, optical properties of DOM, and activities of laccase and peroxidase enzymes. Both bacterial and archaeal richness and rRNA gene abundance were >2 times higher on average in the fen than in the bog, in agreement with a higher pH, labile DOM content, and enhanced enzyme activities in the fen. Fungi were equivalent to an average of 1.4% of total prokaryotes in gene abundance assayed by quantitative PCR. Results revealed statistically distinct spatial patterns between bacterial and fungal communities. Fungal distribution did not covary with pH and DOM optical properties and was vertically stratified, with a prevalence of Ascomycota and Basidiomycota near the surface and much higher representation of Zygomycota in the subsurface. In contrast, bacterial community composition largely varied between environments, with the bog dominated by Acidobacteria (61% of total sequences), while the Firmicutes (52%) dominated in the fen. Acetoclastic Methanosarcinales showed a much higher relative abundance in the bog, in contrast to the dominance of diverse hydrogenotrophic methanogens in the fen. This is the first quantitative and compositional analysis of three microbial domains in peatlands and demonstrates that the microbial abundance, diversity, and activity parallel with the pronounced differences in environmental variables between bog and fen sites. PMID:22843538

Catchment influence on nitrate and dissolved organic matter in Alaskan streams across a latitudinal gradient

DOE PAGES

Harms, Tamara K.; Edmonds, Jennifer W.; Genet, Hélène; ...

2016-01-10

Spatial patterns in carbon (C) and nitrogen (N) cycles of high-latitude catchments have been linked to climate and permafrost and used to infer potential changes in biogeochemical cycles under climate warming. However, inconsistent spatial patterns across regions indicate that factors in addition to permafrost and regional climate may shape responses of C and N cycles to climate change. In this paper, we hypothesized that physical attributes of catchments modify responses of C and N cycles to climate and permafrost. We measured dissolved organic C (DOC) and nitrate (NO 3 ¯) concentrations, and composition of dissolved organic matter (DOM) in 21more » streams spanning boreal to arctic Alaska, and assessed permafrost, topography, and attributes of soils and vegetation as predictors of stream chemistry. Multiple regression analyses indicated that catchment slope is a primary driver, with lower DOC and higher NO 3 ¯ concentration in streams draining steeper catchments, respectively. Depth of the active layer explained additional variation in concentration of DOC and NO 3 ¯. Vegetation type explained regional variation in concentration and composition of DOM, which was characterized by optical methods. Composition of DOM was further correlated with attributes of soils, including moisture, temperature, and thickness of the organic layer. Finally, regional patterns of DOC and NO 3 ¯ concentrations in boreal to arctic Alaska were driven primarily by catchment topography and modified by permafrost, whereas composition of DOM was driven by attributes of soils and vegetation, suggesting that predicting changes to C and N cycling from permafrost-influenced regions should consider catchment setting in addition to dynamics of climate and permafrost.« less

Bioavailability of Dissolved Organic Carbon and Nitrogen From Tropical Montane Rainforest Streams Across a Geologic age Gradient

NASA Astrophysics Data System (ADS)

Wiegner, T. N.

2005-05-01

Dissolved organic matter (DOM) is metabolically important in streams. Its bioavailability is influenced by organic matter sources to streams and inorganic nutrient availability. As forest canopies and soils develop over time, organic matter inputs to streams should switch from algal to watershed sources. Across this succession gradient, nutrient limitation should also change. This study examines how chemical composition and bioavailability of DOM from tropical montane rainforest streams on Hawaii change across a geologic age gradient from 4 ky to 150 ky. Dissolved organic C (DOC) and N (DON) concentrations, chemical characteristics, and bioavailability varied with site age. With increasing stream age, DOC and DON concentrations, DOM aromaticity, and the C:N of the stream DOM increased. Changes in stream DOM chemistry and inorganic nutrient availability affected DOM bioavailability. Fifty percent of the DOC from the 4 ky site was bioavailable, where little to none was bioavailable from the older streams. Inorganic nutrient availability did not affect DOC bioavailability. In contrast, DON bioavailability was similar (12%) across sites and was affected by inorganic nutrient availability. This study demonstrates that the chemistry and metabolism of streams draining forests change with ecosystem age and development.

The influence of natural dissolved organic matter on herbicide toxicity to marine microalgae is species-dependent.

PubMed

Coquillé, Nathalie; Ménard, Dominique; Rouxel, Julien; Dupraz, Valentin; Éon, Mélissa; Pardon, Patrick; Budzinski, Hélène; Morin, Soizic; Parlanti, Édith; Stachowski-Haberkorn, Sabine

2018-05-01

Microalgae, which are the foundation of aquatic food webs, may be the indirect target of herbicides used for agricultural and urban applications. Microalgae also interact with other compounds from their environment, such as natural dissolved organic matter (DOM), which can itself interact with herbicides. This study aimed to evaluate the influence of natural DOM on the toxicity of three herbicides (diuron, irgarol and S-metolachlor), singly and in ternary mixtures, to two marine microalgae, Chaetoceros calcitrans and Tetraselmis suecica, in monospecific, non-axenic cultures. Effects on growth, photosynthetic efficiency (Ф' M ) and relative lipid content were evaluated. The chemical environment (herbicide and nutrient concentrations, dissolved organic carbon and DOM optical properties) was also monitored to assess any changes during the experiments. The results show that, without DOM, the highest irgarol concentration (I0.5: 0.5 mg.L -1 ) and the strongest mixture (M2: irgarol 0.5 μg.L -1  + diuron 0.5 μg.L -1  + S-metolachlor 5.0 μg.L -1 ) significantly decreased all parameters for both species. Similar impacts were induced by I0.5 and M2 in C. calcitrans (around -56% for growth, -50% for relative lipid content and -28% for Ф' M ), but a significantly higher toxicity of M2 was observed in T. suecica (-56% and -62% with I0.5 and M2 for growth, respectively), suggesting a possible interaction between molecules. With DOM added to the culture media, a significant inhibition of these three parameters was also observed with I0.5 and M2 for both species. Furthermore, DOM modulated herbicide toxicity, which was decreased for C. calcitrans (-51% growth at I0.5 and M2) and increased for T. suecica (-64% and -75% growth at I0.5 and M2, respectively). In addition to the direct and/or indirect (via their associated bacteria) use of molecules present in natural DOM, the characterization of the chemical environment showed that the toxic effects observed on microalgae were accompanied by modifications of DOM composition and the quantity of dissolved organic carbon excreted and/or secreted by microorganisms. This toxicity modulation in presence of DOM could be explained by (i) the modification of herbicide bioavailability, (ii) a difference in cell wall composition between the two species, and/or (iii) a higher detoxification capacity of C. calcitrans by the use of molecules contained in DOM. This study therefore demonstrated, for the first time, the major modulating role of natural DOM on the toxicity of herbicides to marine microalgae. Copyright © 2018 Elsevier B.V. All rights reserved.

Microbial Community Response to Terrestrially Derived Dissolved Organic Matter in the Coastal Arctic

PubMed Central

Sipler, Rachel E.; Kellogg, Colleen T. E.; Connelly, Tara L.; Roberts, Quinn N.; Yager, Patricia L.; Bronk, Deborah A.

2017-01-01

Warming at nearly twice the global rate, higher than average air temperatures are the new ‘normal’ for Arctic ecosystems. This rise in temperature has triggered hydrological and geochemical changes that increasingly release carbon-rich water into the coastal ocean via increased riverine discharge, coastal erosion, and the thawing of the semi-permanent permafrost ubiquitous in the region. To determine the biogeochemical impacts of terrestrially derived dissolved organic matter (tDOM) on marine ecosystems we compared the nutrient stocks and bacterial communities present under ice-covered and ice-free conditions, assessed the lability of Arctic tDOM to coastal microbial communities from the Chukchi Sea, and identified bacterial taxa that respond to rapid increases in tDOM. Once thought to be predominantly refractory, we found that ∼7% of dissolved organic carbon and ∼38% of dissolved organic nitrogen from tDOM was bioavailable to receiving marine microbial communities on short 4 – 6 day time scales. The addition of tDOM shifted bacterial community structure toward more copiotrophic taxa and away from more oligotrophic taxa. Although no single order was found to respond universally (positively or negatively) to the tDOM addition, this study identified 20 indicator species as possible sentinels for increased tDOM. These data suggest the true ecological impact of tDOM will be widespread across many bacterial taxa and that shifts in coastal microbial community composition should be anticipated. PMID:28649233

Unveiling the transformation and bioavailability of dissolved organic matter in contrasting hydrothermal vents using fluorescence EEM-PARAFAC.

PubMed

Yang, Liyang; Zhuang, Wan-E; Chen, Chen-Tung Arthur; Wang, Bing-Jye; Kuo, Fu-Wen

2017-03-15

The submarine hydrothermal systems are extreme environments where active cycling of dissolved organic matter (DOM) may occur. However, little is known about the optical properties and bioavailability of hydrothermal DOM, which could provide valuable insights into its transformation processes and biogeochemical reactivity. The quantity, quality, and bioavailability of DOM were investigated for four very different hydrothermal vents east of Taiwan, using dissolved organic carbon (DOC), absorption spectroscopy, and fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC). The DOC and absorption coefficient a 280 were both lower in the two hydrothermal vents off the Orchid Island and on the Green Island than in the surrounding seawater and the two vents off the Kueishantao Island, indicating effective removals of DOM in the former two hydrothermal systems owing to possible adsorption/co-precipitation and thermal degradation respectively. The four hydrothermal DOM showed notable differences in the absorption spectral slope S 275-295 , humification index HIX, biological index BIX, EEM spectra, and the relative distributions of seven PARAFAC components. The results demonstrated a high diversity of chemical composition and transformation history of DOM under contrasting hydrothermal conditions. The little change in the hydrothermal DOC after 28-day microbial incubations indicated a low bioavailability of the bulk DOM, and different PARAFAC components showed contrasting bioavailability. The results have profound implications for understanding the biogeochemical cycling and environmental effects of hydrothermal DOM in the marine environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tracing sources of organic matter in adjacent urban streams having different degrees of channel modification.

PubMed

Duan, Shuiwang; Amon, Rainer M W; Brinkmeyer, Robin L

2014-07-01

Urbanization and stream-channel modifications affect organic matter concentrations and quality in streams, by altering allochthonous organic matter input and in-stream transformation. This study uses multiple tracers (δ(13)C, δ(15)N, C/N ratio, and chlorophyll-a) to track sources of organic matter in two highly urbanized bayous in Houston (Texas, USA). Wastewater treatment plants (WWTPs) are located in headwaters of both bayous and contribute more than 75% to water flow. Low isotopic relatedness to natural end-members and enriched δ(15)N values suggest the influence of WWTPs on the composition of all organic matter fractions. The two bayous differ in degree of channel improvement resulting in different responses to hydrological conditions. During high flow conditions, the influence of terrestrial organic matter and sediment resuspension was much more pronounced in the Buffalo Bayou than in the concrete-lined White Oak Bayou. Particulate organic matter (POM) in White Oak Bayou had similar values of enriched δ(15)N in all subsegments, whereas in Buffalo Bayou, the degree of δ(15)N enrichment was less in the subsegments of the lower watershed. The difference in riparian zone contributions and interactions with sediments/soils was likely responsible for the compositional differences between the two bayous. Phytoplankton inputs were significantly higher in the bayous, especially in slow-flowing sections, relative to the reference sites, and elevated phytoplankton inputs accounted for the observed stable C isotope differences between FPOM and high molecular weight dissolved organic matter (HMW DOM). Relative to POM, HMW DOM in the bayous was similar to WWTP effluents and showed minor longitudinal variability in both streams suggesting that WWTPs contribute much of the DOM in the systems. Urbanization has a major influence on organic matter sources and quality in these urban water bodies and these changes seem further enhanced by stream channel modifications. Copyright © 2014 Elsevier B.V. All rights reserved.

Export of pre-aged, labile DOM from a central California coastal upwelling system: Insights from D/L amino acids and Δ14C signatures

NASA Astrophysics Data System (ADS)

Walker, B. D.; Shen, Y.; Benner, R. H.; Druffel, E. R. M.

2014-12-01

Coastal upwelling zones are among the most productive regions in the world and play a major role in global carbon and nitrogen cycles. Recent research suggests that a substantial fraction of newly fixed organic matter is exported offshore in the form of dissolved organic matter (DOM). However, to date only a few studies have examined DOM composition in the context of production and export from upwelling systems. The ultimate fate and geochemical impact of coastal DOM exported to offshore and mesopelagic ecosystems also remains largely unknown. Between 2007-2009 we conducted a high-resolution biogeochemical time series at the Granite Canyon Marine Pollution Studies Lab in part to evaluate the seasonal production and export of DOM from the Central CA coast. Our previous work demonstrated substantial, albeit disparate, seasonal production of dissolved organic carbon and nitrogen (DOC, DON) - with high DON (and low C:N ratios) produced during upwelling and high DOC produced during summer/fall water column stratification (Walker and McCarthy, 2012). Here we present new total dissolved D/L amino acid (TDAA) and UV-oxidizable DOC radiocarbon (Δ14C) data with the goal of determining the relative sources (heterotrophic vs. autotrophic), bioavailability, microbial processing and 14C-ages of C-rich vs. N-rich DOM exported from this upwelling system. Our results suggest that C-rich DOM produced during water column stratification carries a large microbial signature (i.e. high D/L AA ratios and non-protein AA abundance), whereas N-rich DOM produced during upwelling appears to be fresh, autotrophic DOM (i.e. lowest D/L AA ratios and highest TDAA abundance). DOM Δ14C signatures also did not approximate in situ dissolved inorganic carbon (DIC), and instead were far more negative and highly correlated to water mass density. Together our results indicate a previously unrecognized source of highly labile yet pre-aged DOM potentially impacting offshore and mesopelagic ecosystems.

Trials and Tribulations of Fluorescent Dissolved Organic Matter Chemical Interpretations: A case study of polar ice cores

NASA Astrophysics Data System (ADS)

D'Andrilli, J.

2017-12-01

Excitation emission matrix fluorescence spectroscopy is widely applied for rapid dissolved organic matter (DOM) characterization in aquatic systems. Fluorescent DOM surveys are booming, not only as a central focus in aquatic environments, but also as an important addition to interdisciplinary research (e.g., DOM analysis in concert with ice core paleoclimate reconstructions, stream metabolism, hydrologic regimes, agricultural developments, and biological activity), opening new doors, not just for novelty, but also for more challenges with chemical interpretations. Recently, the commonly used protein- versus humic-like classifications of DOM have been ineffective at describing DOM chemistry in various systems (e.g., ice cores, wastewaters, incubations/engineered). Moreover, the oversimplification of such classifications used to describe fluorescing components, without further scrutiny, has become commonplace, ultimately producing vague reporting. For example, West Antarctic ice core DOM was shown to contain fluorescence in the low excitation/emission wavelength region, however resolved fluorophores depicting tyrosine- and tryptophan-like DOM were not observed. At first, as literature suggested, we reported this result as protein-like, and concluded that microbial contributions were dominant in deep ice. That initial interpretation would disintegrate the conservation paradigm of atmospheric composition during deposition, the crux of ice core research, and contradict other lines of evidence. This begged the question, "How can we describe DOM chemistry without distinct fluorophores?" Antarctic ice core DOM was dominated by neither tyrosine- nor tryptophan-like fluorescence, causing "unusual" looking fluorescent components. After further examination, deep ice DOM was reported to contain fluorescent species most similar to monolignols and tannin-like phenols, describing the precursors of lignin from low carbon producing environments, consistent with marine sediment records. Currently, we are working towards more detailed descriptions of fluorescence, thus accepting variation in and around protein- and humic-like regions, and achieving robust chemical interpretations of DOM chemistry, ultimately providing insight to its interwoven nature in the environment.

A global hotspot for dissolved organic carbon in hypermaritime watersheds of coastal British Columbia

NASA Astrophysics Data System (ADS)

Oliver, Allison A.; Tank, Suzanne E.; Giesbrecht, Ian; Korver, Maartje C.; Floyd, William C.; Sanborn, Paul; Bulmer, Chuck; Lertzman, Ken P.

2017-08-01

The perhumid region of the coastal temperate rainforest (CTR) of Pacific North America is one of the wettest places on Earth and contains numerous small catchments that discharge freshwater and high concentrations of dissolved organic carbon (DOC) directly to the coastal ocean. However, empirical data on the flux and composition of DOC exported from these watersheds are scarce. We established monitoring stations at the outlets of seven catchments on Calvert and Hecate islands, British Columbia, which represent the rain-dominated hypermaritime region of the perhumid CTR. Over several years, we measured stream discharge, stream water DOC concentration, and stream water dissolved organic-matter (DOM) composition. Discharge and DOC concentrations were used to calculate DOC fluxes and yields, and DOM composition was characterized using absorbance and fluorescence spectroscopy with parallel factor analysis (PARAFAC). The areal estimate of annual DOC yield in water year 2015 was 33.3 Mg C km-2 yr-1, with individual watersheds ranging from an average of 24.1 to 37.7 Mg C km-2 yr-1. This represents some of the highest DOC yields to be measured at the coastal margin. We observed seasonality in the quantity and composition of exports, with the majority of DOC export occurring during the extended wet period (September-April). Stream flow from catchments reacted quickly to rain inputs, resulting in rapid export of relatively fresh, highly terrestrial-like DOM. DOC concentration and measures of DOM composition were related to stream discharge and stream temperature and correlated with watershed attributes, including the extent of lakes and wetlands, and the thickness of organic and mineral soil horizons. Our discovery of high DOC yields from these small catchments in the CTR is especially compelling as they deliver relatively fresh, highly terrestrial organic matter directly to the coastal ocean. Hypermaritime landscapes are common on the British Columbia coast, suggesting that this coastal margin may play an important role in the regional processing of carbon and in linking terrestrial carbon to marine ecosystems.

Investigating the composition characteristics of dissolved and particulate/colloidal organic matter in effluent-dominated stream using fluorescence spectroscopy combined with multivariable analysis.

PubMed

Yu, Min-Da; He, Xiao-Song; Xi, Bei-Dou; Gao, Ru-Tai; Zhao, Xian-Wei; Zhang, Hui; Huang, Cai-Hong; Tan, Wenbing

2018-03-01

Fluorescence excitation-emission matrix (EEM) spectroscopy combined with principal component analysis (PCA) and parallel factor analysis (PARAFAC) were used to investigate the compositional characteristics of dissolved and particulate/colloidal organic matter and its correlations with nitrogen, phosphorus, and heavy metals in an effluent-dominated stream, Northern China. The results showed that dissolved organic matter (DOM) was comprised of fulvic-like, humic-like, and protein-like components in the water samples, and fulvic-like substances were the main fraction of DOM among them. Particulate/colloidal organic matter (PcOM) consisted of fulvic-like and protein-like matter. Fulvic-like substances existed in the larger molecular form in PcOM, and they comprised a large amount of nitrogen and polar functional groups. On the other hand, protein-like components in PcOM were low in benzene ring and bound to heavy metals. It could be concluded that nitrogen, phosphorus, and heavy metals in effluent had an effect on the compositional characteristics of natural DOM and PcOM, which may deepen our understanding about the environmental behaviors of organic matter in effluent.

The compositional change of Fluorescent Dissolved Organic Matter across Fram Strait assessed with use of a multi channel in situ fluorometer.

NASA Astrophysics Data System (ADS)

Raczkowska, A.; Kowalczuk, P.; Sagan, S.; Zabłocka, M.; Pavlov, A. K.; Granskog, M. A.; Stedmon, C. A.

2016-02-01

Observations of Colored Dissolved Organic Matter absorption (CDOM) and fluorescence (FDOM) from water samples and an in situ fluorometer and of Inherent Optical Properties (IOP; light absorption and scattering) were carried out along a section across Fram Strait at 79°N. A 3 channel Wetlabs Wetstar fluorometer was deployed, with channels for humic- and protein-like DOM and used to assess distribution of different FDOM fractions. A relationship between fluorescence intensity of the protein-like fraction of FDOM and chlorophyll a fluorescence was found and indicated the importance of phytoplankton biomass in West Spitsbergen Current waters as a significant source of protein-like FDOM. East Greenland Current waters has low concentration of chlorophyll a, and were characterized by high humic-like FDOM fluorescence. An empirical relationship between humic-like FDOM fluorescence intensity and CDOM absorption was derived and confirms the dominance of terrigenous like CDOM on the composition of DOM in the East Greenland Current. These high resolution profile data offer a simple approach to fractionate the contribution of these two DOM source to DOM across the Fram Strait and may help refine estimates of DOC fluxes in and out of the Arctic through this region.

Storage effects on quantity and composition of dissolved organic carbon and nitrogen of lake water, leaf leachate and peat soil water.

PubMed

Heinz, Marlen; Zak, Dominik

2018-03-01

This study aimed to evaluate the effects of freezing and cold storage at 4 °C on bulk dissolved organic carbon (DOC) and nitrogen (DON) concentration and SEC fractions determined with size exclusion chromatography (SEC), as well as on spectral properties of dissolved organic matter (DOM) analyzed with fluorescence spectroscopy. In order to account for differences in DOM composition and source we analyzed storage effects for three different sample types, including a lake water sample representing freshwater DOM, a leaf litter leachate of Phragmites australis representing a terrestrial, 'fresh' DOM source and peatland porewater samples. According to our findings one week of cold storage can bias DOC and DON determination. Overall, the determination of DOC and DON concentration with SEC analysis for all three sample types were little susceptible to alterations due to freezing. The findings derived for the sampling locations investigated here may not apply for other sampling locations and/or sample types. However, DOC size fractions and DON concentration of formerly frozen samples should be interpreted with caution when sample concentrations are high. Alteration of some optical properties (HIX and SUVA 254 ) due to freezing were evident, and therefore we recommend immediate analysis of samples for spectral analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metal complexation properties of freshwater dissolved organic matter are explained by its aromaticity and by anthropogenic ligands.

PubMed

Baken, Stijn; Degryse, Fien; Verheyen, Liesbeth; Merckx, Roel; Smolders, Erik

2011-04-01

Dissolved organic matter (DOM) in surface waters affects the fate and environmental effects of trace metals. We measured variability in the Cd, Cu, Ni, and Zn affinity of 23 DOM samples isolated by reverse osmosis from freshwaters in natural, agricultural, and urban areas. Affinities at uniform pH and ionic composition were assayed at low, environmentally relevant free Cd, Cu, Ni, and Zn activities. The C-normalized metal binding of DOM varied 4-fold (Cu) or about 10-fold (Cd, Ni, Zn) among samples. The dissolved organic carbon concentration ranged only 9-fold in the waters, illustrating that DOM quality is an equally important parameter for metal complexation as DOM quantity. The UV-absorbance of DOM explained metal affinity only for waters receiving few urban inputs, indicating that in those waters, aromatic humic substances are the dominant metal chelators. Larger metal affinities were found for DOM from waters with urban inputs. Aminopolycarboxylate ligands (mainly EDTA) were detected at concentrations up to 0.14 μM and partly explained the larger metal affinity. Nickel concentrations in these surface waters are strongly related to EDTA concentrations (R2=0.96) and this is underpinned by speciation calculations. It is concluded that metal complexation in waters with anthropogenic discharges is larger than that estimated with models that only take into account binding on humic substances.

Release and microbial degradation of dissolved organic matter (DOM) from the macroalgae Ulva prolifera.

PubMed

Zhang, Tao; Wang, Xuchen

2017-12-15

Release and microbial degradation of dissolved organic matter (DOM) and chromophoric dissolved organic matter (CDOM) from the macroalgae Ulva prolifera were studied in laboratory incubation experiments. The release of DOM and CDOM from Ulva prolifera was a rapid process, and hydrolysis played an important role in the initial leaching of the organic compounds from the algae. Bacterial activity enhanced the release of DOM and CDOM during degradation of the algae and utilization of the released organic compounds. It is calculated that 43±2% of the C and 63±3% of the N from Ulva prolifera's biomass were released during the 20-day incubation, and 65±3% of the released C and 87±4% of the released N were utilized by bacteria. In comparison, only 18±1% of the algae's C and 17±1% of its N were released when bacterial activities were inhibited. The fluorescence characteristics of the CDOM indicate that protein-like DOM was the major organic component released from Ulva prolifera that was highly labile and biodegradable. Bacteria played an important role in regulating the chemical composition and fluorescence characteristics of the DOM. Our study suggests that the release of DOM from Ulva prolifera provides not only major sources of organic C and N, but also important food sources to microbial communities in coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemical behavior of dissolved and colloidal organic matter in estuarine and oceanic waters.

PubMed

Zhu, Wen-Zhuo; Yang, Gui-Peng; Zhang, Hong-Hai

2017-12-31

Chromophoric dissolved organic matter (CDOM), carbohydrates, and amino acids were analyzed to investigate the photochemistry of total dissolved (<0.22μm) organic matter (DOM), high-molecular-weight (HMW, 1kDa-0.22μm) DOM and low-molecular-weight (LMW, <1kDa) DOM at stations in the Yangtze River and its coastal area, and in the Western Pacific Ocean. Results revealed that the humic-like and tryptophan-like CDOM fluorescent components in riverine, coastal, and oceanic surface waters were photodegraded during irradiation. However, the photochemical behavior of tyrosine-like component was obscured by the excessive fluorescence intensities of humic- and tryptophan-like fluorescent components. Light sensitivity varied depending on the source material; terrestrially derived DOM was more susceptible to irradiation than autochthonous DOM. In contrast to the expected photodegradation of CDOM, photo-induced synthetic reaction transformed the LMW matters to polysaccharides (PCHO) and degradation reaction decomposed the HMW DOM to Monosaccharides. Colloidal DOM preferentially underwent photodegradation, whereas permeate DOM mainly photosynthesized PCHO. The total hydrolysable amino acid (THAA) pool changed because of the additional input by the photodegradation of DOM or THAA itself. The compositions of THAA changed during the irradiation experiments, indicating that the different photochemical behavior of individual amino acids were related to their different original photoreactivities; the relatively stable amino acids (e.g., Ser and Gly) significantly accumulated during irradiation, whereas photo-active aromatic amino acids (e.g. Tyr and His) were prone to photodegradation. The data presented here demonstrated that irradiation significantly influence the conversion between dissolved and colloid organic matter. These results can promote the understanding of irradiation effect on the carbon and nitrogen cycle in riverine, estuarine and oceanic ecosystems. Copyright © 2017 Elsevier B.V. All rights reserved.

Dissolved organic matter in the unsaturated zone: the view from the cave

NASA Astrophysics Data System (ADS)

Baker, A.; Duan, W.; Rutlidge, H.; McDonough, L.; Oudone, P.; Meredith, K.; Andersen, M. S.; O'Carroll, D. M.; Coleborn, K.; Treble, P. C.

2017-12-01

Soil organic matter content is typically a few percent of the total soil composition. Diffuse recharge can mobilise some of this soil-derived organic matter. While soil pore water dissolved organic matter (DOM) concentrations are up to 100 ppm, the resulting groundwater dissolved organic matter concentration is typically less than 2ppm. Dissolved organic matter transported from the soil can be both biodegraded and sorbed to minerals, and the relative importance of these two processes in the unsaturated zone is poorly understood. Caves in karstified limestone uniquely provide direct access to water percolating from the soil to the groundwater. Cave percolation waters can be analysed for their DOM concentration and character. This provides insights into the extent and type of biological and chemical processing of DOM during transport from the soil to the groundwater. We determine the concentration and characteristics of DOM in cave percolation waters using liquid chromatography (LC-OCD) and optical spectrophotometry (fluorescence and absorbance). We sample DOM from multiple caves in SE Australia (Cathedral Cave, Wellington; South Glory and Harrie Wood Caves, Yarrangobilly), permitting comparison of unsaturated zone DOM properties at different depths (up to 30m below land surface) and different climate zones (montane and temperate). We use caves with long-term hydrological monitoring programs so that DOM in waters of contrasting residence times can be compared. Additionally, we compare these cave percolation water DOM characteristics to those from local and regional groundwater, sampled from nearby wells. Our results will help improve our understanding of how DOM is processed from soil to groundwater, and is also relevant to speleothem scientists interested in using organic matter preserved in speleothems as a paleoclimate or paleoenvironmental proxy.

Molecular signatures of biogeochemical transformations in dissolved organic matter from ten World Rivers

NASA Astrophysics Data System (ADS)

Riedel, Thomas; Zark, Maren; Vähätalo, Anssi; Niggemann, Jutta; Spencer, Robert; Hernes, Peter; Dittmar, Thorsten

2016-09-01

Rivers carry large amounts of dissolved organic matter (DOM) to the oceans thereby connecting terrestrial and marine element cycles. Photo-degradation in conjunction with microbial turnover is considered a major pathway by which terrigenous DOM is decomposed. To reveal globally relevant patterns behind this process, we performed photo-degradation experiments and year-long bio-assays on DOM from ten of the largest world rivers that collectively account for more than one-third of the fresh water discharge to the global ocean. We furthermore tested the hypothesis that the terrigenous component in deep ocean DOM may be far higher than biomarker studies suggest, because of the selective photochemical destruction of characteristic biomolecules from vascular plants. DOM was molecularly characterized by a combination of non-targeted ultrahigh-resolution mass spectrometry and quantitative molecular tracer analyses. We show that the reactivity of DOM is globally related to broad catchment properties. Basins that are dominated by forest and grassland export more photo-degradable DOM than other rivers. Chromophoric compounds are mainly vascular plant-derived polyphenols, and partially carry a pyrogenic signature from vegetation fires. These forest and grassland dominated rivers lost up to 50% of dissolved organic carbon (DOC) during irradiation, and up to 85% of DOC was lost in total if subsequently bio-incubated for one year. Basins covered by cropland, on the other hand, export DOM with a higher proportion of photo-resistant and bio-available DOM which is enriched in nitrogen. In these rivers, 30% or less of DOC was photodegraded. Consistent with previous studies, we found that riverine DOM resembled marine DOM in its broad molecular composition after extensive degradation, mainly due to almost complete removal of aromatics. More detailed molecular fingerprinting analysis (based on the relative abundance of >4000 DOM molecular formulae), however, revealed clear differences between degraded riverine and deep-sea DOM (molecular Bray-Curtis dissimilarity of 50%). None of our experimental treatments enhanced the molecular similarity between the rivers and the deep ocean. We conclude that terrigenous DOM retains a specific molecular signature during photo-degradation on much longer time scales than previously assumed and that substantial, thus far unknown, molecular transformations occur prior to downward convection into the deep oceanic basins.

Three-dimensional fluorescence excitation-emission matrix (EEM) spectroscopy with regional integration analysis for assessing waste sludge hydrolysis treated with multi-enzyme and thermophilic bacteria.

PubMed

Guo, Liang; Lu, Mingmin; Li, Qianqian; Zhang, Jiawen; Zong, Yan; She, Zonglian

2014-11-01

The hydrolysis effect of waste sludge after multi-enzyme and thermophilic bacteria pretreatments is investigated using excitation-emission matrix (EEM) with fluorescence regional integration (FRI) in this study. The compositional characteristics of extracellular polymeric substances (EPS) and dissolved organic matters (DOM) were analyzed to evaluate the sludge disintegration. The EPS and cell wall in sludge were disrupted after hydrolysis which led to carbohydrate, protein and soluble chemical oxygen demand (SCOD) of DOM increasing in sludge supernatant. The bio-degradability level in the extracted fractions of EPS and DOM depending on the fluorescence zones was found after hydrolysis. The highest proportion of percent fluorescence response (Pi,n) in EPS and DOM was soluble microbial by-product and humic acid-like organics. A significant increase of humic acid-like organics in DOM after thermophilic bacteria hydrolysis was obtained. The assessment of hydrolysis using EEM coupled with FRI provided a new insight toward the bio-utilization process of waste sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

Critical analysis of commonly used fluorescence metrics to characterize dissolved organic matter.

PubMed

Korak, Julie A; Dotson, Aaron D; Summers, R Scott; Rosario-Ortiz, Fernando L

2014-02-01

The use of fluorescence spectroscopy for the analysis and characterization of dissolved organic matter (DOM) has gained widespread interest over the past decade, in part because of its ease of use and ability to provide bulk DOM chemical characteristics. However, the lack of standard approaches for analysis and data evaluation has complicated its use. This study utilized comparative statistics to systematically evaluate commonly used fluorescence metrics for DOM characterization to provide insight into the implications for data analysis and interpretation such as peak picking methods, carbon-normalized metrics and the fluorescence index (FI). The uncertainty associated with peak picking methods was evaluated, including the reporting of peak intensity and peak position. The linear relationship between fluorescence intensity and dissolved organic carbon (DOC) concentration was found to deviate from linearity at environmentally relevant concentrations and simultaneously across all peak regions. Comparative analysis suggests that the loss of linearity is composition specific and likely due to non-ideal intermolecular interactions of the DOM rather than the inner filter effects. For some DOM sources, Peak A deviated from linearity at optical densities a factor of 2 higher than that of Peak C. For carbon-normalized fluorescence intensities, the error associated with DOC measurements significantly decreases the ability to distinguish compositional differences. An in-depth analysis of FI determined that the metric is mostly driven by peak emission wavelength and less by emission spectra slope. This study also demonstrates that fluorescence intensity follows property balance principles, but the fluorescence index does not. Copyright © 2013 Elsevier Ltd. All rights reserved.

The biogeochemistry of carbon across a gradient of streams and rivers within the Congo Basin

NASA Astrophysics Data System (ADS)

Mann, P. J.; Spencer, R. G. M.; Dinga, B. J.; Poulsen, J. R.; Hernes, P. J.; Fiske, G.; Salter, M. E.; Wang, Z. A.; Hoering, K. A.; Six, J.; Holmes, R. M.

2014-04-01

Dissolved organic carbon (DOC) and inorganic carbon (DIC, pCO2), lignin biomarkers, and theoptical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin, with the aim of examining how vegetation cover and hydrology influences the composition and concentration of fluvial carbon (C). Three sampling campaigns (February 2010, November 2010, and August 2011) spanning 56 sites are compared by subbasin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated shifting rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp subbasins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2,600 and 11,922 µatm, with swamp regions exhibiting extremely high pCO2 (10,598-15,802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers are largely driven by terrestrial ecosystem structure and that anthropogenic land use or climate change may impact fluvial C composition and reactivity, with ramifications for regional C budgets and future climate scenarios.

Detection and structural identification of dissolved organic matter in Antarctic glacial ice at natural abundance by SPR-W5-WATERGATE 1H NMR spectroscopy.

PubMed

Pautler, Brent G; Simpson, André J; Simpson, Myrna J; Tseng, Li-Hong; Spraul, Manfred; Dubnick, Ashley; Sharp, Martin J; Fitzsimons, Sean J

2011-06-01

Dissolved organic matter (DOM) is ubiquitous in aquatic ecosystems and is derived from various inputs that control its turnover. Glaciers and ice sheets are the second largest water reservoir in the global hydrologic cycle, but little is known about glacial DOM composition or contributions to biogeochemical cycling. Here we employ SPR-W5-WATERGATE (1)H NMR spectroscopy to elucidate and quantify the chemical structures of DOM constituents in Antarctic glacial ice as they exist in their natural state (average DOC of 8 mg/L) without isolation or preconcentration. This Antarctic glacial DOM is predominantly composed of a mixture of small recognizable molecules differing from DOM in marine, lacustrine, and other terrestrial environments. The major constituents detected in three distinct types of glacial ice include lactic and formic acid, free amino acids, and a mixture of simple sugars and amino sugars with concentrations that vary between ice types. The detection of free amino acid and amino sugar monomer components of peptidoglycan within the ice suggests that Antarctic glacial DOM likely originates from in situ microbial activity. As these constituents are normally considered to be biologically labile (fast cycling) in nonglacial environments, accelerated glacier melt and runoff may result in a flux of nutrients into adjacent ecosystems.

Extensive processing of sediment pore water dissolved organic matter during anoxic incubation as observed by high-field mass spectrometry (FTICR-MS).

PubMed

Valle, Juliana; Gonsior, Michael; Harir, Mourad; Enrich-Prast, Alex; Schmitt-Kopplin, Philippe; Bastviken, David; Conrad, Ralf; Hertkorn, Norbert

2018-02-01

Dissolved organic matter (DOM) contained in lake sediments is a carbon source for many microbial degradation processes, including aerobic and anaerobic mineralization. During anaerobic degradation, DOM is partially consumed and transformed into new molecules while the greenhouse gases methane (CH 4 ) and carbon dioxide (CO 2 ) are produced. In this study, we used ultrahigh resolution mass spectrometry to trace differences in the composition of solid-phase extractable (PPL resin) pore water DOM (SPE-DOM) isolated from surface sediments of three boreal lakes before and after 40 days of anoxic incubation, with concomitant determination of CH 4 and CO 2 evolution. CH 4 and CO 2 production detected by gas chromatography varied considerably among replicates and accounted for fractions of ∼2-4 × 10 -4 of sedimentary organic carbon for CO 2 and ∼0.8-2.4 × 10 -5 for CH 4 . In contrast, the relative changes of key bulk parameters during incubation, such as relative proportions of molecular series, elemental ratios, average mass and unsaturation, were regularly in the percent range (1-3% for compounds decreasing and 4-10% for compounds increasing), i.e. several orders of magnitude higher than mineralization alone. Computation of the average carbon oxidation state in CHO molecules of lake pore water DOM revealed rather non-selective large scale transformations of organic matter during incubation, with depletion of highly oxidized and highly reduced CHO molecules, and formation of rather non-labile fulvic acid type molecules. In general, proportions of CHO compounds slightly decreased. Nearly saturated CHO and CHOS lipid-like substances declined during incubation: these rather commonplace molecules were less specific indicators of lake sediment alteration than the particular compounds, such as certain oxygenated aromatics and carboxyl-rich alicyclic acids (CRAM) found more abundant after incubation. There was a remarkable general increase in many CHNO compounds during incubation across all lakes. Differences in DOM transformation between lakes corresponded with lake size and water residence time. While in the small lake Svarttjärn, CRAM increased during incubation, lignin-and tannin-like compounds were enriched in the large lake Bisen, suggesting selective preservation of these rather non-labile aromatic compounds rather than recent synthesis. SPE-DOM after incubation may represent freshly synthesized compounds, leftover bulk DOM which is primarily composed of intrinsically refractory molecules and/or microbial metabolites which were not consumed in our experiments. In spite of a low fraction of the total DOM being mineralized to CO 2 and CH 4 , the more pronounced change in molecular DOM composition during the incubation indicates that diagenetic modification of organic matter can be substantial compared to complete mineralization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spatio-temporal variations of organic matter along the Seine estuary (France)

NASA Astrophysics Data System (ADS)

Thibault, Alexandre; Huguet, Arnaud; Parlanti, Edith; Derenne, Sylvie

2017-04-01

Organic matter (OM) in aquatic systems plays an important role in water quality and biogeochemical processes. It is thus essential to characterize OM, especially in estuaries which are the place of the transport and the reactivity of natural and anthropogenic compounds. However, the characterization of OM in estuaries is complex due to its heterogeneity and variability in addition to specific features of these environments (salinity, turbidity…). Two types of aquatic OM, namely particulate (POM) and dissolved (DOM) are commonly distinguished by filtration. Due to its low concentration in estuaries (few mg/L), DOM has to be concentrated prior to its molecular (or structural) analysis. However, this step also induces the concentration of salts which are predominant (several g/L) in coastal environments. To overcome this issue, DOM has been isolated by a combination of reverse osmosis and electrodialysis. This method is more efficient than classical ones (ultrafiltration, solid phase techniques) in the isolation of representative DOM material. As a result, DOM can be characterized just as POM and sedimentary OM. The aim of this study is to characterize the spatiotemporal variability of DOM, POM and sedimentary OM along the Seine estuary (France) so as to understand its role in the functioning of this ecosystem. To this end, 5 sampling campaigns were performed in the Seine estuary between January 2015 and April 2016, during which large water samples (100 L) and sediment cores (10 cm) were collected. These campaigns covered the whole estuary. The three OM pools were analyzed through (i) elemental and isotopic analyses (Elemental Analysis-isotope ratio Mass Spectrometry, 14C ages) and (ii) structural analyses (13C solid state nuclear magnetic resonance, pyrolysis coupled with gas chromatography and mass spectrometry and ultrahigh resolution mass spectrometry), allowing to obtain both bulk and molecular information. The combination of these chemical characterization and statistical analyses shows that the 2 main factors driving the composition of OM in the Seine estuary are the OM pool (DOM, POM or sedimentary) and its origin (marine vs freshwater) whereas seasonal variations appear less pronounced. Indeed, OM exhibits higher C/N ratio and is richer in aliphatic and alkoxyl carbons than POM and sedimentary OM. The latter share the same elemental and isotopic composition but POM is enriched in aliphatic carbons with respect to sedimentary OM. These results confirm the higher hydrophilic nature of DOM when compared to POM and that the sedimentary OM in the Seine estuary is close to POM. Moreover, the dating of OM shows that DOM and POM are recent (> 1950 AD) contrary to sedimentary OM. When going downstream along the estuary, DOM is depleted in aliphatic carbons and enriched in alkoxyl carbons, the reverse trend being observed for POM. Both are enriched in δ13C.

Analysing Submarine Groundwater Discharge (SGD)-borne Dissolved Organic Matter (DOM) in a karstic aquifer, Co. Galway, Ireland.

NASA Astrophysics Data System (ADS)

Kelly, Tara; Rocha, Carlos

2014-05-01

Submarine Groundwater Discharge (SGD) constitutes an "invisible" link between land and sea, transporting allochthonous and autochthonous dissolved organic matter (DOM), nutrients and metals to the ocean via the subterranean estuary. The latter acts as a powerful bioreactor where groundwater, in transit from land to sea, mixes with seawater leading to active modulation of both DOM content and chemical makeup of SGD. DOM in freshwater systems is a key component of the global carbon cycle. Climate change may hence increase the concentration of allochthonous carbon entering the oceans as terrestrial DOC is released from soils at higher temperatures, and transported via SGD. Presently, little is known about the effects of SGD-borne DOM on coastal carbon cycling. SGD therefore represents a dynamic reservoir and analysis is critical to forecast future environmental management programmes, both on a local and global scale. Labile DOM plays a crucial role in microbial remineralisation processes, and as it breaks down it contributes to the groundwater nutrient pool. Locally, this could add to eutrophication. However, if refractory carbon is present, it will be recalcitrant to mineralisation in transit and at the subterranean estuary. This putative additional input will thus imply the contribution of SGD to oceanic carbon storage. This study is focused on Kinvara Bay (Galway, western Ireland), the focal point for waters discharging from the Gort-Kinvara karstic aquifer. This aquifer represents the ideal study location for evaluation of SGD contribution to the coastal DOM pool, as SGD is focused in the bay, surface drainage is very limited, and groundwater travels across a large catchment area with a short residence time, minimising DOM modification in transit. DOM samples collected in the field have been analysed using Three-Dimensional Excitation Emission Matrix Fluorescence (3D-EEMF) and High Temperature Catalytic Oxidation. PARAFAC is subsequently used as a tool to elucidate the types, sources (marine vs terrigeneous) and fractional composition of DOM, both in SGD plumes and in surface waters.

After the flood: consistency in DOM response to the 2010/2011 Australian floods

NASA Astrophysics Data System (ADS)

Shutova, Y.; Baker, A.; Bridgeman, J.; Henderson, R.

2014-12-01

The 2010/2011 floods in Eastern Australia were one of the worst on record, causing more than one billion AUD of damages and killing 35 people. This field campaign, monitoring raw water DOM concentration and character on three contrasting rivers across the region captured the late recession curve (October 2011- September 2012). DOM was characterized using fluorescence excitation-emission matrix (EEM) spectra with PARAFAC analysis; δ 13C-DOC; and molecular size using liquid chromatography with organic carbon, UV254 and nitrogen detection (LC-OCD) to identify DOC fractions: biopolymers, humic substance (HS), building blocks (BB), low molecular weight acids, and low molecular weight neutrals. Despite the difference in catchment and climatic zones, similar trends were observed in all three rivers, where DOC concentrations gradually decreased in river streams over a year from 8-11 mgCL-1 to 3-4 mgCL-1, followed by similar changes of HS, BB and fluorescent terrestrially delivered DOM components (C1-C3). In Allyn and Patterson rivers the proportion of HS, fluorescent terrestrially delivered DOM components (C1, C2) in DOC have decreased, in contrast to Logan River, where the ratio of HS/DOC was highly variable and showed no particular trends. The proportion of other DOC components remained almost the same. Molecular weight of the HS declined from 700 gmol-1 to 610 gmol-1 in all sites. δ 13C-DOC increased during monitoring, this could be linked to general decrease of DOM proportion delivered from C4 type plants after the flood. Overall, although DOC concentration decreased over the year post flood at all sites, most importantly the composition of DOM changed, with major changes occurring in proportion of humic-like and fluorescent terrestrially delivered DOM. Therefore it is important to monitor DOM character to be able to assess the impact of climate change and extreme weather events on the DOM transport and transformation.

Linking the mobilization of dissolved organic matter in catchments and its removal in drinking water treatment to its molecular characteristics.

PubMed

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

2017-04-15

Drinking water reservoirs in the Northern Hemisphere are largely affected by the decadal-long increase in riverine dissolved organic carbon (DOC) concentrations. The removal of DOC in drinking water treatment is costly and predictions are needed to link DOC removal efficiency to its mobilization in catchments, both of which are determined by the molecular composition. To study the effect of hydrological events and land use on the molecular characteristics of dissolved organic matter (DOM), 36 samples from three different catchment areas in the German low mountain ranges, with DOC concentrations ranging from 3 to 32 mg L -1 , were examined. Additionally, nine pairs of samples from downstream drinking water reservoirs were analyzed before and after flocculation. The molecular composition and the age of DOM were analyzed using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and radiocarbon ( 14 C) analysis. At elevated discharge in a forested catchment comparatively younger, more oxygenated and unsaturated molecules of higher molecular weight were preferentially mobilized, likely linked to the reductive mobilization of iron. DOM with highly similar molecular characteristics (O/C ratio > 0.5, m/z > 500) could also be efficiently removed through flocculation in drinking water treatment. The proportion of DOM removed through flocculation ranged between 43% and 73% of DOC and was highest at elevated discharge. In catchment areas with a higher percentage of grassland and agriculture a higher proportion of DOM molecules containing sulfur and nitrogen was detected, which in turn could be less efficiently flocculated. Altogether, it was shown that DOM that is released during large hydrological events can be efficiently flocculated again, suggesting a reversal of similar chemical mechanisms in both processes. Since the occurrence of heavy rainfall events is predicted to increase in the future, event-driven mobilization of DOC may continue to challenge drinking water production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spatio-seasonal variability in dissolved organic matter optical properties and its bioavailability in a subalpine lake

NASA Astrophysics Data System (ADS)

Stadler, Masumi; Ejarque, Elisabet; Kainz, Martin J.

2017-04-01

Allochthonous and autochothonous dissolved organic matter (DOM) in lakes mainly originate from terrestrial and aquatic primary production, respectively. Due to their differing biochemical composition the degradability of DOM by microorganisms is expected to vary. The carbon use efficiency of bacteria and DOM biodegradability determine whether the consumed DOM is incorporated into microbial biomass or respired to CO2 and ultimately emitted into the atmosphere. Thus, understanding the interaction of biodegradable DOM and its consumers is crucial to increase our knowledge on the role of lakes in the global carbon cycling. However, interactions of specific aquatic DOM signatures and the microbial population still remain widely debated. The aim of this study was to explore how DOM biodegradability changes along a stream-lake continuum at different seasons of the year. We monitored DOM quantity and its optical properties, inorganic nutrients, CO2 and bacterial growth over 20 days in dark bioassays with water from the inflow, outflow and at three layers of an oligotrophic subalpine lake. Preliminary results reveal highest microbial abundance in the metalimnion in winter and summer (0.7 106 and 2.5 106 cells mL-1, respectively) and the inflow in spring and autumn (1 106 and 1.4 106 cells mL-1, respectively) after 20 days. Surprisingly, with the exception of winter samples final inflow bacterial abundance results high, despite its lowest initial natural cell concentration, providing evidence for effective utilisation of terrestrial DOM, even with its high humic signature as indicated by the humification index (HIX). Nonetheless, after a microbial biomass peak with the inflow yielding mostly highest after three days, at the final experimental stage microbial biomass does only marginally differ between all sites with the exception of autumn samples where outflow and metalimnion turn out most productive. Even though the DOM of all lake sites and the lake outflow were characterised by lower molecular weight (indicated by the slope ratio (SR)) and a higher autochthonous signature (BIX) in all seasons, rapid growth of inflow bacteria highlight the potential of terrestrially-derived DOM to support bacterial growth, and challenge previous ideas that autchthonously-produced DOM would be more labile than DOM of terrestrial origin.

Linking groundwater dissolved organic matter to sedimentary organic matter from a fluvio-lacustrine aquifer at Jianghan Plain, China by EEM-PARAFAC and hydrochemical analyses.

PubMed

Huang, Shuang-bing; Wang, Yan-xin; Ma, Teng; Tong, Lei; Wang, Yan-yan; Liu, Chang-rong; Zhao, Long

2015-10-01

The sources of dissolved organic matter (DOM) in groundwater are important to groundwater chemistry and quality. This study examined similarities in the nature of DOM and investigated the link between groundwater DOM (GDOM) and sedimentary organic matter (SOM) from a lacustrine-alluvial aquifer at Jianghan Plain. Sediment, groundwater and surface water samples were employed for SOM extraction, optical and/or chemical characterization, and subsequent fluorescence excitation-emission matrix (EEM) and parallel factor analyses (PARAFAC). Spectroscopic properties of bulk DOM pools showed that indices indicative of GDOM (e.g., biological source properties, humification level, aromaticity and molecule mobility) varied within the ranges of those of two extracted end-members of SOM: humic-like materials and microbe-associated materials. The coexistence of PARAFAC compositions and the sustaining internal relationship between GDOM and extracted SOM indicate a similar source. The results from principal component analyses with selected spectroscopic indices showed that GDOM exhibited a transition trend regarding its nature: from refractory high-humification DOM to intermediate humification DOM and then to microbe-associated DOM, with decreasing molecular weight. Correlations of spectroscopic indices with physicochemical parameters of the groundwater suggested that GDOM was released from SOM and was modified by microbial diagenetic processes. The current study demonstrated the associations of GDOM with SOM from a spectroscopic viewpoint and provided new evidence supporting SOM as the source of GDOM. Copyright © 2015 Elsevier B.V. All rights reserved.

Selective Leaching of Dissolved Organic Matter From Alpine Permafrost Soils on the Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Wang, Yinghui; Xu, Yunping; Spencer, Robert G. M.; Zito, Phoebe; Kellerman, Anne; Podgorski, David; Xiao, Wenjie; Wei, Dandan; Rashid, Harunur; Yang, Yuanhe

2018-03-01

Ongoing global temperature rise has caused significant thaw and degradation of permafrost soils on the Qinghai-Tibetan Plateau (QTP). Leaching of organic matter from permafrost soils to aquatic systems is highly complex and difficult to reproduce in a laboratory setting. We collected samples from natural seeps of active and permafrost layers in an alpine swamp meadow on the QTP to shed light on the composition of mobilized dissolved organic matter (DOM) by combining optical measurements, ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry, radiocarbon (14C), and solid-state 13C nuclear magnetic resonance spectroscopy. Our results show that even though the active layer soils contain large amounts of proteins and carbohydrates, there is a selective release of aromatic components, whereas in the deep permafrost layer, carbohydrate and protein components are preferentially leached during the thawing process. Given these different chemical characteristics of mobilized DOM, we hypothesize that photomineralization contributes significantly to the loss of DOM that is leached from the seasonally thawed surface layer. However, with continued warming, biodegradation will become more important since biolabile materials such as protein and carbohydrate are preferentially released from deep-layer permafrost soils. This transition in DOM leachate source and associated chemical composition has ramifications for downstream fluvial networks on the QTP particularly in terms of processing of carbon and associated fluxes.

Insight into the composition and degradation potential of dissolved organic matter with different hydrophobicity in landfill leachates.

PubMed

He, Xiao-Song; Xi, Bei-Dou; Gao, Ru-Tai; Zhang, Hui; Dang, Qiu-Ling; Li, Dan; Huang, Cai-Hong

2016-02-01

Dissolved organic matter (DOM) isolated from the leachates with different landfill ages was fractionated into hydrophobic acid (HOA), hydrophobic neutral (HON), hydrophobic base (HOB) fractions and hydrophilic matter (HIM) based on hydrophobicity, and the composition and degradation potential of the bulk DOM and its fractions were investigated by excitation-emission matrix fluorescence spectra coupled with parallel factor analysis. Results showed that the bulk DOM comprised fulvic-, humic-, tryptophan- and tyrosine-like substances, as well as component C1, whose composition and origin was unidentified. Landfill process increased the content of component C1, fulvic- and humic-like matter. The HON fractions comprised primarily component C1 and tyrosine-like matter. The HOA, HOB and HIM fractions isolated from the young leachates consisted mainly of tryptophan- and tyrosine-like substances. As to the intermediate and old leachates, the HOA and HOB fractions comprised mainly component C1, while the HIM comprised mainly fulvic-like matter. The HIM showed the most resistant against biodegradation among the four fractions, and was the main component of leachate treatment. Advanced oxidation and/or membrane treatment are recommended to remove the HIM fraction due to its hydrophilic and stable characteristics. Copyright © 2015 Elsevier Ltd. All rights reserved.

Soft-template construction of three-dimensionally ordered inverse opal structure from Li2FeSiO4/C composite nanofibers for high-rate lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Donglin; Zhang, Wei; Sun, Ru; Yong, Hong-Tuan-Hua; Chen, Guangqi; Fan, Xiaoyong; Gou, Lei; Mao, Yiyang; Zhao, Kun; Tian, Miao

2016-06-01

Exploring a new method to fabricate small-sized nanofibers is essential to achieve superior performances for energy conversion and storage devices. Here, a novel soft-template strategy is developed to synthesize a three-dimensionally ordered macroporous (3DOM) architecture constructed from small-sized nanofibers. The effectiveness of a nanofiber-assembled three-dimensional inverse opal material as an electrode for high-rate lithium-ion batteries is demonstrated. The small-sized Li2FeSiO4/C composite nanofibers with a diameter of 20-30 nm are grown by employing a tri-block copolymer P123 as a structure directing agent. Accordingly, the macro-mesoporous hierarchical 3DOM architecture constructed from Li2FeSiO4/C nanofibers is further templated from P123 for the nanofibers and a polystyrene colloidal crystal array for the 3DOM architecture. We find that the thermal stability of the nanofiber morphology depends on the self-limited growth of Li2FeSiO4 nanocrystals in a crystalline-amorphous hybrid. As a cathode for a lithium-ion battery, the 3D hierarchical macro-mesoporous cathodes exhibit outstanding high-rate and ultralong-life performances with a capacity retention of 84% after 1500 cycles at 5 C in the voltage window of 1.5-4.5 V, which is greatly improved compared with a simple 3DOM Li2FeSiO4/C nanocomposite.Exploring a new method to fabricate small-sized nanofibers is essential to achieve superior performances for energy conversion and storage devices. Here, a novel soft-template strategy is developed to synthesize a three-dimensionally ordered macroporous (3DOM) architecture constructed from small-sized nanofibers. The effectiveness of a nanofiber-assembled three-dimensional inverse opal material as an electrode for high-rate lithium-ion batteries is demonstrated. The small-sized Li2FeSiO4/C composite nanofibers with a diameter of 20-30 nm are grown by employing a tri-block copolymer P123 as a structure directing agent. Accordingly, the macro-mesoporous hierarchical 3DOM architecture constructed from Li2FeSiO4/C nanofibers is further templated from P123 for the nanofibers and a polystyrene colloidal crystal array for the 3DOM architecture. We find that the thermal stability of the nanofiber morphology depends on the self-limited growth of Li2FeSiO4 nanocrystals in a crystalline-amorphous hybrid. As a cathode for a lithium-ion battery, the 3D hierarchical macro-mesoporous cathodes exhibit outstanding high-rate and ultralong-life performances with a capacity retention of 84% after 1500 cycles at 5 C in the voltage window of 1.5-4.5 V, which is greatly improved compared with a simple 3DOM Li2FeSiO4/C nanocomposite. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07783d

Trace metal mobilization by organic soil amendments: insights gained from analyses of solid and solution phase complexation of cadmium, nickel and zinc.

PubMed

Welikala, Dharshika; Hucker, Cameron; Hartland, Adam; Robinson, Brett H; Lehto, Niklas J

2018-05-01

The accumulation of Cd in soils worldwide has increased the demand for methods to reduce the metal's plant bioavailability. Organic matter rich soil amendments have been shown to be effective in achieving this. However, it is not known how long these amendments can retain the Cd, and whether dissolved organic matter (DOM) released from them can enhance the metal's mobility in the environment. In this study we sought to test the Cd binding capacity of various organic soil amendments, and evaluate differences in characteristics of the DOM released to see if they can explain the lability of the Cd-DOM complexes. We collected ten organic soil amendments from around New Zealand: five different composts, biosolids from two sources, two types of peat and spent coffee grounds. We characterised the amendments' elemental composition and their ability to bind the Cd. We then selected two composts and two peats for further tests, where we measured the sorption of Ni or Zn by the amendments. We analysed the quality of the extracted DOM from the four amendments using 3D Excitation Emission Matrix analysis, and tested the lability of the metal-DOM complexes using an adapted diffusive gradients in thin-films (DGT) method. We found that composts bound the most Cd and that the emergent Cd-DOM complexes were less labile than those from the peats. Ni-DOM complexes were the least labile. The aromaticity of the extracted DOM appears to be an important factor in determining the lability of Ni complexes, but less so for Zn and Cd. Copyright © 2018 Elsevier Ltd. All rights reserved.

High Frequency Monitoring of the Quantity and Quality of Dissolved Organic Matter Flux Between Salt Marshes and Plum Island Sound, MA

NASA Astrophysics Data System (ADS)

Zhao, Y.; Raymond, P.

2012-12-01

Salt marshes are highly productive continental margin ecosystems, due to abundant solar radiation, water, and nutrients provided by tidal water. The unique bi-directional water movement introduced by tidal effect has a major impact on the formation and productivity of salt marsh and the material exchange between salt marsh and adjacent estuary. As a major term in carbon, energy, and nutrient budget for aquatic ecosystem, dissolved organic matter (DOM) has broad impact on food webs, carbon cycle, and nutrient retention/release. The frequency and period of DOM measurement is greatly increased by the use of reagent-free, low-cost, and reliable measurement with fluorescent and UV sensors measuring the chromophoric fraction of total DOM. Although fluorescent sensors can only measure concentration, UV absorbance in a wide spectral range (200nm-380nm) could potentially provide information on DOM composition. With the help of accurate direct real time water flux measurement and lab analysis of lability, DON, and 3D excitation emission matrix spectroscopy (EEMs), a database of DOM quantity and quality exchanged between several comparative salt marshes and Plum Island Sound, MA could be established to study the dynamics of DOM behavior in the salt marsh-estuary system. Understanding DOM source and fate is very important for evaluating the role of salt marsh in the carbon cycle and food web in coastal and global scale because coastal carbon cycling represents up to 21% of the ocean's primary production (Jahnke 2008). In addition, the approaches outlined in this proposal have broad applicability to study DOM quantity and quality in the material exchange theme between systems.

Shifts in the Source and Composition of Dissolved Organic Matter in Southwest Greenland Lakes Along a Regional Hydro-climatic Gradient

NASA Astrophysics Data System (ADS)

Osburn, Christopher L.; Anderson, Nicholas J.; Stedmon, Colin A.; Giles, Madeline E.; Whiteford, Erika J.; McGenity, Terry J.; Dumbrell, Alex J.; Underwood, Graham J. C.

2017-12-01

Dissolved organic matter (DOM) concentration and quality were examined from Arctic lakes located in three clusters across south-west (SW) Greenland, covering the regional climatic gradient: cool, wet coastal zone; dry inland interior; and cool, dry ice-marginal areas. We hypothesized that differences in mean annual precipitation between sites would result in a reduced hydrological connectivity between lakes and their catchments and that this concentrates degraded DOM. The DOM in the inland lake group was characterized by a lower aromaticity and molecular weight, a low soil-like fluorescence, and carbon stable isotope (δ13C-DOC) values enriched by 2‰ relative to the coastal group. DOC-specific absorbance (SUVA254) and DOC-specific soil-like fluorescence (SUVFC1) revealed seasonal and climatic gradients across which DOM exhibited a dynamic we term "pulse-process": Pulses of DOM exported from soils to lakes during snow and ice melt were followed by pulses of autochthonous DOM inputs (possibly from macrophytes), and their subsequent photochemical and microbial processing. These effects regulated the dynamics of DOM in the inland lakes and suggested that if circumpolar lakes currently situated in cool wetter climatic regimes with strong hydrological connectivity have reduced connectivity under a drier future climate, they may evolve toward an end-point of large stocks of highly degraded DOC, equivalent to the inland lakes in the present study. The regional climatic gradient across SW Greenland and its influence on DOM properties in these lakes provide a model of possible future changes to lake C cycling in high-latitude systems where climatic changes are most pronounced.

Physical and chemical evolution of dissolved organic matter across the ablation season on a glacier in the central Tibet Plateau

NASA Astrophysics Data System (ADS)

Feng, L.; An, Y.; Xu, J.; Kang, S.; Xiaofei, L.

2017-12-01

The physical evolution (metamorphism) of snow is known to affect the chemical composition of dissolved organic matter (DOM) within it. Here we present a comprehensive study on the Dongkemadi glacier in the central Tibetan Plateau by collecting surface snow/ice samples from May to October 2015. The samples were grouped into four categories based on their physical descriptions, representing the different stages of the snowmelt (i.e., fresh snow, fine firn, coarse firn, and glacier ice). The concentrations of dissolved organic carbon (DOC) decreased from fresh snow (26.8 μmol L-1) to fine firn (15.0 μmol L-1) and enriched from fine firn to coarse firn (26.1 μmol L-1) and glacier ice (34.4 μmol L-1). This reflected the dynamic variation of DOC during the snowmelt. Excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) identified three protein-like components (C1, C2 and C4) and one microbial humic-like component (C3), which indicated a significant microbially derived DOM in the surface snow/ice. Molecular level composition of DOM identified by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) also shown newly produced molecular during the snowmelt. These results suggest that the snowmelt could not only induce a loss of DOM but also intensified the in situ microbial activities that enriched and modified it. These findings are important in understanding the evolution of the physical and chemical characteristics of the DOM during the ablation season and shed some light on the nature of the biogeochemical cycles in cryospheric regions.

Microbial response to different phytoplankton-derived dissolved organic matter sources in the Ross Sea, Antarctica

NASA Astrophysics Data System (ADS)

Sipler, R. E.; Spackeen, J.; McQuaid, J.; Bertrand, E. M.; Roberts, Q. N.; Baer, S. E.; Hutchins, D. A.; Allen, A. E.; Bronk, D. A.

2016-02-01

Western Antarctic shelves are highly productive regions that play an important role in global carbon and nitrogen cycles, specifically serving as a critical sink for carbon dioxide. Fixed carbon is stored within the phytoplankton cell as particulate organic matter or released into the surrounding water as dissolved organic matter (DOM). These phytoplankton-derived sources of organic matter support higher trophic levels as well as heterotrophic bacterial growth and respiration. The composition of the phytoplankton-derived organic matter is a function of the taxa as well as the environmental conditions under which it is produced. Phytoplankton community composition within western Antarctic Seas changes throughout Austral spring and summer with early production dominated by ice algae, switching to pelagic diatoms and flagellates later in the season. The goal of this study was to compare the response of Ross Sea microbial communities to DOM produced by ice algae or late season diatoms, specifically recent isolates of Pseudo nitzschia obtained from the Ross Sea. During 5-day bioassay studies, exudates from a natural ice algal community and from Pseudo nitzschia sp. isolates were added to natural microbial communities collected from two different Ross Sea locations, an ice-edge and an ice-covered site. The bacterial response to the DOM additions was greatest in the ice-covered community with a 5 and 3-fold higher bacterial abundance in the ice algae DOM and Pseudo nitzschia DOM treatments, respectively, relative to the control. The ice edge bacterial community responded similarly to both sources with a 2-fold increase in bacterial abundance compared to the control. Unlike the bacterial response, there was little difference in chlorophyll a concentrations between treatments, indicating that phytoplankton growth was not stimulated or inhibited by our additions.

Photochemical Reactions of Particulate Organic Matter: Deciphering the Role of Direct and Indirect Processes

NASA Astrophysics Data System (ADS)

Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

2016-12-01

Photochemical reactions of natural organic matter (NOM) represent potentially important pathways for biologically recalcitrant material to be chemically altered in aquatic systems. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools, however, a molecular level understanding of this chemically dynamic system is currently lacking. Photochemical reactions of a target molecule proceed by the direct absorption of a photon, or through reaction with a second photolytically generated species (i.e. the hydroxyl radical, singlet oxygen, excited triplet state NOM, hydrogen peroxide, etc.). Here, we isolate the major direct and indirect photochemical reactions of a lignocellulose-rich POM material (Phragmites australis) to determine their relative importance in changing the the chemical structure of the parent POM, and in the production of DOM. We measured POM molecular structure using a combination of NMR and FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry, while the chemical composition of photo-produced DOM was measured using ultra-high resolution mass spectrometry. Results are discussed in the context of the differences in chemical composition of both NOM pools resulting from the isolated photochemical pathways. All treatments result in an increase in DOM with reaction time, indicating that the larger POM matrix is likely fragmenting into smaller more soluble species. Spectroscopic measurements, on the other hand, point to functionalization reactions which increase the abundance of alcohol, acid, and carbonyl moieties in both carbon pools. This unique dataset provides new insight into how photochemical reactions alter the chemical composition of NOM while highlighting the relative importance of indirect pathways.

Size distribution of absorbing and fluorescing DOM in Beaufort Sea, Canada Basin

NASA Astrophysics Data System (ADS)

Gao, Zhiyuan; Guéguen, Céline

2017-03-01

The molecular weight (MW) of dissolved organic matter (DOM) is considered as an important factor affecting the bioavailability of organic matter and associated chemical species. Colored DOM (CDOM) MW distribution was determined, for the first time, in the Beaufort Sea (Canada Basin) by asymmetrical flow field-flow fractionation (AF4) coupled with online diode array ultra violet-visible photometer and offline fluorescence detectors. The apparent MW ranged from 1.07 to 1.45 kDa, congruent with previous studies using high performance size exclusion chromatography and tangential flow filtration. Interestingly, a minimum in MW was associated with the Pacific Summer Waters (PSW), while higher MW was associated with the Pacific Winter Waters (PWW). The Arctic Intermediate Waters (AIW) did not show any significant change in MW and fluorescence intensities distribution between stations, suggesting homogeneous DOM composition in deep waters. Three fluorescence components including two humic-like components and one protein-like component were PARAFAC-validated. With the increase of MW, protein-like fluorescence component became more dominant while the majority remained as marine/microbially derived humic-like components. Overall, it is concluded that water mass origin influenced DOM MW distribution in the Arctic Ocean.

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.

Determination of natural organic matter and iron binding capacity in fen samples

NASA Astrophysics Data System (ADS)

Kügler, Stefan; Cooper, Rebecca E.; Frieder Mohr, Jan; Wichard, Thomas; Küsel, Kirsten

2017-04-01

Natural organic matter (NOM) plays an important role in ecosystem processes such as soil carbon stabilization, nutrient availability and metal complexation. Iron-NOM-complexes, for example, are known to increase the solubility and, as a result, the bioavailability of iron in natural environments leading to several effects on the microbial community. Due to the various functions of NOM in natural environments, there is a high level of interest in the characterization of the molecular composition. The complexity of NOM presents a significant challenge in the elucidation of its composition. However, the development and utilization of high resolution mass spectrometry (HR-MS) as a tool to detect single compounds in complex samples has spearheaded the effort to elucidate the composition of NOM. Over the past years, the accuracy of ion cyclotron- or Orbitrap mass spectrometers has increased dramatically resulting in the possibility to obtain a mass differentiation of the large number of compounds in NOM. Together these tools provide significant and powerful insight into the molecular composition of NOM. In the current study, we aim to understand abiotic and biotic interactions between NOM and metals, such as iron, found in the Schlöppnerbrunnen fen (Fichtelgebirge, Germany) and how these interactions impact the microbial consortia. We characterized the dissolved organic matter (DOM) as well as basic chemical parameters in the iron-rich (up to 20 mg (g wt peat)-1), slightly acidic (pH 4.8) fen to gain more information about DOM-metal interactions. This minerotrophic peatland connected to the groundwater has received Fe(II) released from the surrounding soils in the Lehstenbach catchment. Absorption spectroscopy (AAS), differential pulse polarography (DPP) and high resolution electrospray ionization mass spectrometry (HR-ESI-Orbitrap-MS) was applied to characterize the molecular composition of DOM in the peat water extract (PWE). We identified typical patterns for DOM illustrated by van Krevelen plots, which indicate the presence of different substance classes including condensed aromatics, lignins and tannins known to complex iron. Our results indicate a variety of potential Fe-DOM-complexes present in the PWE samples when iron is incorporated into the elemental composition search. Using DPP we determine the complexation capacity of iron in the natural matrix of the fen along with the identification of ligands in order to estimate the iron bioavailability for bacteria. As the microbial redox system of the fen is impacted by other metals in the environment, we perform comprehensive analysis of the entirety of metal ions and concentrations in the water samples. Dialysis chambers are currently installed in the iron-rich fen from which pore water samples will be collected at 1 cm increments between 0-20 cm depth to determine the depth profiles of Fe(II)- and Fe(III)-concentration and evaluate the influence of the depth profiles on the interplay between microorganism comprising the natural microbial redox system of the fen. We have shown that metal-DOM-pH interactions affect the bioavailable metal concentration in fen water systems. This information will pave the way for a better understanding of the bacterial recruitment of trace elements and microbial redox reactions.

Whole-body vibration and the prevention and treatment of delayed-onset muscle soreness.

PubMed

Aminian-Far, Atefeh; Hadian, Mohammad-Reza; Olyaei, Gholamreza; Talebian, Saeed; Bakhtiary, Amir Hoshang

2011-01-01

Numerous recovery strategies have been used in an attempt to minimize the symptoms of delayed-onset muscle soreness (DOMS). Whole-body vibration (WBV) has been suggested as a viable warm-up for athletes. However, scientific evidence to support the protective effects of WBV training (WBVT) on muscle damage is lacking. To investigate the acute effect of WBVT applied before eccentric exercise in the prevention of DOMS. Randomized controlled trial. University laboratory. A total of 32 healthy, untrained volunteers were randomly assigned to either the WBVT (n  =  15) or control (n  =  17) group. Volunteers performed 6 sets of 10 maximal isokinetic (60°/s) eccentric contractions of the dominant-limb knee extensors on a dynamometer. In the WBVT group, the training was applied using a vibratory platform (35 Hz, 5 mm peak to peak) with 100° of knee flexion for 60 seconds before eccentric exercise. No vibration was applied in the control group. Muscle soreness, thigh circumference, and pressure pain threshold were recorded at baseline and at 1, 2, 3, 4, 7, and 14 days postexercise. Maximal voluntary isometric and isokinetic knee extensor strength were assessed at baseline, immediately after exercise, and at 1, 2, 7, and 14 days postexercise. Serum creatine kinase was measured at baseline and at 1, 2, and 7 days postexercise. The WBVT group showed a reduction in DOMS symptoms in the form of less maximal isometric and isokinetic voluntary strength loss, lower creatine kinase levels, and less pressure pain threshold and muscle soreness (P < .05) compared with the control group. However, no effect on thigh circumference was evident (P < .05). Administered before eccentric exercise, WBVT may reduce DOMS via muscle function improvement. Further investigation should be undertaken to ascertain the effectiveness of WBVT in attenuating DOMS in athletes.

Important property of polymer spheres for the preparation of three-dimensionally ordered macroporous (3DOM) metal oxides by the ethylene glycol method: the glass-transition temperature.

PubMed

Sadakane, Masahiro; Sasaki, Keisuke; Nakamura, Hiroki; Yamamoto, Takashi; Ninomiya, Wataru; Ueda, Wataru

2012-12-21

We demonstrate that the glass-transition temperature (T(g)) of a polymer sphere template is a crucial factor in the production of three-dimensionally ordered macroporous (3DOM) materials. Metal nitrate dissolved in ethylene glycol-methanol was infiltrated into the void of a face-centered, close-packed colloidal crystal of poly(methyl methacrylate) (PMMA)-based spheres. The metal nitrate reacts with EG to form a metal oxalate (or metal glycoxylate) solid (nitrate oxidation) in the void of the template when the metal nitrate-EG-PMMA composite is heated. Further heating converts metal oxalate to metal oxide and removes PMMA to form 3DOM materials. We investigated the effect of T(g) of PMMA templates and obtained clear evidence that the solidification temperature of the metal precursor solution (i.e., nitration oxidation temperature) should be lower than the T(g) of the polymer spheres to obtain a well-ordered 3DOM structure.

Dissolved Organic Matter in the Gulf of Maine: Implications for Blue Carbon Cycling in Coastal Waters

NASA Astrophysics Data System (ADS)

Aiken, G.

2016-12-01

Nutrients and dissolved organic matter (DOM) delivered from terrestrial sources to coastal oceans are critical for ocean productivity and the blue carbon cycle. Assessing influences of these inputs on marine productivity is difficult due to the difficulty in monitoring the processes controlling carbon cycling over short time frames, as well as the lack of historical data to assess possible trends. In this presentation, results of a long-term study designed to assess productivity and water quality in the Gulf of Maine (GoM), and waters delivering terrestrially derived DOM to the GoM are presented. DOM in the major tributaries and discrete samples collected along transects in the GoM were characterized by many analytical approaches including measurement of DOM optical properties, DOM fractionation, isotopic , 13C-NMR and FTICR-MS analyses. The compositional information provided by these was combined with optical data obtained by an in-situ glider and remotely sensed satellite data. Results indicate that DOM associated with inflowing waters to the GoM is rich in aromatic compounds resulting in a large influx of terrestrially derived, chromophoric DOM. The net result of these inflows is that DOM in the GoM is more chromophoric than samples from the Sargasso Sea and mid-Pacific Ocean. Hydrologic analyses using discharge:concentration relationships along with historical river discharge data indicate that the amount of DOM from rivers to the GoM has increased over the past 80 years leading to a `yellowing' of the waters in the GoM. Indeed, comparisons of ocean color between the present study and observations made by Henry Bigelow in 1912-1913 using the Forel-Ule color scale indicate an increase in chromophoric DOM in the past century. Chromophoric DOM influences the productivity of aquatic systems by reducing light available for phytoplankton photosynthesis and growth. Over the course of this study, a decline in primary productivity was also observed, perhaps resulting from increased DOM fluxes to the GoM. Climate and hydrologic models predict increasing precipitation and runoff in the GoM watershed during this century, possibly resulting in an increase of terrestrial OM delivered to the GoM of 30% during the next 80 years. This could potentially influence productivity and blue carbon cycling in this marine system.

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg-DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 -4. Heteroatomic molecules, especially those containing multiple S and N atoms, were found to bemore » among the most important in forming strong complexes with Hg. Major Hg-DOM complexes of C10H21N2S4Hg+ and C8H17N2S4Hg+ were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. These findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg-DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE PAGES

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.; ...

2016-12-22

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Molecular characterization of phytoplankton dissolved organic matter (DOM) and sulfur components using high resolution Orbitrap mass spectrometry.

PubMed

Mangal, Vaughn; Stock, Naomi L; Guéguen, Celine

2016-03-01

Orbitrap high resolution mass spectrometry (HRMS) with electrospray ionization in both positive and negative polarity was conducted on Suwannee River fulvic acid (SRFA), Pony Lake fulvic acid (PLFA) standards, and dissolved organic matter (DOM) released by freshwater phytoplankton (Scenedesmus obliquus, Euglena mutabilis, and Euglena gracilis). Three-dimensional van Krevelen diagrams expressing various oxygenation states of sulfur molecules and abundance plots of sulfur-containing species were constructed. Orbitrap HRMS analysis of SRFA found a high density of peaks in the lignin region (77 %) and low density of protein material (6.53 %), whereas for PLFA, 25 % of the total peaks were lignin related compared to 56 % of peaks in protein regions, comparable with other HRMS studies. Phytoplankton-derived DOM of S. obliquus, E. mutabilis, and E. gracilis was dominated by protein molecules at respective percentages of 36, 46, and 49 %, and is consistent with previous experiments examining phytoplankton-derived DOM composition. The normalized percentage of SO-containing compounds was determined among the three phytoplankton to be 56 % for Scenedesmus, 54 % for E. mutabilis, and 47 % for E. gracilis, suggesting variation between sulfur content in phytoplankton-derived DOM and differences in metal binding capacities. These results suggest the level of resolution by Orbitrap mass spectrometry is sufficient for preliminary characterization of phytoplankton DOM at an affordable cost relative to other HRMS techniques.

Fate and behavior of dissolved organic matter in a submerged anoxic-aerobic membrane bioreactor (MBR).

PubMed

Zhang, Dongqing; Trzcinski, Antoine Prandota; Luo, Jinxue; Stuckey, David C; Tan, Soon Keat

2018-02-01

In this study, the production, composition, and characteristics of dissolved organic matter (DOM) in an anoxic-aerobic submerged membrane bioreactor (MBR) were investigated. The average concentrations of proteins and carbohydrates in the MBR aerobic stage were 3.96 ± 0.28 and 8.36 ± 0.89 mg/L, respectively. After membrane filtration, these values decreased to 2.9 ± 0.2 and 2.8 ± 0.2 mg/L, respectively. High performance size exclusion chromatograph (HP-SEC) analysis indicated a bimodal molecular weight (MW) distribution of DOMs, and that the intensities of all the peaks were reduced in the MBR effluent compared to the influent. Three-dimensional fluorescence excitation emission matrix (FEEM) indicated that fulvic and humic acid-like substances were the predominant DOMs in biological treatment processes. Precise identification and characterization of low-MW DOMs was carried out using gas chromatography-mass spectrometry (GC-MS). The GC-MS analysis indicated that the highest peak numbers (170) were found in the anoxic stage, and 54 (32%) compounds were identified with a similarity greater than 80%. Alkanes (28), esters (11), and aromatics (7) were the main compounds detected. DOMs exhibited both biodegradable and recalcitrant characteristics. There were noticeable differences in the low-MW DOMs present down the treatment process train in terms of numbers, concentrations, molecular weight, biodegradability, and recalcitrance.

Comparing molecular composition of dissolved organic matter in soil and stream water: Influence of land use and chemical characteristics.

PubMed

Seifert, Anne-Gret; Roth, Vanessa-Nina; Dittmar, Thorsten; Gleixner, Gerd; Breuer, Lutz; Houska, Tobias; Marxsen, Jürgen

2016-11-15

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) was used to examine the molecular composition of dissolved organic matter (DOM) from soils under different land use regimes and how the DOM composition in the catchment is reflected in adjacent streams. The study was carried out in a small area of the Schwingbach catchment, an anthropogenic-influenced landscape in central Germany. We investigated 30 different soil water samples from 4 sites and different depths (managed meadow (0-5cm, 40-50cm), deciduous forest (0-5cm), mixed-coniferous forest (0-5cm) and agricultural land (0-5cm, 40-50cm)) and 8 stream samples. 6194 molecular formulae and their magnitude-weighted parameters ((O/C)w, (H/C)w, (N/C)w, (AI-mod)w, (DBE/C)w, (DBE/O)w, (DBE-O)w, (C#)w, (MW)w) were used to describe the molecular composition of the samples. The samples can be roughly divided in three groups. Group 1 contains samples from managed meadow 40-50cm and stream water, which are characterized by high saturation compared to samples from group 2 including agricultural samples and samples from the surface meadow (0-5cm), which held more nitrogen containing and aromatic compounds. Samples from both forested sites (group 3) are characterized by higher molecular weight and O/C ratio. Environmental parameters vary between sites and among these parameters pH and nitrate significantly affect chemical composition of DOM. Results indicate that most DOM in streams is of terrestrial origin. However, 120 molecular formulae were detected only in streams and not in any of the soil samples. These compounds share molecular formulae with peptides, unsaturated aliphatics and saturated FA-CHO/FA-CHOX. Compounds only found in soil samples are much more aromatic, have more double bonds and a much lower H/C ratio but higher oxygen content, which indicates the availability of fresh plant material and less microbial processed material compared to stream samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterising Event-Based DOM Inputs to an Urban Watershed

NASA Astrophysics Data System (ADS)

Croghan, D.; Bradley, C.; Hannah, D. M.; Van Loon, A.; Sadler, J. P.

2017-12-01

Dissolved Organic Matter (DOM) composition in urban streams is dominated by terrestrial inputs after rainfall events. Urban streams have particularly strong terrestrial-riverine connections due to direct input from terrestrial drainage systems. Event driven DOM inputs can have substantial adverse effects on water quality. Despite this, DOM from important catchment sources such as road drains and Combined Sewage Overflows (CSO's) remains poorly characterised within urban watersheds. We studied DOM sources within an urbanised, headwater watershed in Birmingham, UK. Samples from terrestrial sources (roads, roofs and a CSO), were collected manually after the onset of rainfall events of varying magnitude, and again within 24-hrs of the event ending. Terrestrial samples were analysed for fluorescence, absorbance and Dissolved Organic Carbon (DOC) concentration. Fluorescence and absorbance indices were calculated, and Parallel Factor Analysis (PARAFAC) was undertaken to aid sample characterization. Substantial differences in fluorescence, absorbance, and DOC were observed between source types. PARAFAC-derived components linked to organic pollutants were generally highest within road derived samples, whilst humic-like components tended to be highest within roof samples. Samples taken from the CSO generally contained low fluorescence, however this likely represents a dilution effect. Variation within source groups was particularly high, and local land use seemed to be the driving factor for road and roof drain DOM character and DOC quantity. Furthermore, high variation in fluorescence, absorbance and DOC was apparent between all sources depending on event type. Drier antecedent conditions in particular were linked to greater presence of terrestrially-derived components and higher DOC content. Our study indicates that high variations in DOM character occur between source types, and over small spatial scales. Road drains located on main roads appear to contain the poorest quality DOM of the sources studied due to the presence of hydrocarbons. In order to prevent storm-derived DOM degradation of water quality of urban streams, greater knowledge of links between these drainage sources, and their pathways to streams is required.

Photoproduction of hydrated electrons from natural organic solutes in aquatic environments

USGS Publications Warehouse

Zepp, R.G.; Braun, A.M.; Hoigne, J.; Leenheer, J.A.

1987-01-01

Laser flash photolysis was used to investigate the transients formed on absorption of 355-nm light by dissolved organic matter (DOM) from natural water bodies and from soil. Absorption spectra and quenching studies of the transients provided confirming evidence that hydrated electrons were formed by all of the DOM that were studied. The DOM from the Suwannee River in Georgia and from the Greifensee, a Swiss lake, exhibited great variability in light-absorbing properties. Despite this high variability in absorption coefficients, the primary quantum yields for electron ejection from the Greifensee and Suwannee DOM fell in a narrow range (0.005-0.008). Steady-state irradiations (355 nm) of the DOM with 2-chloroethanol (0.02 M) present as an electron scavenger produced chloride ions with quantum yields that were about 2 orders of magnitude lower than the primary quantum yields. This result indicates that most of the photoejected electrons recombine with cations before escaping into bulk solution. Irradiations of DOM solutions under sunlight (April, latitude 34?? N) photoproduced electrons at rates falling in the range of 0.2-0.4 ??mol/[(mg of DOC) h]. These results indicate that hydrated electrons can play a significant role in the environmental photoreduction of persistent, electronegative pollutants but may be relatively unimportant in the environmental production of hydrogen peroxide. ?? 1987 American Chemical Society.

Molecular characterization of dissolved organic matter from subtropical wetlands: a comparative study through the analysis of optical properties, NMR and FTICR/MS

NASA Astrophysics Data System (ADS)

Hertkorn, N.; Harir, M.; Cawley, K. M.; Schmitt-Kopplin, P.; Jaffé, R.

2015-08-01

Wetlands provide quintessential ecosystem services such as maintenance of water quality, water supply and biodiversity, among others; however, wetlands are also among the most threatened ecosystems worldwide. They are usually characterized by high levels of natural dissolved organic matter (DOM), representing a critical component in wetland biogeochemistry. This study describes the first detailed, comparative, molecular characterization of DOM in sub-tropical, pulsed, wetlands, namely the Everglades (USA), the Pantanal (Brazil) and the Okavango Delta (Botswana), using optical properties, high field nuclear magnetic resonance (NMR) and ultrahigh resolution mass spectrometry (FT-ICRMS), and compares compositional features to variations in organic matter sources and flooding characteristics (i.e. differences in hydroperiod). While optical properties showed both similarities and differences between these ecosystems, these differences were mainly based on the degree of aromaticity of the DOM. Analogies were such that an established excitation emission matrix fluorescence parallel factor analysis (EEM-PARAFAC) model for the Everglades was perfectly applicable to the other two wetlands. High-field (500 and 800 MHz) NMR spectra with cryogenic detection provided exceptional coverage and chemical description of wetland solid phase extracted (SPE) DOM. Area-normalized 1H NMR spectra of selected samples revealed clear distinctions of samples along with pronounced congruence within the three pairs of wetland DOM. Within sample pairs (long vs. short hydroperiod sites), internal differences mainly referred to intensity variations (denoting variable abundance) rather than to alterations of NMR resonances positioning (denoting diversity of molecules). The relative disparity was largest between the Everglades long and short hydroperiod samples, whereas Pantanal and Okavango samples were more alike among themselves. Otherwise, molecular divergence was most obvious in the case of unsaturated protons (δH > 5 ppm). The larger discrimination observed between 1H NMR spectra of DOM from different wetlands in comparison with the intrinsic variance among DOM within each wetland readily suggests the presence of an individual molecular signature, characteristic of each particular wetland. 2-D NMR spectroscopy for a particular sample revealed a large richness of aliphatic and unsaturated substructures, likely derived from microbial sources such as periphyton in the Everglades. In contrast, the chemical diversity of aromatic wetland DOM likely originates from a combination of higher plant sources, progressive microbial and photochemical oxidation, and contributions from combustion-derived products (e.g. black carbon). In addition, FT-ICRMS spectra allowed far-reaching classifications of wetland DOM. While DOM of both Okavango and Pantanal showed near 57 ± 2 % CHO, 8 ± 2 % CHOS, 33 ± 2 CHNO, and < 1 % CHNOS molecules, the mass spectra of Everglades samples were fundamentally different compared to those as well as among long and short hydroperiod samples, as they were markedly enriched in CHOS and CHNOS at the expense of CHO and CHNO compounds. Here, four groups of CHOS molecules were differentiated as (a) saturated sulfolipids, (b) unsaturated sulfolipids, (c) molecularly diverse DOM-type CHOS molecules, (d) and particularly enriched in the Everglades short hydroperiod site, a large set of aromatic and oxygen-deficient "black sulphur" compounds. The significantly higher proportion of CHOS compounds in general for the Everglades samples is likely the result of higher inputs of agriculture-derived and sea spray derived sulphate to this wetland compared to the others. Although wetland DOM samples were found to share many molecular features, each sample was unique in its composition, which reflected specific environmental drivers and/or specific biogeochemical processes.

Characterising DOC, DON and DOP flux in two contrasting lowland UK catchments: impacts of contrasting source character and connectivity on reach scale DOM signature

NASA Astrophysics Data System (ADS)

Yates, C. A.; Johnes, P.; Spencer, R. G.

2012-12-01

Riverine DOM is a significant component of C, N and P transport from source to sea. Research to date has focused on characterising DOC in upland and boreal moorland and forested catchments. Here we present the results of an investigation of DOM character and DOC, DON and DOP flux relative to C, N and P flux in two contrasting lowland UK catchments: the Wylye and Millersford Brook. Both were sampled at daily frequency at 3 sites over a 2 year period, (2010-11 WY, 2011-12 WY) with fluorescence EEMs and UV-Vis determined weekly. The Wylye is a Chalk catchment, underlain by a major aquifer. It has predominantly calcareous brown earth soils, intensive arable agriculture, scattered farms and riparian villages with a major settlement in the lower reaches of the river. There are few natural organic sources in the catchment and flows are baseflow dominated with a BFI of 0.93. DOC (NPOC) concentrations averaged 2.59 mg C/l in water year 2011-12, while Total N concentrations averaged 10.0 mg N/l, with DON averaging 0.9 mg N/l, and Total P concentrations averaged 0.18 mg/l with DOP averaging 0.026 mg/l. Millersford Brook drains peaty soils over glacial sands and clays, with moorland and forestry as the dominant land uses. Flows are dominated by overland and subsurface quick flow through with a BFI of 0.34. There is some low intensity grazing, no fertiliser use and no dwellings in the headwaters of the catchment. As a result nutrient concentrations are lower, but C flux is higher, with mean annual concentrations in WY 2011-12 of 0.93 mg TN/l, 0.051 mg TP/l, 8.83 mg DOC/l, 0.55 mg DON/l and 0.029 mg DOP/l. DOM character in Millersford Brook is comparable for that observed in other catchments with peaty soils and low acid neutralising capacity. The character of DOM varies along the length of the river, with HMW compounds dominating the signal in the headwaters, and LMW fluorescence intensities added to the signal in the lower reaches of the river, where septic tank effluent discharges and livestock wastes from small areas of improved grassland contribute to the DOM flux. The signal for the Wylye differs markedly from that for Millersford Brook. DOM character varies markedly along the length of the river to a greater extent than in Millersford Brook, with fluorescence centres indicating a high proportion of LMW material peaking downstream from septic tank and STW discharges. However, in the summer months lack of dilution of bankside septic tank and STW discharges leads to a high concentration of N-rich LMW DOM in the river, with C:N ratios approaching 1:1. This contrasts with data recorded for Millersford Brook, where DOM flux is dominated by HMW matter with low N content and a much higher N:C ratio. The results from this programme illustrate the variability in the composition of DOM relative to source character, both downstream within catchments, and between catchments of differing character. The specific composition of DOM varies markedly between peaty catchments and lowland intensively farmed catchments in sedimentary environments, and along gradients of nutrient enrichment within each catchment, changing the ecological significance of the DOM flux relative to stoichiometric ratios for differing biotic groups

Impacts of diverted freshwater on dissolved organic matter and microbial communities in Barataria Bay, Louisiana, U.S.A.

PubMed

Bianchi, Thomas S; Cook, Robert L; Perdue, E Michael; Kolic, Paulina E; Green, Nelson; Zhang, Yaoling; Smith, Richard W; Kolker, Alexander S; Ameen, Alex; King, Gary; Ojwang, Loice M; Schneider, Caroline L; Normand, Anna E; Hetland, Robert

2011-12-01

Here we present results of an initial assessment of the impacts of a water diversion event on the concentrations and chemical composition of dissolved organic matter (DOM) and bacterioplankton community composition in Barataria Bay, Louisiana U.S.A, an important estuary within the Mississippi River Delta complex. Concentrations and spectral properties of DOM, as reflected by UV/visible absorbance and fluorescence, were strikingly similar at 26 sites sampled along transects near two western and two eastern areas of Barataria Bay in July and September 2010. In September 2010, dissolved organic carbon (DOC) was significantly higher (568.1-1043 μM C, x=755.6+/-117.7 μM C, n=14) than in July 2010 (249.1-577.1 μM C, x=383.7+/-98.31 μM C, n=14); conversely, Abs254 was consistently higher at every site in July (0.105-0.314) than in September (0.080-0.221), averaging 0.24±0.06 in July and 0.15±0.04 in September. Fluorescence data via the fluorescence index (FI450/500) revealed that only 30% (8 of 26) of the July samples had an FI450/500 above 1.36, compared to 96% (25 of 26) for the September samples. This indicates a more terrestrial origin for the July DOM. Bacterioplankton from eastern sites differed in composition from bacterioplankon in western sites in July. These differences appeared to result from reduced salinities caused by the freshwater diversion. Bacterioplankton communities in September differed from those in July, but no spatial structure was observed. Thus, the trends in bacterioplankton and DOM were likely due to changes in water masses (e.g., input of Mississippi River water in July and a return to estuarine waters in September). Discharge of water from the Davis Pond Freshwater Diversion (DPFD) through Barataria Bay may have partially mitigated some adverse effects of the oil spill, inasmuch as DOM is concerned. Copyright © 2011 Elsevier Ltd. All rights reserved.

Temperature and chemical composition controls on sorption of DOC to iron hydroxides under dynamic flow conditions

NASA Astrophysics Data System (ADS)

Daugherty, E.; Lobo, G.; Pallud, C. E.; Borch, T.

2017-12-01

Mineral-organic associations contribute substantially to the long-term preservation of soil organic matter (SOM) and carbon sequestration. Iron-organic associations are especially important because iron (hydr)oxide minerals and surface coatings are prevalent and effective sorbents of SOM. While mineral-organic associations, and iron-organic associations in particular have been studied extensively, it remains unclear how the abiotic interactions between these soil components will be affected by shifting climate. Will DOM adsorption increase or decrease with rising temperature? Does the adsorption response to temperature depend on the type of DOM? To answer these questions, we investigated the impacts of temperature (7, 25, and 45˚C) and dissolved organic matter (DOM) type on DOM sorption to ferrihydrite-coated sand in a fixed bed column at neutral pH. Breakthrough curves of the standard humic substances at 25˚C indicated that humic acids were in general retained less than fulvic acids. Response to temperature varied from no effect to a marked increase in the quantity adsorbed. Modeling of DOM breakthrough curves using the advection-diffusion equation with a linear adsorption isotherm showed that the equilibrium distribution coefficient increased over time, with retardation factors increasing 4 to 10 times for every simulation. This suggests that the DOM adsorbed to the ferrihydrite-coated sand acts as a sorbent that is 4 to 10 times more powerful than the coated sand alone. Differences in breakthrough due to DOM type and temperature became less pronounced at slower flow rates, and breakthrough occurred at nearly half as many pore volumes at a flow rate of 0.01 mL min-1 vs. 0.05 mL min-1. These results suggest DOM adsorption was diffusion controlled at low flow rates and kinetically controlled at high flow rates, which may explain the increased temperature sensitivity at high flow rates. Analyses to determine adsorptive fractionation are ongoing, but preliminary data suggest that aromatic moieties may be selectively retained during initial contact between DOM and ferrihydrite. Our results suggest that water flow rate is likely to play an important role in determining the relative effects of temperature on DOM sorption to iron minerals.

Non-riverine pathways of terrigenous carbon to the ocean

NASA Astrophysics Data System (ADS)

Dittmar, T.

2007-12-01

The extent and nature of non-riverine fluxes of carbon from land to ocean are poorly understood. Tidal pumping from highly productive coastal environments, atmospheric deposition and submarine groundwater discharge can be significant transport mechanisms for carbon to the ocean. Evidence is mounting that tidally-induced porewater fluxes ("outwelling") of dissolved organic matter (DOM) from mangroves and salt marshes alone may be similar in magnitude as the global riverine flux of DOM. Tidal pumping of dissolved inorganic carbon (DIC) might exceed organic carbon fluxes by far, but the existing knowledge on DIC outwelling is too scarce for a first global estimate. Results from two case studies on the biogeochemistry of DOM outwelling are presented, from the mangroves in Northern Brazil and the salt marshes in the Northern Gulf of Mexico. Ongoing research in the Northern Gulf of Mexico indicates that outwelling and groundwater inputs probably exceed riverine DOM fluxes in this region. Similar observations were made in Northern Brazil. There, the fate of mangrove-derived DOM could be traced from its source in the mangrove sediments to the outer North Brazil shelf by using a combination of isotopic and molecular approaches. Reversed-phase liquid chromatography / mass spectrometry (LC/MS) provided a multifaceted array of information that mirrors the molecular complexity of DOM. Statistical analyses on these data revealed significant differences between mangrove and open-ocean DOM which successively disappeared by irradiating the samples with natural sunlight. Nuclear magnetic resonance analyses yielded concurrent results. Ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) is the only technique capable of resolving and identifying individual elemental compositions in these complex mixtures. We applied this technique for characterizing mangrove-derived DOM and to assess the molecular changes that occur in the initial stages of outwelling. The different approaches concordantly show the presence of photodegraded mangrove DOM on the North Brazil shelf. During transport offshore, sunlight efficiently destroyed aromatic molecules, removing about one third of mangrove-derived DOM. The remainder was refractory and may thus be distributed over the oceans.

The source and distribution of thermogenic dissolved organic matter in the ocean

NASA Astrophysics Data System (ADS)

Dittmar, T.; Suryaputra, I. G. N. A.; Paeng, J.

2009-04-01

Thermogenic organic matter (ThOM) is abundant in the environment. ThOM is produced at elevated temperature and pressure in deep sediments and earth's crust, and it is also a residue of fossil fuel and biomass burning ("black carbon"). Because of its refractory character, it accumulates in soils and sediments and, therefore, may sequester carbon from active cycles. It was hypothesized that a significant component of marine dissolved organic matter (DOM) might be thermogenic. Here we present a detailed data set on the distribution of thermogenic DOM in major water masses of the deep and surface ocean. In addition, several potential sources of thermogenic DOM to the ocean were investigated: active seeps of brine fluids in the deep Gulf of Mexico, rivers, estuaries and submarine groundwaters. Studies on deep-sea hydrothermal vents and aerosol deposition are ongoing. All DOM samples were isolated from seawater via solid phase extraction (SPE-DOM). ThOM was quantified in the extracts as benzene-polycarboxylic acids (BPCAs) after nitric acid oxidation via high-performance liquid chromatography and diode array detection (HPLC-DAD). BPCAs are produced exclusively from fused ring systems and are therefore unambiguous molecular tracers for ThOM. In addition to BPCA determination, the molecular composition and structure of ThOM was characterized in detail via ultrahigh resolution mass spectrometry (FT-ICR-MS). All marine and river DOM samples yielded significant amounts of BPCAs. The cold seep system in the deep Gulf of Mexico, but also black water rivers (like the Suwannee River) were particularly rich in ThOM. Up to 10% of total dissolved organic carbon was thermogenic in both systems. The most abundant BPCA was benzene-pentacarboxylic acid (B5CA). The molecular composition of BPCAs and the FT-ICR-MS data indicate a relatively small number (5-8) of fused aromatic rings per molecule. Overall, the molecular BPCA patterns were very similar independent of the source of ThOM. Petroleum-derived ThOM in the deep Gulf of Mexico had very similar structures than fused ring systems in asphaltenes, but also ThOM in the rivers and groundwaters was similar. First data on aerosols, on the other had, show a clear difference between particulate and dissolved samples. ThOM from aerosols and most soils was characterized by an abundance of benzene-hexacarboxylic acid (B6CA), different from thermogenic DOM. Dissolution processes may cause partial breakdown of larger fused ring systems and thus cause similar structural units in all DOM samples. In the deep ocean, the distribution of thermogenic DOM was relatively homogeneous throughout the water column. The concentration of carbon that resides in thermogenic polycyclic aromatic hydrocarbon varied between 610 and 800 nM (1.5-2% of total dissolved organic carbon). The total amount of thermogenic DOM in the deep ocean is approx. one Peta mole carbon globally. The relatively homogenous distribution of thermogenic DOM in the abyssal ocean indicates that thermogenic DOM behaves virtually inert in the abyssal environment. One of the most striking features is that the oldest water masses, which are not enriched in industrial products (such as the Freon CFC-12) showed highest concentrations of thermogenic DOM. The younger water masses such as Antarctic bottom and intermediate waters are not particularly enriched in thermogenic DOM. This distribution suggests a preindustrial origin of ThOM in the deep ocean. Rivers and deep-sea seep systems were both identified as potential sources of ThOM to the deep ocean. Radiocarbon dating on BPCAs will provide further evidence for the origin of BC in the deep ocean.

PARAFAC Modeling of Irradiation- and Oxidation-Induced Changes in Fluorescent Dissolved Organic Matter Extracted from Poultry Litter.

PubMed

Mangalgiri, Kiranmayi P; Timko, Stephen A; Gonsior, Michael; Blaney, Lee

2017-07-18

Parallel factor analysis (PARAFAC) applied to fluorescence excitation emission matrices (EEMs) allows quantitative assessment of the composition of fluorescent dissolved organic matter (DOM). In this study, we fit a four-component EEM-PARAFAC model to characterize DOM extracted from poultry litter. The data set included fluorescence EEMs from 291 untreated, irradiated (253.7 nm, 310-410 nm), and oxidized (UV-H 2 O 2 , ozone) poultry litter extracts. The four components were identified as microbial humic-, terrestrial humic-, tyrosine-, and tryptophan-like fluorescent signatures. The Tucker's congruence coefficients for components from the global (i.e., aggregated sample set) model and local (i.e., single poultry litter source) models were greater than 0.99, suggesting that the global EEM-PARAFAC model may be suitable to study poultry litter DOM from individual sources. In general, the transformation trends of the four fluorescence components were comparable for all poultry litter sources tested. For irradiation at 253.7 nm, ozonation, and UV-H 2 O 2 advanced oxidation, transformation of the humic-like components was slower than that of the tryptophan-like component. The opposite trend was observed for irradiation at 310-410 nm, due to differences in UV absorbance properties of components. Compared to the other EEM-PARAFAC components, the tyrosine-like component was fairly recalcitrant in irradiation and oxidation processes. This novel application of EEM-PARAFAC modeling provides insight into the composition and fate of agricultural DOM in natural and engineered systems.

Deciphering associations between dissolved organic molecules and bacterial communities in a pelagic marine system

PubMed Central

Osterholz, Helena; Singer, Gabriel; Wemheuer, Bernd; Daniel, Rolf; Simon, Meinhard; Niggemann, Jutta; Dittmar, Thorsten

2016-01-01

Dissolved organic matter (DOM) is the main substrate and energy source for heterotrophic bacterioplankton. To understand the interactions between DOM and the bacterial community (BC), it is important to identify the key factors on both sides in detail, chemically distinct moieties in DOM and the various bacterial taxa. Next-generation sequencing facilitates the classification of millions of reads of environmental DNA and RNA amplicons and ultrahigh-resolution mass spectrometry yields up to 10 000 DOM molecular formulae in a marine water sample. Linking this detailed biological and chemical information is a crucial first step toward a mechanistic understanding of the role of microorganisms in the marine carbon cycle. In this study, we interpreted the complex microbiological and molecular information via a novel combination of multivariate statistics. We were able to reveal distinct relationships between the key factors of organic matter cycling along a latitudinal transect across the North Sea. Total BC and DOM composition were mainly driven by mixing of distinct water masses and presumably retain their respective terrigenous imprint on similar timescales on their way through the North Sea. The active microbial community, however, was rather influenced by local events and correlated with specific DOM molecular formulae indicative of compounds that are easily degradable. These trends were most pronounced on the highest resolved level, that is, operationally defined ‘species', reflecting the functional diversity of microorganisms at high taxonomic resolution. PMID:26800236

Characterization of aquatic dissolved organic matter by asymmetrical flow field-flow fractionation coupled to UV-Visible diode array and excitation emission matrix fluorescence.

PubMed

Guéguen, Céline; Cuss, Chad W

2011-07-08

Flow field-flow fractionation (FlFFF) with on-line UV/Visible diode array detector (DAD) and excitation emission matrix (EEM) fluorescence detector has been developed for the characterization of optical properties of aquatic dissolved organic matter (DOM) collected in the Otonabee River (Ontario, Canada) and Athabasca River (Alberta, Canada). The molecular weight (MW) distribution of DOM was estimated using a series of organic macromolecules ranging from 479 to 66,000 Da. Both the number-average (M(n)) and weight-average (M(w)) molecular weights of Suwannee River fulvic acid (SRFA) and Suwannee River humic acid (SRHA) determined using these macromolecular standards were comparable to those obtained using polystyrenesulfonate (PSS) standards, suggesting that organic macromolecules can be used to estimate MW of natural organic colloids. The MW of eight river DOM samples determined by this method was found to have an M(n) range of 0.8-1.1 kDa, which agrees with available literature estimates. The FlFFF-DAD-EEM system provided insight into the MW components of river DOM including the optical properties by on-line absorbance and fluorescence measurement. A red-shift in emission and excitation wavelength maxima associated with lower spectral slope ratios (S(R)=S₂₇₅₋₂₉₅:S₃₅₀₋₄₀₀) was related to higher MW DOM. However, DOM of different origins at similar MW also showed significant difference in optical properties. A difference of 47 and 40 nm in excitation and emission peak C maxima was found. This supports the hypothesis that river DOM is not uniform in size and optical composition. Copyright © 2010 Elsevier B.V. All rights reserved.

A coupled geochemical and biogeochemical approach to characterize the bioreactivity of dissolved organic matter from a headwater stream

NASA Astrophysics Data System (ADS)

Sleighter, Rachel L.; Cory, Rose M.; Kaplan, Louis A.; Abdulla, Hussain A. N.; Hatcher, Patrick G.

2014-08-01

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31-45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1-0.5 or (2) low H/C of 0.5-1.0 spanning O/C 0.2-0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0-1.5, O/C 0.25-0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition.

Impacts of beaver ponds on dissolved organic matter cycling in small temperate streams.

NASA Astrophysics Data System (ADS)

Larsen, J.; Lambert, T.; Larsen, A.; Lane, S.

2017-12-01

Beavers are engineers that modify the structure of river reaches and their hydrological functioning. By building dams, they modify the travel time of running waters and can lead to the flooding of surrounding soils and terrestrial vegetation, with potentially significant impact on biogeochemical cycles. Contradictory effects of beaver ponds on dissolved organic matter (DOM) concentration and composition have however been reported, and the underlying reasons are still unclear. In this study, we aimed to investigate the role of the landscape morphology as an important driver determining how a beaver population can affect stream DOM cycling. Four streams localized in Switzerland and Germany were visited during different seasons (spring, summer, winter) and monitored at upstream and downstream locations of beaver ponds across a hydrological cycle. The sites differed in terms of river channel morphology, presence or absence of floodplain, and vegetation cover. DOM composition was investigated through absorbance and fluorescence measurements coupled with parallel factor analysis (PARAFAC) along with stream water quality (nutrients, pH, dissolved oxygen and water temperature). The results show that the effects of beaver dams were variable, and emphasizes the importance of the geomorphological context.

Delayed onset muscle soreness : treatment strategies and performance factors.

PubMed

Cheung, Karoline; Hume, Patria; Maxwell, Linda

2003-01-01

Delayed onset muscle soreness (DOMS) is a familiar experience for the elite or novice athlete. Symptoms can range from muscle tenderness to severe debilitating pain. The mechanisms, treatment strategies, and impact on athletic performance remain uncertain, despite the high incidence of DOMS. DOMS is most prevalent at the beginning of the sporting season when athletes are returning to training following a period of reduced activity. DOMS is also common when athletes are first introduced to certain types of activities regardless of the time of year. Eccentric activities induce micro-injury at a greater frequency and severity than other types of muscle actions. The intensity and duration of exercise are also important factors in DOMS onset. Up to six hypothesised theories have been proposed for the mechanism of DOMS, namely: lactic acid, muscle spasm, connective tissue damage, muscle damage, inflammation and the enzyme efflux theories. However, an integration of two or more theories is likely to explain muscle soreness. DOMS can affect athletic performance by causing a reduction in joint range of motion, shock attenuation and peak torque. Alterations in muscle sequencing and recruitment patterns may also occur, causing unaccustomed stress to be placed on muscle ligaments and tendons. These compensatory mechanisms may increase the risk of further injury if a premature return to sport is attempted.A number of treatment strategies have been introduced to help alleviate the severity of DOMS and to restore the maximal function of the muscles as rapidly as possible. Nonsteroidal anti-inflammatory drugs have demonstrated dosage-dependent effects that may also be influenced by the time of administration. Similarly, massage has shown varying results that may be attributed to the time of massage application and the type of massage technique used. Cryotherapy, stretching, homeopathy, ultrasound and electrical current modalities have demonstrated no effect on the alleviation of muscle soreness or other DOMS symptoms. Exercise is the most effective means of alleviating pain during DOMS, however the analgesic effect is also temporary. Athletes who must train on a daily basis should be encouraged to reduce the intensity and duration of exercise for 1-2 days following intense DOMS-inducing exercise. Alternatively, exercises targeting less affected body parts should be encouraged in order to allow the most affected muscle groups to recover. Eccentric exercises or novel activities should be introduced progressively over a period of 1 or 2 weeks at the beginning of, or during, the sporting season in order to reduce the level of physical impairment and/or training disruption. There are still many unanswered questions relating to DOMS, and many potential areas for future research.

[Three-dimensional Fluorescence Spectral Characteristics of Different Molecular Weight Fractionations of Dissolved Organic Matter in the Water-level Fluctuation Zones of Three Gorges Reservoir Areas].

PubMed

Chen, Xue-shuang; Jiang, Tao; Lu, Song; Wei, Shi-qiang; Wang, Ding-yong; Yan, Jin-long

2016-03-15

The study of the molecular weight (MW) fractions of dissolved organic matter (DOM) in aquatic environment is of interests because the size plays an important role in deciding the biogeochemical characteristics of DOM. Thus, using ultrafiltration ( UF) technique combined with three-dimensional fluorescence spectroscopy, DOM samples from four sampling sites in typical water-level fluctuation zones of Three Gorge Reservoir areas were selected to investigate the differences of properties and sources of different DOM MW fractions. The results showed that in these areas, the distribution of MW fractions was highly dispersive, but the approximately equal contributions from colloidal (Mr 1 x 10³-0.22 µm) and true dissolved fraction (Mr < 1 x 10³) to the total DOC concentration were found. Four fluorescence signals (humic-like A and C; protein-like B and T) were observed in all MW fractions including bulk DOM, which showed the same distribution trend: true dissolved > low MW (Mr 1 x 10³-10 x 10³) > medium MW (Mr 10 x 10³-30 x 10³) > high MW (Mr 30 x 10³-0.22 µm). Additionally, with decreasing MW fraction, fluorescence index (FI) and freshness index (BIX) increased suggesting enhanced signals of autochthonous inputs, whereas humification index ( HIX) decreased indicating lowe humification degree. It strongly suggested that terrestrial input mainly affected the composition and property of higher MW fractions of DOM, as compared to lower MW and true dissolved fractions that were controlled by autochthonous sources such as microbial and alga activities, instead of allochthonous sources. Meanwhile, the riparian different land-use types also affected obviously on the characteristics of DOM. Therefore, higher diversity of land-use types, and also higher complexity of ecosystem and landscapes, induced higher heterogeneity of fluorescence components in different MW fraction of DOM.

Molecular Signature of Organic Carbon Along a Salinity Gradient in Suwannee River Plume

NASA Astrophysics Data System (ADS)

Liu, Y.; Bianchi, T. S.; Ward, N. D.; Arellano, A. R.; Paša-Tolić, L.; Tolic, N.; Kuo, L. J.

2016-12-01

Humic and fulvic acid isolates from Suwannee River dissolved organic matter (DOM) have served as reference standards for the International Humic Substances Society (IHSS) for many decades. The large database on Suwannee DOM provides an excellent framework to further expand the application of Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) in characterizing the chemical composition of aquatic DOM. In this study, we examined the DOM signature of the lower Suwannee River and plume region at 5 stations along a salinity gradient (0 to 28) using FT-ICR-MS. The chemical characteristics of DOM show distinct differences across this steep salinity gradient. In general, samples collected from the coastal station have lower carbon number and are less aromatic. Molecular level analysis reveals that the magnitude weighted proportion of lipids increased as salinity increased. Interestingly, a similar trend was observed for lignin-like compounds. Target quantification of lignin-phenols showed that while the concentrations of these compounds were lower at the coastal station, the DOC-normalized concentrations were not significantly different between the river and coastal stations. In addition to traditional DOM moieties, we identified for the first time, halogenated organic compounds (HOC). We observed more chlorinated compounds in DOM and increased Cl/C as salinity increased. A relatively high proportion of halogenated lipids (compared to non-halogenated) were observed in the total pool of HOC across all stations. Although not significant in relative proportion, halogenated lignin-like compounds were the most abundant HOC moieties in our samples. CO2 concentrations decreased and became more 13C-enriched along the salinity gradient, ranging from 3,990 ppm (13CO2 = -17.3‰) at salinity 0 to 520 ppm (13CO2 = -7.5‰) at salinity 28, indicating high levels of DOM degradation in the river and a shift to primary production in the marine receiving waters, which is consistent with trends of lipid and lignin-like compounds observed with FT-ICR-MS.

Aps and Tep Chemical Characterization: Link Between The Dom and Pom Pools

NASA Astrophysics Data System (ADS)

Gogou, A.; Repeta, D. J.

The ocean inventory of dissolved organic carbon (DOC) is approximately 750 GT, comprising one of the Earth's largest carbon reservoirs on Earth. Despite its potential significance, the mechanisms that lead to DOM production and to spatial and temporal variations of DOM concentration in the world ocean are poorly understood. Chemical characterization studies show that up to 50% of HMW DOM is a structurally well-defined class of acylated polysaccharides (APS), which exhibits novel molecular-level characteris tics. Although APS synthesis occurs in the euphotic zone, a large fraction of the marine inventory of APS (appr. 10-30 GT C), resides in the deep ocean, and is approximately equal in mass to the total marine inventory of particulate organic carbon. While radiocarbon dating of deep sea DOC yields very old apparent ages (4000-6000 ybp), radiocarbon measurements made by our group on individual APS sugars shows that APS in the deep ocean has a radiocarbon value of +56 per mil, equivalent to surface water POC and DIC. This is the first clear evidence for the presence of "young" DOC in the deep ocean. One mechanism that could be important for the rapid removal of APS from surface seawater is physical removal by macroaggregates. To investigate the significance of this mechanism, we studied the chemical composition of surface-active POM (TEP) produced naturally on surface waters and in laboratory experiments, after bubbling of HMW DOM isolated from algal cultures. 1H-NMR spectral properties and molecular-level distribution of neutral sugars in natural and artificially produced TEP closely resembled those observed for cultured and oceanic HMW DOM, while they are significantly different from those of suspended particulate matter in the ocean (Gogou and Repeta, 2000). The results of these experiments provide evidence that POM with similar chemical characteristics to HMW DOM can be produced from algal-derived DOM in the surface ocean.

Influence of DOM components, salinity, pH, nitrate, and bicarbonate on the indirect photodegradation of acetaminophen in simulated coastal waters.

PubMed

Bai, Ying; Cui, Zhengguo; Su, Rongguo; Qu, Keming

2018-04-18

The indirect photodegradation behaviors of acetaminophen (APAP) were investigated in the presence of four kinds of dissolved organic matter (DOM) and were also assessed in the presence of seawater components and conditions such as salinity, pH, nitrate and bicarbonate. The results showed three important findings: firstly, in the indirect photolysis of APAP, the contributions of 3 DOM*, ·OH and 1 O 2 were >85.0%, 2.3-9.9% and 0.8-2.6% at pH 8.0. Secondly, DOM was divided into four terrestrial humic-like components by Excitation-emission matrix spectroscopy (EEMs) combined with parallel factor analysis (PARAFAC). This study showed a good linearity between DOM fluorescence components and the indirect photodegradation of APAP (R 2  = 0.92) and the differences in photodegradation rates of APAP among various DOM solutions were due to the diverse compositions of DOM. Finally, salinity was an important factor influencing the removal of APAP, and the APAP photodegradation rate constants increased from (3.33 ± 0.07) × 10 -5 s -1 to (1.25 ± 0.05) × 10 -4 s -1 with increasing salinity. The increased pseudo-first-order rate constants for photolysis of APAP with increasing salinity, pH and nitrate were attributed to the enhanced generation of reactive intermediates (RI) and easier reactions between RI and APAP. The increased APAP removal rate constant with increasing bicarbonate was likely ascribed to the yield of ∙CO 3 - . This is the first report of the roles of DOM components and salinity on the indirect photolysis of APAP. These findings would be essential to predict the photochemical fate of APAP and would also allow for a better understanding of the environmental fate of other phenolic contaminants. Copyright © 2018 Elsevier Ltd. All rights reserved.

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 of the hypothesis that part of marine DOM is of terrestrial origin, being the result of a long-term carbon sedimentation, has been obtained from several studies discussed herein.

Evidence for major input of riverine organic matter into the ocean

USGS Publications Warehouse

Cao, Xiaoyan; Aiken, George R.; Butler, Kenna D.; Huntington, Thomas G.; Balch, William M.; Mao, Jingdong; Schmidt-Rohr, Klaus

2018-01-01

The changes in the structure of XAD-8 isolated dissolved organic matter (DOM) samples along a river (Penobscot River) to estuary (Penobscot Bay) to ocean (across the Gulf of Maine) transect and from the Pacific Ocean were investigated using selective and two dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy coupled with elemental and carbon isotope analysis. The results provide important insights into the nature of relatively stable structures in the river-to-ocean continuum and the enigma of the fate of terrestrial DOM in the marine system. First, lignin and carboxyl-rich alicyclic molecules (CRAMs), which are indistinguishable from mass spectrometry, were clearly differentiated with NMR spectroscopy. NMR unambiguously showed that CRAMs persisted along the river-to-ocean transect and in the Pacific Ocean, while lignin residues dramatically decreased in abundance from the river to the coastal ocean and the Pacific Ocean. The results challenge a previous conclusion that lignin-derived compounds are refractory and can accumulate in the coastal ocean. The loss of terrestrial plant-derived aromatic compounds such as lignin and tannin residues throughout the sequence of riverine, coastal, and open ocean DOM extracts could also partially explain the decreasing organic carbon recovery by XAD-8 isolation and the change in carbon stable isotope composition from riverine DOM (δ13C −27.6‰) to ocean DOM (δ13C −23.0‰) extracts. The observation, from advanced NMR, of similar CRAM molecules in XAD-8 isolated DOM samples from the Penobscot River to the Penobscot Bay and from the ocean refutes a previous conclusion that XAD-isolated DOM samples from seawater and river are distinctly different. The alicyclic structural features of CRAMs and their presence as the major structural units in DOM extracts from the Penobscot River to Gulf of Maine transect, together with the deduced old 14C age of CRAMs in the ocean, imply that terrestrial CRAMs may persist on timescales long enough to be transported into the ocean.

Synthesis of three-dimensionally ordered macroporous manganese dioxide-carbon nanocomposites for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Zhi; Tan, Xiuli; Gao, Xin; Song, Lihong

2014-12-01

In this article, we report a composite of MnO2 nanoparticles supported by three-dimensionally ordered macroporous carbon (MnO2/3DOM carbon nanocomposites) fabricated by means of a simple multi-component infiltration of three-dimensional templates. MnO2 nanoparticles of 2 nm-6 nm are observed to be highly dispersed on the 3DOM carbon scaffolds. Cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy techniques are employed to assess the properties of these nanocomposites for use in supercapacitors. The results demonstrate that MnO2 can be effectively utilized with assistance of the 3DOM carbon in the electrode. The specific capacitance of the nanocomposite electrode can reach as high as 347 F g-1 at a current density of 0.5 A g-1. Moreover, the electrode exhibit excellent charge/discharge rate and good cycling stability, retaining over 92% of its initial charge after 5500 cycles at a current density of 2.5 A g-1. Such MnO2/3DOM carbon nanocomposite represents a promising exploring direction for enhancing the device performance of metal oxide-based electrochemical supercapacitors.

High soil solution carbon und nitrogen concentrations in a drained Atlantic bog are reduced to natural levels by 10 yr of rewetting

NASA Astrophysics Data System (ADS)

Frank, S.; Tiemeyer, B.; Gelbrecht, J.; Freibauer, A.

2013-10-01

Artificial drainage of peatlands causes dramatic changes in the release of greenhouse gases and in the export of dissolved carbon (C) and nutrients to downstream ecosystems. Rewetting anthropogenically altered peatlands offers a possibility to reduce nitrogen (N) and C losses. In this study, we investigate the impact of drainage and rewetting on the cycling of dissolved C and N as well as on dissolved gases over a period of 1 yr and 4 month, respectively. The peeper technique was used to receive a high vertical sampling resolution. Within one Atlantic bog complex a near natural site, two drained grasslands sites with different mean water table positions, and a former peat cutting area rewetted 10 yr ago were chosen. Our results clearly indicate that drainage increased the concentration of dissolved organic carbon (DOC), ammonia, nitrate and dissolved organic nitrogen (DON) compared to the near natural site. Drainage depth further determined the release and therefore the concentration level of DOC and N species, but the biochemical cycling and therefore dissolved organic matter (DOM) quality and N species composition were unaffected. Thus, especially deep drainage can cause high DOC losses. In general, DOM at drained sites was enriched in aromatic moieties as indicated by SUVA280 and showed a higher degradation status (lower DOC to DON ratio) compared to the near natural site. At the drained sites, equal C to N ratios of uppermost peat layer and DOC to DON ratio of DOM in soil solution suggest that the uppermost degraded peat layer is the main source of DOM. Nearly constant DOC to DON ratios and SUVA280 values with depth furthermore indicated that DOM moving downwards through the drained sites remained largely unchanged. DON and ammonia contributed most to the total dissolved nitrogen (TN). The subsoil concentrations of nitrate were negligible due to strong decline in nitrate around mean water table depth. Methane production during the winter months at the drained sites moved downwards to areas which were mostly water saturated over the whole year (>40 cm). Above these depths, the recovery of the water table in winter months led to the production of nitrous oxide around mean water table depth at drained sites. 10 yr after rewetting, the DOM quality (DOC to DON ratio and SUVA280) and quantity were comparable to the near natural site, indicating the re-establishment of mostly pristine biochemical processes under continuously water logged conditions. The only differences occur in elevated dissolved methane and ammonia concentrations reflecting the former disturbance by drainage and peat extraction. Rewetting via polder technique seems to be an appropriate way to revitalize peatlands on longer timescales and to improve the water quality of downstream water bodies.

Stream dissolved organic matter bioavailability and composition in watersheds underlain with discontinuous permafrost

Treesearch

Kelly L. Balcarczyk; Jeremy B. Jones; Rudolf Jaffe; Nagamitsu Maie

2009-01-01

We examined the impact of permafrost on dissolved organic matter (DOM) composition in Caribou-Poker Creeks Research Watershed (CPCRW), a watershed underlain with discontinuous permafrost, in interior Alaska. The stream draining the high permafrost watershed had higher DOC and dissolved organic nitrogen (DON) concentrations, higher DOCDON and greater specific...

Investigating the Sources and Dynamics of Dissolved Organic Matter in an Agricultural Watershed in California (U.S.A.)

NASA Astrophysics Data System (ADS)

Dyda, R. Y.; Hernes, P. J.; Spencer, R. G.; Ingrum, T. D.; Pellerin, B. A.; Bergamaschi, B. A.

2007-12-01

Dissolved organic matter (DOM) is ubiquitous and plays critical roles in nutrient cycling, aquatic food webs and numerous other biogeochemical processes. Furthermore, various factors control the quality and quantity of DOM, including land use, soil composition, in situ production, microbial uptake and assimilation and hydrology. As a component of DOM, dissolved organic carbon (DOC) has been recently identified as a drinking water constituent of concern due to its propensity to form EPA-regulated carcinogenic compounds when disinfected for drinking water purposes. Therefore, understanding the sources, cycling and modification of DOC across various landscapes is of direct relevance to a wide range of studies. The Willow Slough watershed is located in the Central Valley of California (U.S.A.) and is characterized by both diverse geomorphology as well as land use. The watershed drains approximately 425 km2 and is bordered by Cache and Putah Creeks to the north and south. The study area in the watershed includes the eastern portion of the foothills of the inner Coast Range and the alluvial plain and encompasses diverse land uses, including orchards, viticulture, dairy, pasture and natural grasslands. The Willow Slough watershed represents a unique opportunity to examine DOC dynamics through multiple land uses and hydrologic flow paths that are common throughout California. Preliminary data show that DOC concentrations at the watershed mouth peak during winter storms and also increase gradually throughout the summer months during the agricultural irrigation season. The increasing DOC concentrations during the summer months may result from agricultural runoff and/or primary production in channel. In addition, initial results using the chromophoric DOM (CDOM) absorption coefficient and spectral slope parameters indicate seasonal differences in the composition of the DOM. Spectral slopes decreased during both the summer irrigation season and winter storms relative to winter base flow, consistent with an increase in terrestrial signature. Biomolecular markers such as lignin phenols provide diagnostic source information on DOM as they are derived uniquely from vascular plants. Lignin can be used to differentiate angiosperm and gymnosperm tissues, but more importantly for this study, carbon-normalized yields can help to constrain the proportions of the increasing DOC during irrigation that come from vascular plants versus in situ production. In addition to supplying useful source information, dissolved lignin phenols undergo rapid photodegradation when exposed to adequate solar radiation, and this process is "imprinted" through increases in the acidic components of lignin and decreases in the syringyl phenols, thus providing insight into DOM cycling in agriculture-dominated watersheds. Data will be presented highlighting the use of a range of analytical and spectrophotometric measurements including lignin phenols, 13C of DOC and CDOM in the Willow Slough watershed for investigating sources and dynamics of DOM throughout the watershed.

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

NASA Astrophysics Data System (ADS)

Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna; Mao, Jingdong; Schmidt-Rohr, Klaus

2016-05-01

Seasonal (spring freshet, summer-autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV-visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64-74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63-77%) and TPIA (54-78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13-17% of HPOA and 15-20% of TPIA) and isolated O-CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C-O and O-C-O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

USGS Publications Warehouse

Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna D.; Mao, Jingdong; Schmidt-Rohr, Klaus

2016-01-01

Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

The molecular characteristics of pyrogenic organic materials and their aqueous leachates

NASA Astrophysics Data System (ADS)

Wozniak, A. S.; Hatcher, P.; Mitra, S.; Bostick, K. W.; Zimmerman, A. R.

2016-12-01

Pyrogenic organic matter (Py-OM), or black carbon, is known to impact soil chemistry, pollutant transport, regional and global carbon cycling, and climate. Py-OM is incorporated into soils via atmospheric deposition (e.g., from biomass, fossil fuel combustion) or direct applications by humans (e.g., biochars applied for agricultural production). Due to its presumed refractory and immobile nature, soil Py-OM is thought to be efficiently buried, sequestering atmospheric CO2. However, tracers of dissolved Py-OM (Py-DOM) have been detected in appreciable quantities in riverine, estuarine, and oceanic waters suggesting that Py-OM is more mobile in the environment than expected. The molecular characteristics of Py-OM are likely to be a controlling factor in the quantities and impacts of Py-DOM released to aqueous systems. Yet, little is known about the detailed molecular composition of these materials, let alone how those molecular characteristics vary with combustion conditions or are altered by environmental processes. Here, we examine oak and grass Py-OM (combusted over a range of temperatures), natural Py-OM (chars aged in the environment for variable lengths of time), and their Py-DOM leachates via nuclear magnetic resonance spectroscopy (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Multi-CP 13C NMR analyses of Py-OM materials and 1H NMR analyses of corresponding Py-DOM leachates reveal that Py-OM combustion temperature, environmental exposure, and molecular characteristics are reflected in Py-DOM quantities and characteristics. The relative amounts of aromatic C in Py-OM 1) decreases with environmental exposure, the relative oxygen-content in both Py-OM and Py-DOM, and the amount of Py-DOC released per g of Py-OC but 2) is positively correlated with combustion temperature and the relative contributions of acetate and aliphatic hydrogens (CH2) in Py-DOM. Preliminary FTICR-MS analyses show Py-DOM produced from oak at 400 °C to have lost carbohydrate-like compounds found in 250 °C Py-DOM and to contain an abundance of oxygenated aromatic compounds. Oak combusted at 650 °C produces Py-DOM characterized by high H/C, low O/C compounds. The results from this work will improve our understanding of Py-OM transport within and between terrestrial and aqueous systems.

Assessing the drivers of dissolved organic matter export from two contrasting lowland catchments, U.K.

PubMed

Yates, Christopher A; Johnes, Penny J; Spencer, Robert G M

2016-11-01

Two lowland catchments in the U.K. were sampled throughout 2010-11 to investigate the dominant controls on dissolved organic matter quantity and composition. The catchments had marked differences in terms of nutrient status, land cover and contrasting lithologies resulting in differences in the dominant flow pathways (groundwater vs. surface water dominated). The Upper Wylye is a chalk stream with a baseflow index of 0.98, draining a catchment dominated by intensive agricultural production. Millersford Brook is a lowland peat catchment with a baseflow index of 0.43, draining a semi-natural catchment with heather moorland and coniferous forest. Samples were collected weekly between October 2010 and September 2011 from eleven sampling locations. Samples were analysed to determine dissolved organic carbon, nitrogen and phosphorus fractions with DOM composition evaluated via the DOC:DON ratio, DOC:DOP ratio, specific UV absorption at 254nm, absorbance ratio (a250:a365) and the spectral slope parameter between 350 and 400nm (S350-400). Significant differences were observed in all determinands between the catchments, over time, and spatially along nutrient enrichment and geoclimatic gradients. Seasonal variation in preferential flow pathways mobilising groundwater-derived DOM were identified as likely controls on the delivery of DOM in the permeable chalk dominated catchment. Steeper S350-400 values and elevated a250:a365 ratios in this catchment suggest material of a lower bulk aromatic C content and molecular weight delivered during the winter months when compared to the summer. DOC:DON ratios were markedly lower in the chalk catchment than the peatland catchment, reflecting the paucity of organic matter within the mineral soils of the chalk landscape, and higher fertiliser application rates. This manuscript highlights that DOM composition varies according to catchment landscape character and hydrological function. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

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.

Metabolic and structural response of hyporheic microbial communities to variations in supply of dissolved organic matter

USGS Publications Warehouse

Findlay, S.E.G.; Sinsabaugh, R. L.; Sobczak, W.V.; Hoostal, M.

2003-01-01

Hyporheic sediment bacterial communities were exposed to dissolved organic matter (DOM) from a variety of sources to assess the interdependence of bacterial metabolism and community composition. Experiments ranged from small-scale core perfusions with defined compounds (glucose, bovine serum albumin) to mesocosms receiving natural leaf leachate or water from different streams. Response variables included bacterial production, oxygen consumption, extracellular enzyme activity, and community similarity as manifest by changes in banding patterns of randomly amplified polymorphic DNA (RAPD). All DOM manipulations generated responses in at least one metabolic variable. Additions of both labile and recalcitrant materials increased either oxygen consumption, production, or both depending on background DOM. Enzyme activities were affected by both types of carbon addition with largest effects from the labile mixture. Cluster analysis of RAPD data showed strong divergence of communities exposed to labile versus recalcitrant DOM. Additions of leaf leachate to mesocosms representing hyporheic flow-paths caused increases in oxygen consumption and some enzyme activities with weaker effects on production. Community structure yeas strongly affected; samples from the leachate-amended mesocosms clustered separately from the control samples. In mesocosms receiving water from streams ranging in DOC (0.5-4.5 mg L-1), there were significant differences in bacterial growth, oxygen consumption, and enzyme activities. RAPD analysis showed strongest clustering of samples by stream type with more subtle effects of position along the flowpaths. Responses in community metabolism were always accompanied by shifts in community composition, suggesting carbon supply affects both functional and structural attributes of hyporheic bacterial communities.

A mutli-technique search for the most primitive CO chondrites

NASA Astrophysics Data System (ADS)

Alexander, C. M. O'D.; Greenwood, R. C.; Bowden, R.; Gibson, J. M.; Howard, K. T.; Franchi, I. A.

2018-01-01

As part of a study to identify the most primitive COs and to look for weakly altered CMs amongst the COs, we have conducted a multi-technique study of 16 Antarctic meteorites that had been classified as primitive COs. For this study, we have determined: (1) the bulk H, C and N abundances and isotopes, (2) bulk O isotopic compositions, (3) bulk modal mineralogies, and (4) for some selected samples the abundances and compositions of their insoluble organic matter (IOM). Two of the 16 meteorites do appear to be CMs - BUC 10943 seems to be a fairly typical CM, while MIL 090073 has probably been heated. Of the COs, DOM 08006 appears to be the most primitive CO identified to date and is quite distinct from the other members of its pairing group. The other COs fall into two groups that are less primitive than DOM 08006 and ALH 77307, the previously most primitive CO. The first group is composed of members of the DOM 08004 pairing group, except DOM 08006. The second group is composed of meteorites belonging to the MIL 03377 and MIL 07099 pairing groups. These two pairing groups should probably be combined. There is a dichotomy in the bulk O isotopes between the primitive (all Antarctic finds) and the more metamorphosed COs (mostly falls). This dichotomy can only partly be explained by the terrestrial weathering experienced by the primitive Antarctic samples. It seems that the more equilibrated samples interacted to a greater extent with 16O-poor material, probably water, than the more primitive meteorites.

PAEs and BPA removal in landfill leachate with Fenton process and its relationship with leachate DOM composition.

PubMed

He, Pin-Jing; Zheng, Zhong; Zhang, Hua; Shao, Li-Ming; Tang, Qiong-Yao

2009-08-15

An increasing attention has been paid to the trace endocrine disrupting compounds (EDCs) in landfill leachate. In this paper, the removal of EDCs including phthalic acid esters (PAEs) and bisphenol A (BPA) from the fresh and mature landfill leachate by Fenton treatment was studied. More than 40% of PAEs and about 62% of BPA were removed from the raw mature leachate while only 20% of PAEs and 37% of BPA in the raw fresh leachate were reduced, respectively. After the fresh and mature leachates were spiked with PAEs to 1.5 mg L(-1) and BPA to 0.08 mg L(-1), the removal efficiencies of BPA and PAEs increased to more than 88%. The results indicated that the removing efficiencies of the EDCs in the leachate had a relationship with their concentrations, and that the trace levels of EDCs in leachate challenged the treatment capacity of the Fenton process. Most of the EDCs in the enriched leachate were removed by oxidation, which had no clear correlation with the hydrophobicity of the EDCs. The flocculation played an important role in the removal of di-(2-ethylhexyl) phthalate that could not be completely oxidized in the Fenton process, in that the EDCs with high n-octanol/water partition coefficient inclined to precipitate after the Fenton process. The dissolved organic matter (DOM) in the fresh leachate inhibited the EDCs removal more than the DOM in the mature leachate did. Both the composition of the leachate DOM and the characteristics of the EDCs determined the removing efficiencies of the EDCs in the Fenton process.

Chemical composition and cycling of dissolved organic matter in the Mid-Atlantic Bight

NASA Astrophysics Data System (ADS)

Aluwihare, Lihini I.; Repeta, Daniel J.; Chen, Robert F.

This study focuses on the chemical characterization of high molecular-weight dissolved organic matter (HMW DOM) isolated from the Middle Atlantic Bight in April 1994 and March 1996. Using proton nuclear magnetic resonance spectroscopy ( 1HNMR) and monosaccharide analysis we compared both spatial and temporal variations in the chemical structure of HMW DOM across this region. Our analyses support the presence of at least two compositionally distinct components to HMW DOM. The major component is acyl polysaccharide (APS), a biopolymer rich in carbohydrates, acetate and lipid, accounting for between 50% and 80% of the total high molecular-weight dissolved organic carbon (HMW DOC) in surface samples. APS is most abundant in fully marine, surface-water samples, and is a product of autochthonous production. Organic matter with spectral properties characteristic of humic substances is the second major component of HMW DOM. Humic substances are most abundant (up to 49% of the total carbon) in samples collected from estuaries, near the coast, and in deep water, suggesting both marine and perhaps terrestrial sources. Radiocarbon analyses of neutral monosaccharides released by the hydrolysis of APS have similar and modern (average 71‰) Δ 14C values. Radiocarbon data support our suggestion that these sugars occur as part of a common macromolecule, with an origin via recent biosynthesis. Preliminary radiocarbon data for total neutral monosaccharides isolated from APS at 300 and 750 m show this fraction to be substantially enriched relative to total HMW DOC and DOC. The relatively enriched radiocarbon values of APS at depth suggest APS is rapidly transported into the deep ocean.

Whole-Body Vibration and the Prevention and Treatment of Delayed-Onset Muscle Soreness

PubMed Central

Aminian-Far, Atefeh; Hadian, Mohammad-Reza; Olyaei, Gholamreza; Talebian, Saeed; Bakhtiary, Amir Hoshang

2011-01-01

Abstract Context: Numerous recovery strategies have been used in an attempt to minimize the symptoms of delayed-onset muscle soreness (DOMS). Whole-body vibration (WBV) has been suggested as a viable warm-up for athletes. However, scientific evidence to support the protective effects of WBV training (WBVT) on muscle damage is lacking. Objective: To investigate the acute effect of WBVT applied before eccentric exercise in the prevention of DOMS. Design: Randomized controlled trial. Setting: University laboratory. Patients or Other Participants: A total of 32 healthy, untrained volunteers were randomly assigned to either the WBVT (n  =  15) or control (n  =  17) group. Intervention(s): Volunteers performed 6 sets of 10 maximal isokinetic (60°/s) eccentric contractions of the dominant-limb knee extensors on a dynamometer. In the WBVT group, the training was applied using a vibratory platform (35 Hz, 5 mm peak to peak) with 100° of knee flexion for 60 seconds before eccentric exercise. No vibration was applied in the control group. Main Outcome Measure(s): Muscle soreness, thigh circumference, and pressure pain threshold were recorded at baseline and at 1, 2, 3, 4, 7, and 14 days postexercise. Maximal voluntary isometric and isokinetic knee extensor strength were assessed at baseline, immediately after exercise, and at 1, 2, 7, and 14 days postexercise. Serum creatine kinase was measured at baseline and at 1, 2, and 7 days postexercise. Results: The WBVT group showed a reduction in DOMS symptoms in the form of less maximal isometric and isokinetic voluntary strength loss, lower creatine kinase levels, and less pressure pain threshold and muscle soreness (P < .05) compared with the control group. However, no effect on thigh circumference was evident (P < .05). Conclusions: Administered before eccentric exercise, WBVT may reduce DOMS via muscle function improvement. Further investigation should be undertaken to ascertain the effectiveness of WBVT in attenuating DOMS in athletes. PMID:21214349

Complex Catchment Processes that Control Stream Nitrogen and Organic Matter Concentrations in a Northeastern USA Upland Catchment

NASA Astrophysics Data System (ADS)

Sebestyen, S. D.; Shanley, J. B.; Pellerin, B.; Saraceno, J.; Aiken, G. R.; Boyer, E. W.; Doctor, D. H.; Kendall, C.

2009-05-01

There is a need to understand the coupled biogeochemical and hydrological processes that control stream hydrochemistry in upland forested catchments. At watershed 9 (W-9) of the Sleepers River Research Watershed in the northeastern USA, we use high-frequency sampling, environmental tracers, end-member mixing analysis, and stream reach mass balances to understand dynamic factors affect forms and concentrations of nitrogen and organic matter in streamflow. We found that rates of stream nitrate processing changed during autumn baseflow and that up to 70% of nitrate inputs to a stream reach were retained. At the same time, the stream reach was a net source of the dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) fractions of dissolved organic matter (DOM). The in-stream nitrate loss and DOM gains are examples of hot moments of biogeochemical transformations during autumn when deciduous litter fall increases DOM availability. As hydrological flowpaths changed during rainfall events, the sources and transformations of nitrate and DOM differed from baseflow. For example, during storm flow we measured direct inputs of unprocessed atmospheric nitrate to streams that were as large as 30% of the stream nitrate loading. At the same time, stream DOM composition shifted to reflect inputs of reactive organic matter from surficial upland soils. The transport of atmospheric nitrate and reactive DOM to streams underscores the importance of quantifying source variation during short-duration stormflow events. Building upon these findings we present a conceptual model of interacting ecosystem processes that control the flow of water and nutrients to streams in a temperate upland catchment.

Using In-Situ Optical Sensors to Understand the Biogeochemistry of Dissolved Organic Matter Across a Stream Network

NASA Astrophysics Data System (ADS)

Wymore, Adam S.; Potter, Jody; Rodríguez-Cardona, Bianca; McDowell, William H.

2018-04-01

The advent of high-frequency in situ optical sensors provides new opportunities to study the biogeochemistry of dissolved organic matter (DOM) in aquatic ecosystems. We used fDOM (fluorescent dissolved organic matter) to examine the spatial and temporal variability in dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) across a heterogeneous stream network that varies in NO3- concentration. Across the ten study streams fDOM explained twice the variability in the concentration of DOC (r2 = 0.82) compared to DON (r2 = 0.39), which suggests that the N-rich fraction of DOM is either more variable in its sources or more bioreactive than the more stable C-rich fraction. Among sites, DON molar fluorescence was approximately 3x more variable than DOC molar fluorescence and was correlated with changes in inorganic N, indicating that DON is both more variable in composition as well as highly responsive to changes in inorganic N. Laboratory results also indicate that the fDOM sensors we used perform as well as the excitation-emission wavelength pair generally referred to as the "tryptophan-like" peak when measured under laboratory conditions. However, since neither the field sensor not the laboratory measurements explained a large percentage of variation in DON concentrations, challenges still remain for monitoring the ambient pool of dissolved organic nitrogen. Sensor networks provide new insights into the potential reactivity of DOM and the variability in DOC and DON biogeochemistry across sites. These insights are needed to build spatially explicit models describing organic matter dynamics and water quality.

Tracking variations in fluorescent-dissolved organic matter in an aerobic submerged membrane bioreactor using excitation-emission matrix spectra combined with parallel factor analysis.

PubMed

Hur, Jin; Shin, Jaewon; Kang, Minsun; Cho, Jinwoo

2014-08-01

In this study, the variations in the fluorescent components of dissolved organic matter (DOM) were tracked for an aerobic submerged membrane bioreactor (MBR) at three different operation stages (cake layer formation, condensation, and after cleaning). The fluorescent DOM was characterized using excitation-emission matrix (EEM) spectroscopy combined with parallel factor analysis (PARAFAC). Non-aromatic carbon structures appear to be actively involved in the membrane fouling for the cake layer formation stage as revealed by much higher UV-absorbing DOM per organic carbon found in the effluent versus those inside the reactor. Four fluorescent components were successfully identified from the reactor and the effluent DOMs by EEM-PARAFAC modeling. Among those in the reactor, microbial humic-like fluorescence was the most abundant component at the cake layer formation stage and tryptophan-like fluorescence at the condensation stage. In contrast to the reactor, relatively similar composition of the PARAFAC components was exhibited for the effluent at all three stages. Tryptophan-like fluorescence displayed the largest difference between the reactor and the effluent, suggesting that this component could be a good tracer for membrane fouling. It appears that the fluorescent DOM was involved in membrane fouling by cake layer formation rather than by internal pore adsorption because its difference between the reactor and the effluent was the highest among all the four components, even after the membrane cleaning. Our study provided an insight into the fate and the behavior fluorescent DOM components for an MBR system, which could be an indicator of the membrane fouling.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2016-09-01

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Role of Physical and Human Landscape Properties on Carbon Composition of Organic Matter in Tropical Rivers

NASA Astrophysics Data System (ADS)

Ballester, M. R.; Krusche, A. V.; Victoria, R. L.; Richey, J. E.; Deegan, L.; Neill, C.

2011-12-01

To evaluate physical and human controls organic matter carbon composition in tropical rivers, we applied an integrated analysis of landscape properties and riverine isotopic composition. Our goal was to establish the relationships between basin attributes and forms and composition of dissolved and particulate organic matter in rivers. A GIS template was developed as tool to support the understanding of the biogeochemistry of the surface waters of the Ji-Paraná (Western Amazonia) and the Piracicaba (southeastern of Brazil)rivers. Each basin was divided into drainage units, organized according to river network morphology and degree of land-use impact. The delineated drainage areas were individually characterized in terms of topography, soils and land use using data sets compiled as layers in ArcGis and ERDAS-IMAGINE software. DOM and POM carbon stable isotopic composition were determined at several sites along the main tributaries and small streams. The effects of these drivers on the fluvial carbon was quantified by a multiple linear regression analysis, relating basin characteristics and river isotopic composition. The results showed that relatively recent land cover changes have already had an impact on the composition of the riverine DOM and POM, indicating that, as in natural ecosystems, the vegetation plays a key role in the composition of the riverine organic matter in agricultural systems.

Photochemical Alternation of Phragmites australis Plant Litter: New Insight into the Chemical Evolution of Particulate Organic Matter

NASA Astrophysics Data System (ADS)

Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

2015-12-01

The photolysis of natural organic matter (NOM) is a potential pathway for the alteration of material that is not easily biodegraded. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools. However, a detailed understanding of the underlying chemical changes to the material in both phases is lacking. Here, we use a suspension of particles derived from Phragmites australis, a common marsh reed with high lignin content, as our model "recalcitrant" POM substrate. The solution was irradiated for three weeks with regular sampling, and the composition of the POM and the photo-produced DOM were measured separately using a suite of mass spectrometric and spectroscopic techniques. The chemical composition of individual molecules was measured by coupling soft ionization techniques (electrospray (ESI) and matrix assisted laser desorption (MALDI) to high-resolution mass spectrometry. Structural information, including the distribution of the major carbon containing functional groups, was obtained using a combination of FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry. Results are discussed in the context of differences in chemical composition and structure with increased irradiation time for both organic matter pools. We observed a general shift in the mass spectra of POM towards lower molecular weight masses and an increase in the abundance of ions in DOM as a function of irradiation time- hence the larger POM matrix is likely fragmenting into smaller species that are more soluble. Spectroscopic measurements indicate that the abundance of acidic and alcohol functionalities increased with irradiation in both carbon pools. These complementary approaches provide new detailed information about how the chemical composition of recalcitrant NOM evolves as it is exposed to sunlight.

Chemical and spectroscopic characterization of dissolved humic substances in a mangrove-fringed estuary in the eastern coast of Hainan Island, China

NASA Astrophysics Data System (ADS)

Zhang, Yaoling; Du, Jinzhou; Peng, Bo; Zhang, Fenfen; Zhao, Xin; Zhang, Jing

2013-03-01

Mangrove-derived dissolved organic matter (DOM) has an important effect on estuarine and coastal area on a large scale. In order to improve the understanding of origin, composition, and fate of DOM in mangrove-fringed estuarine and coastal areas, dissolved humic substances (DHS) were isolated from one mangrove pore-water sample and one near-shore seawater sample downstream the mangrove pore-water site in the eastern coast of Hainan Island, South China. Fulvic acids, humic acids and XAD-4 fractions were obtained from the two water samples by using a two-column array of XAD-8 and XAD-4 resins. Chemical and spectroscopic methods were used to analyze the features of these DHS. Compared to the mangrove pore-water DHS, the near-shore seawater DHS were found rich in 13C with lower C/N ratios and more aliphatic compounds and carbohydrates, but less aromatic structures and carboxyl groups. As for the three fractions of the two DHS, XAD-4 fractions contain more aliphatics, carbohydrates, carboxyl groups, and enrich in 13C with respect to both fulvic and humic acids. Photo-oxidation transformation and contribution from marine-derived DOM were considered as the main reasons resulted in the difference in compositional features for these DHS in this study.

Using fluorescence spectroscopy coupled with chemometric analysis to investigate the origin, composition, and dynamics of dissolved organic matter in leachate-polluted groundwater.

PubMed

He, Xiao-Song; Xi, Bei-Dou; Gao, Ru-Tai; Wang, Lei; Ma, Yan; Cui, Dong-Yu; Tan, Wen-Bing

2015-06-01

Groundwater was collected in 2011 and 2012, and fluorescence spectroscopy coupled with chemometric analysis was employed to investigate the composition, origin, and dynamics of dissolved organic matter (DOM) in the groundwater. The results showed that the groundwater DOM comprised protein-, fulvic-, and humic-like substances, and the protein-like component originated predominantly from microbial production. The groundwater pollution by landfill leachate enhanced microbial activity and thereby increased microbial by-product-like material such as protein-like component in the groundwater. Excitation-emission matrix fluorescence spectra combined with parallel factor analysis showed that the protein-like matter content increased from 2011 to 2012 in the groundwater, whereas the fulvic- and humic-like matter concentration exhibited no significant changes. In addition, synchronous-scan fluorescence spectra coupled with two-dimensional correlation analysis showed that the change of the fulvic- and humic-like matter was faster than that of the protein-like substances, as the groundwater flowed from upstream to downstream in 2011, but slower than that of the protein-like substance in 2012 due to the enhancement of microbial activity. Fluorescence spectroscopy combined with chemometric analysis can investigate groundwater pollution characteristics and monitor DOM dynamics in groundwater.

Application of fecal near-infrared spectroscopy and nutritional balance software to monitor diet quality and body condition in beef cows grazing Arizona rangeland.

PubMed

Tolleson, D R; Schafer, D W

2014-01-01

Monitoring the nutritional status of range cows is difficult. Near-infrared spectroscopy (NIRS) of feces has been used to predict diet quality in cattle. When fecal NIRS is coupled with decision support software such as the Nutritional Balance Analyzer (NUTBAL PRO), nutritional status and animal performance can be monitored. Approximately 120 Hereford and 90 CGC composite (50% Red Angus, 25% Tarentaise, and 25% Charolais) cows grazing in a single herd were used in a study to determine the ability of fecal NIRS and NutbalPro to project BCS (1 = thin and 9 = fat) under commercial scale rangeland conditions in central Arizona. Cattle were rotated across the 31,000 ha allotment at 10 to 20 d intervals. Cattle BCS and fecal samples (approximately 500 g) composited from 5 to 10 cows were collected in the pasture approximately monthly at the midpoint of each grazing period. Samples were frozen and later analyzed by NIRS for prediction of diet crude protein (CP) and digestible organic matter (DOM). Along with fecal NIRS predicted diet quality, animal breed type, reproductive status, and environmental conditions were input to the software for each fecal sampling and BCS date. Three different evaluations were performed. First, fecal NIRS and NutbalPro derived BCS was projected forward from each sampling as if it were a "one-time only" measurement. Second, BCS was derived from the average predicted weight change between 2 sampling dates for a given period. Third, inputs to the model were adjusted to better represent local animals and conditions. Fecal NIRS predicted diet quality varied from a minimum of approximately 5% CP and 57% DOM in winter to a maximum of approximately 11% CP and 60% DOM in summer. Diet quality correlated with observed seasonal changes and precipitation events. In evaluation 1, differences in observed versus projected BCS were not different (P > 0.1) between breed types but these values ranged from 0.1 to 1.1 BCS in Herefords and 0.0 to 0.9 in CGC. In evaluation 2, differences in observed versus projected BCS were not different (P > 0.1) between breed types but these values ranged from 0.00 to 0.46 in Hereford and 0.00 to 0.67 in CGC. In evaluation 3, the range of differences between observed and projected BCS was 0.04 to 0.28. The greatest difference in projected versus observed BCS occurred during periods of lowest diet quality. Body condition was predicted accurately enough to be useful in monitoring the nutrition of range beef cows under the conditions of this study.

Relationship between dissolved organic matter quality and microbial community composition across polar glacial environments.

PubMed

Smith, H J; Dieser, M; McKnight, D M; SanClements, M D; Foreman, C M

2018-05-14

Vast expanses of Earth's surface are covered by ice, with microorganisms in these systems affecting local and global biogeochemical cycles. We examined microbial assemblages from habitats fed by glacial meltwater within the McMurdo Dry Valleys, Antarctica, and on the west Greenland Ice Sheet, (GrIS) evaluating potential physicochemical factors explaining trends in community structure. Microbial assemblages present in the different Antarctic dry valley habitats were dominated by Sphingobacteria and Flavobacteria, while Gammaproteobacteria and Sphingobacteria prevailed in west GrIS supraglacial environments. Microbial assemblages clustered by location (Canada Glacier, Cotton Glacier, west GrIS) and were separated by habitat type (i.e. ice, cryoconite holes, supraglacial lakes, sediment, and stream water). Community dissimilarities were strongly correlated with dissolved organic matter (DOM) quality. Microbial meltwater assemblages were most closely associated with different protein-like components of the DOM pool. Microbes in environments with mineral particles (i.e. stream sediments, cryoconite holes) were linked to DOM containing more humic-like fluorescence. Our results demonstrate the establishment of distinct microbial communities within ephemeral glacial meltwater habitats, with DOM-microbe interactions playing an integral role in shaping communities on local and polar spatial scales.

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 sources. Information generated by our study will provide a valuable data set for better understanding DOM bio-geochemical dynamics along the Florida Keys ecosystem and information for future studies linking DOM and the coral community.

Compositional Characteristics of Dissolved Organic Matter released from the sediment of Han river in Korea.

NASA Astrophysics Data System (ADS)

Oh, H.; Choi, J. H.

2017-12-01

The dissolved organic matter (DOM) has variable characteristics depending on the sources. The DOM of a river is affected by rain water, windborne material, surface and groundwater flow, and sediments. In particular, sediments are sources and sinks of nutrients and pollutants in aquatic ecosystems by supplying large amounts of organic matter. The DOM which absorbs ultraviolet and visible light is called colored dissolved organic matter (CDOM). CDOM is responsible for the optical properties of natural waters in several biogeochemical and photochemical processes and absorbs UV-A (315-400 nm) and UV-B (280-315), which are harmful to aquatic ecosystems (Helms et al., 2008). In this study, we investigated the quantity and quality of DOM and CDOM released from the sediments of Han river which was impacted by anthropogenic activities and hydrologic alternation of 4 Major River Restoration Project. The target area of this study is Gangchenbo (GC), Yeojubo (YJ), and Ipobo(IP) of the Han River, Korea. Sediments and water samples were taken on July and August of 2016 and were incubated at 20° up to 7 days. Absorbance was measured with UV-visible spectrophotometer (Libra S32 PC, Biochrom). Fluorescence intensity determined with Fluorescence EEMs (F-7000, Hitachi). Absorbance and fluorescence intensity were used to calculate Specific Ultraviolet Absorbance (SUVA254), Humification index (HIX), Biological index (BIX), Spectral slope (SR) and component analysis. The DOC concentration increased after 3 days of incubation. According to the SUVA254 analysis, the microbial activity is highest in the initial overlying water of IP. HIX have range of 1.35-4.08, and decrease poly aromatic structures of organic matter during incubation. From the results of the BIX, autochthonous organic matter was released from the sediments. In all sites, Humic-like DOM, Microbial humic-like DOM and Protein-like DOM increased significantly between Day 0 and 3(except Humic-like, Microbial humic-like DOM in IP). Spectral slope ratio of all sites increased according to incubation, which means that the amount of CDOM increased from the sediment to overlying water.

Zinc oxide nanoparticle toxicity in embryonic zebrafish: Mitigation with different natural organic matter.

PubMed

Kteeba, Shimaa M; El-Adawi, Hala I; El-Rayis, Osman A; El-Ghobashy, Ahmed E; Schuld, Jessica L; Svoboda, Kurt R; Guo, Laodong

2017-11-01

Exposure experiments were conducted to evaluate the influence of dissolved organic matter (DOM) on the toxicity of ZnO-NPs (10-30 nm) and dissolved Zn at sub-lethal doses (50 and 5 ppm, respectively) to zebrafish (Danio rerio). Humic acid, alginic acid, bovine serum albumin and various natural DOM isolated from rivers as the Milwaukee River-WI (NOMW), Yukon River-AK (NOMA) and Suwannee River-GA DOM (NOMS) were used to represent humic substances (HA), carbohydrates (CHO), proteins (PTN), and natural organic matter (NOM), respectively. Initial experiments were carried out to confirm the toxic effect of ZnO-NPs at 50 ppm, followed by mitigation experiments with different types and concentrations of DOM (0.4-40 mg-C/L). Compared to 0% hatch of 50 ppm ZnO-NPs exposed embryos at 72 h post fertilization (hpf), NOMS, NOMW and HA had the best mitigative effects on hatching (53-65%), followed by NOMA, CHO and PTN (19-35%); demonstrating that the mitigation effects on ZnO-NPs toxicity were related to DOM's quantity and composition. At 96 hpf, 20% of embryos exposed to 50 ppm ZnO-NPs hatched, 100% of embryos reared in embryo medium hatched, and close to 100% of the embryos hatched upon mitigation, except for those mitigated with PTN which had less effect. Dissolved Zn (5 ppm) also exhibited the same toxicity on embryos as ZnO-NPs (50 ppm). However, in the presence of HA, NOM and CHO, the hatching rates at 72 and 96 hpf increased significantly compared to 5% hatch without DOM. The overall mitigation effects produced by DOM followed the order of HA ≥ NOMS > NOM (A&W) > CHO > PTN, although specific mitigation effects varied with DOM concentration and functionalities. Our results also indicate that the toxicity of ZnO-NPs to embryos was mostly derived from NPs although dissolved Zn released from ZnO-NPs also interacted with embryos, affecting hatching, but to a less extent. Copyright © 2017 Elsevier Ltd. All rights reserved.

Long-Term Experimental Acidification Drives Watershed Scale Shift in Dissolved Organic Matter Composition and Flux.

PubMed

SanClements, Michael D; Fernandez, Ivan J; Lee, Robert H; Roberti, Joshua A; Adams, Mary Beth; Rue, Garret A; McKnight, Diane M

2018-03-06

Over the last several decades dissolved organic carbon concentrations (DOC) in surface waters have increased throughout much of the northern hemisphere. Several hypotheses have been proposed regarding the drivers of this phenomenon including decreased sulfur (S) deposition working via an acidity- change mechanism. Using fluorescence spectroscopy and data from two long-term (24+ years at completion of this study) whole watershed acidification experiments, that is, the Bear Brook Watershed in Maine (BBWM) and Fernow Experimental Forest in West Virginia (FEF) allowed us to control for factors other than the acidity-change mechanism (e.g., differing vegetation, shifting climate), resulting in the first study we are aware of where the acidity change mechanism could be experimentally isolated at the whole ecosystem and decadal scales as the driver of shifts in DOM dynamics. The multidecadal record of stream chemistry at BBWM demonstrates a significantly lower DOC concentration in the treated compared to the reference watershed. Additionally, at both BBWM and FEF we found significant and sustained differences in stream fluorescence index (FI) between the treated and reference watersheds, with the reference watersheds demonstrating a stronger terrestrial DOM signature. These data, coupled with evidence of pH shifts in upper soil horizons support the hypotheses that declines in S deposition are driving changes in the solubility of soil organic matter and increased flux of terrestrial DOC to water bodies.

An initial investigation into the organic matter biogeochemistry of the Congo River

NASA Astrophysics Data System (ADS)

Spencer, Robert G. M.; Hernes, Peter J.; Aufdenkampe, Anthony K.; Baker, Andy; Gulliver, Pauline; Stubbins, Aron; Aiken, George R.; Dyda, Rachael Y.; Butler, Kenna D.; Mwamba, Vincent L.; Mangangu, Arthur M.; Wabakanghanzi, Jose N.; Six, Johan

2012-05-01

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ13C, Δ14C, δ15N) and biochemical composition (lignin phenols) of coarse particulate (>63 μm; CPOM) and fine particulate (0.7-63 μm; FPOM) OM and DOC, δ13C, Δ14C and lignin phenol composition with respect to dissolved OM (<0.7 μm; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (˜82-89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (˜81-91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean Δ14C = -62.2 ± -13.2‰, n = 5) compared to CPOM and DOM (mean Δ14C = 55.7 ± 30.6‰, n = 4 and 73.4 ± 16.1‰, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67-1.12 (mg(100 mg OC)-1)) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2-27.1) and Λ8 values (4.56-7.59 (mg(100 mg OC)-1)). In relation to CPOM, the aged FPOM fraction (320-580 ybp 14C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4-14.3), lower Λ8 (2.80-4.31 (mg(100 mg OC)-1)) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (˜350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

The Influences of Riverine Dissolved Organic Matter in the Gulf of Maine

NASA Astrophysics Data System (ADS)

Aiken, G.; Cao, X.; Mao, J.; Spencer, R. G.; Balch, W. M.; Huntington, T. G.

2014-12-01

Dissolved organic matter (DOM) exported from the Gulf of St. Lawrence and by rivers in Maine, Nova Scotia, and New Brunswick is being studied to quantify and characterize optical proxies in the receiving waters of the Gulf of Maine (GoM). Measurements of DOC concentrations, absorption coefficients (254nm, 350 nm and 412 nm), specific ultraviolet absorbance (SUVA254), spectral slope, and fluorescence, and DOC fractionation and isotopic analyses were used to determine the amount and nature of DOM from major inflowing rivers, marine waters, and the GoM. In addition, lignin phenols, 14C-age, 13C-NMR and FTICR-MS analyses were performed on the hydrophobic (HPOA) and transphilic organic acid fractions of the DOM isolated using XAD resins for a smaller subset of samples from the Penobscot River, Penobscot Bay, GoM waters in the Eastern Maine Coastal Current (EMCC), a sample from the eastern portion of the GoM (Scotian Shelf waters), and the Pacific Ocean. These samples provide detailed DOM compositional data in support of the more easily collected concentration and optical data obtained from discrete samples, optical data obtained by in situ glider, and remotely sensed satellite observations. Optical measurements, 13C-NMR, and lignin phenol analyses showed that DOM associated with inflowing rivers to the GoM is rich in aromatic compounds resulting in a large flux of terrestrially derived chromophoric DOM (CDOM). As a result, GoM DOM is more aromatic and younger than open ocean samples collected from the Sargasso Sea and from the Pacific Ocean near Hawaii. This observation is consistent with isotopic data that indicated δ 13C values for the HPOA fractions from the Gulf samples (δ 13C= -27‰ and -25‰) were considerably depleted in comparison to the whole DOM sample (δ 13C = -19‰; which also includes algal-produced DOM) and are more similar to those from the terrestrial sources. Samples from the EMCC were the most heavily influenced by terrestrial sources. While NMR analyses indicated decreases in the aromaticity of the HPOA fractions moving from the rivers to the open ocean, NMR signals associated with carboxyl-rich alicyclic organic matter were observed for all samples. Results from this study are being used to develop relationships for predicting DOC concentration in the GoM from remotely sensed, satellite optical data.

Distributions and Transformations of Natural Abundance 14C and 13C in Dissolved and Particulate Lipids in a Major Temperate Estuary

NASA Astrophysics Data System (ADS)

Bauer, J. E.; Canuel, E. A.; McIntosh, H.; Barrett, A.; Ferer, E.; Hossler, K.

2013-12-01

Limited previous studies have shown major differences in the natural 14C and 13C isotopic signatures and radiocarbon ages of different biochemical classes (e.g., proteins, carbohydrates, lipid, etc.) in river, estuarine and marine dissolved and particulate organic matter (DOM and POM, respectively). Of particular note are the much greater radiocarbon ages of lipophilic materials than other compound classes. Possible explanations for these findings include greater-than-expected inputs of fossil and highly aged lipid-containing organic matter to rivers and estuaries, extended sorptive-protection of lipophilic materials from degradation and/or lower overall reactivities of lipids vs. other major biochemical classes. We measured the Delta 14C and del 13C signatures and 14C ages of lipid classes in DOM and POM in a major temperate estuary, Delaware Bay (USA) over two years. Changes in DOM were also followed during large volume dark and light incubations to assess the microbial and photochemical reactivity and processing of DOM and lipids. Neutral lipids in DOM were among the most highly aged (> 30,000 yrs BP) of any materials measured in natural waters to date, and were significantly older than co-occurring polar lipids (~4,000-5,000 yrs BP). In general, DOM lipid ages were significantly greater than POM lipid ages across the river-estuary transect, arguing against sorptive protection as the major factor explaining greater ages of lipid than those of other compound classes. Both dark and light incubations of DOM resulted in losses of very highly aged material (30-50,000 y BP), with the remnant exported lipids being correspondingly younger. The microbial and photochemical alterations were most pronounced for lipids from freshwater reaches of the system (i.e., the Delaware River). These findings suggest that a) dissolved vs. particulate lipids have fundamentally different sources and/or physico-chemical partitioning, b) different lipid classes (e.g., neutral vs. polar) derive from uniquely aged sources and/or are processed at dissimilar rates, and c) biological and photochemical alteration and physical mixing during estuarine transport of DOM and POM can result in significant changes to the composition and ages of the exported materials. The implications of these findings for land-to-ocean fluxes of carbon and organic matter and impacts on oceanic DOM and POM are also examined.

Novel applications of the dispersive optical model

NASA Astrophysics Data System (ADS)

Dickhoff, W. H.; Charity, R. J.; Mahzoon, M. H.

2017-03-01

A review of recent developments of the dispersive optical model (DOM) is presented. Starting from the original work of Mahaux and Sartor, several necessary steps are developed and illustrated which increase the scope of the DOM allowing its interpretation as generating an experimentally constrained functional form of the nucleon self-energy. The method could therefore be renamed as the dispersive self-energy method. The aforementioned steps include the introduction of simultaneous fits of data for chains of isotopes or isotones allowing a data-driven extrapolation for the prediction of scattering cross sections and level properties in the direction of the respective drip lines. In addition, the energy domain for data was enlarged to include results up to 200 MeV where available. An important application of this work was implemented by employing these DOM potentials to the analysis of the (d, p) transfer reaction using the adiabatic distorted wave approximation. We review these calculations which suggest that physically meaningful results are easier to obtain by employing DOM ingredients as compared to the traditional approach which relies on a phenomenologically-adjusted bound-state wave function combined with a global (nondispersive) optical-model potential. Application to the exotic 132Sn nucleus also shows great promise for the extrapolation of DOM potentials towards the drip line with attendant relevance for the physics of FRIB. We note that the DOM method combines structure and reaction information on the same footing providing a unique approach to the analysis of exotic nuclei. We illustrate the importance of abandoning the custom of representing the non-local Hartree-Fock (HF) potential in the DOM by an energy-dependent local potential as it impedes the proper normalization of the solution of the Dyson equation. This important step allows for the interpretation of the DOM potential as representing the nucleon self-energy permitting the calculations of spectral amplitudes and spectral functions above and below the Fermi energy. The latter feature provides access to quantities like the momentum distribution, charge density, and particle number which were not available in the original work of Mahaux and Sartor. When employing a non-local HF potential, but local dispersive contributions (as originally proposed by Mahaux and Sartor), we illustrate that it is impossible to reproduce the particle number and the measured charge density. Indeed, the use of local absorptive potentials leads to a substantial overestimate of particle number. However from detailed comparisons with self-energies calculated with ab initio many-body methods that include both short- and long-range correlations, we demonstrate that it is essential to introduce non-local absorptive potentials in order to remediate these deficiencies. We review the fully non-local DOM potential fitted to 40Ca where elastic-scattering data, level information, particle number, charge density and high-momentum-removal (e,e\\prime p) cross sections obtained at Jefferson Lab were included in the analysis. All these quantities are accurately described by assuming more or less traditional functional forms for the potentials but allowing for non-locality and the abandonment of complete symmetry around the Fermi energy for surface absorption which is suggested by ab initio theory. An important consequence of this new analysis is the finding that the spectroscopic factor for the removal of valence protons in this nucleus comes out larger by about 0.15 than the results obtained from the NIKHEF analysis of their (e,e\\prime p) data. This issue is discussed in detail and its implications clarified. Another important consequence of this analysis is that it can shed light on the relative importance of two-body and three-body interactions as far as their contribution to the energy of the ground state is concerned through application of the energy sum rule.

High abundances of presolar grains and 15N-rich organic matter in CO3.0 chondrite Dominion Range 08006

NASA Astrophysics Data System (ADS)

Nittler, Larry R.; Alexander, Conel M. O'D.; Davidson, Jemma; Riebe, My E. I.; Stroud, Rhonda M.; Wang, Jianhua

2018-04-01

NanoSIMS C-, N-, and O-isotopic mapping of matrix in CO3.0 chondrite Dominion Range (DOM) 08006 revealed it to have in its matrix the highest abundance of presolar O-rich grains (257 +76/-96 ppm, 2σ) of any meteorite. It also has a matrix abundance of presolar SiC of 35 (+25/-17, 2σ) ppm, similar to that seen across primitive chondrite classes. This provides additional support to bulk isotopic and petrologic evidence that DOM 08006 is the most primitive known CO meteorite. Transmission electron microscopy of five presolar silicate grains revealed one to have a composite mineralogy similar to larger amoeboid olivine aggregates and consistent with equilibrium condensation, two non-stoichiometric amorphous grains, and two olivine grains, though one is identified as such solely based on its composition. We also found insoluble organic matter (IOM) to be present primarily as sub-micron inclusions with ranges of C- and N-isotopic anomalies similar to those seen in primitive CR chondrites and interplanetary dust particles. In contrast to other primitive extraterrestrial materials, H isotopic imaging showed normal and homogeneous D/H. Most likely, DOM 08006 and other CO chondrites accreted a similar complement of primitive and isotopically anomalous organic matter to that found in other chondrite classes and IDPs, but the very limited amount of thermal metamorphism experienced by DOM 08006 has caused loss of D-rich organic moieties, while not substantially affecting either the molecular carriers of C and N anomalies or most inorganic phases in the meteorite. One C-rich grain that was highly depleted in 13C and 15N was identified; we propose it originated in the Sun's parental molecular cloud.

Determining sources of dissolved organic carbon and disinfection byproduct precursors to the McKenzie River, Oregon

USGS Publications Warehouse

Kraus, Tamara E.C.; Anderson, Chauncey W.; Morgenstern, Karl; Downing, Bryan D.; Pellerin, Brian A.; Bergamaschi, Brian A.

2010-01-01

This study was conducted to determine the main sources of dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors to the McKenzie River, Oregon (USA). Water samples collected from the mainstem, tributaries, and reservoir outflows were analyzed for DOC concentration and DBP formation potentials (trihalomethanes [THMFPs] and haloacetic acids [HAAFPs]). In addition, optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) were measured to provide insight into DOM composition and assess whether optical properties are useful proxies for DOC and DBP precursor concentrations. Optical properties indicative of composition suggest that DOM in the McKenzie River mainstem was primarily allochthonous - derived from soils and plant material in the upstream watershed. Downstream tributaries had higher DOC concentrations than mainstem sites (1.6 ?? 0.4 vs. 0.7 ?? 0.3 mg L-1) but comprised <5% of mainstem flows and had minimal effect on overall DBP precursor loads. Water exiting two large upstream reservoirs also had higher DOC concentrations than the mainstem site upstream of the reservoirs, but optical data did not support in situ algal production as a source of the added DOC during the study. Results suggest that the first major rain event in the fall contributes DOM with high DBP precursor content. Although there was interference in the absorbance spectra in downstream tributary samples, fluorescence data were strongly correlated to DOC concentration (R 2 = 0.98), THMFP (R2 = 0.98), and HAAFP (R2 = 0.96). These results highlight the value of using optical measurements for identifying the concentration and sources of DBP precursors in watersheds, which will help drinking water utilities improve source water monitoring and management programs. Copyright ?? 2010 by the American Society of Agronomy.

Dynamics of dissolved organic matter in riverine sediments affected by weir impoundments: Production, benthic flux, and environmental implications.

PubMed

Chen, Meilian; Kim, Sung-Han; Jung, Heon-Jae; Hyun, Jung-Ho; Choi, Jung Hyun; Lee, Hyo-Jin; Huh, In-Ae; Hur, Jin

2017-09-15

In order to understand the characteristics and dynamics of dissolved organic matter (DOM) in the sediment of rivers affected by impoundments, we examined the vertical profiles and the benthic fluxes of DOM in four different core sediments located at upstream sites of weirs in major rivers of South Korea. In three out of four sites, exponential accumulation of dissolved organic carbon (DOC) with depth was observed with the signature of seasonal variability. Except for the site displaying a below-detection limit of Fe(II), the general accumulation trends of DOC with depth was concurrent with the increases of Fe(II) and NH 4 + and the decrease of PO 4 3- , signifying a close linkage of the DOM dynamics with anaerobic respiration via iron reduction, an important early diagenesis pathway. The estimated benthic fluxes from the cores revealed that the sediments likely serve as DOC, chromophoric DOM (CDOM), and fluorescent DOM (FDOM) sources to the overlying water. The benthic effluxes based on DOC were comparable to the ranges previously reported in lake and coastal areas, and those of CDOM and FDOM showed even higher levels. These findings imply that impoundment-affected river systems would change the DOM composition of the overlying water, ultimately influencing the subsequent water treatment processes such as disinfection byproducts production and membrane fouling. A simple mass balance model indicated that the impoundment-affected river sediments may operate as a net carbon sink in the environments due to a greater extent of sedimentation compared to the estimated benthic efflux and sediment biological respiration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Insight into photocatalytic degradation of dissolved organic matter in UVA/TiO₂ systems revealed by fluorescence EEM-PARAFAC.

PubMed

Phong, Diep Dinh; Hur, Jin

2015-12-15

Photocatalytic degradation of dissolved organic matter (DOM) using TiO2 as a catalyst and UVA as a light source was examined under various experimental settings with different TiO2 doses, solution pH, and the light intensities. The changes in UV absorbance and fluorescence with the irradiation time followed a pseudo-first order model much better than those of dissolved organic carbon. In general, the degradation rates were increased by higher TiO2 doses and light intensities. However, the exact photocatalytic responses of DOM to the irradiation were affected by many other factors such as aggregation of TiO2, light scattering, hydroxyl radicals produced, and DOM sorption on TiO2. Fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) revealed that the DOM changes in fluorescence could be described by the combinations of four dissimilar components including one protein-like, two humic-like, and one terrestrial humic-like components, each of which followed well the pseudo-first order model. The photocatalytic degradation rates were higher for protein-like versus humic-like component, whereas the opposite order was displayed for the degradation rates in the absence of TiO2, suggesting different dominant mechanisms operating between the systems with and without TiO2. Our results based on EEM-PARAFAC provided new insights into the underlying mechanisms associated with the photocatalytic degradation of DOM as well as the potential environmental impact of the treated water. This study demonstrated a successful application of EEM-PARAFAC for photocatalytic systems via directly comparing the kinetic rates of the individual DOM components with different compositions. Copyright © 2015 Elsevier Ltd. All rights reserved.

High-frequency in situ optical measurements during a storm event: Assessing relationships between dissolved organic matter, sediment concentrations, and hydrologic processes

USGS Publications Warehouse

Saraceno, John F.; Pellerin, Brian A.; Downing, Bryan D.; Boss, Emmanuel; Bachand, Philip A. M.; Bergamaschi, Brian A.

2009-01-01

Dissolved organic matter (DOM) dynamics during storm events has received considerable attention in forested watersheds, but the extent to which storms impart rapid changes in DOM concentration and composition in highly disturbed agricultural watersheds remains poorly understood. In this study, we used identical in situ optical sensors for DOM fluorescence (FDOM) with and without filtration to continuously evaluate surface water DOM dynamics in a 415 km2agricultural watershed over a 4 week period containing a short-duration rainfall event. Peak turbidity preceded peak discharge by 4 h and increased by over 2 orders of magnitude, while the peak filtered FDOM lagged behind peak turbidity by 15 h. FDOM values reported using the filtered in situ fluorometer increased nearly fourfold and were highly correlated with dissolved organic carbon (DOC) concentrations (r2 = 0.97), providing a highly resolved proxy for DOC throughout the study period. Discrete optical properties including specific UV absorbance (SUVA254), spectral slope (S290–350), and fluorescence index (FI) were also strongly correlated with in situ FDOM and indicate a shift toward aromatic, high molecular weight DOM from terrestrially derived sources during the storm. The lag of the peak in FDOM behind peak discharge presumably reflects the draining of watershed soils from natural and agricultural landscapes. Field and experimental evidence showed that unfiltered FDOM measurements underestimated filtered FDOM concentrations by up to ∼60% at particle concentrations typical of many riverine systems during hydrologic events. Together, laboratory and in situ data provide insights into the timing and magnitude of changes in DOM quantity and quality during storm events in an agricultural watershed, and indicate the need for sample filtration in systems with moderate to high suspended sediment loads.

Characterization of Whole Porewater Dissolved Organic Matter by 1H NMR

NASA Astrophysics Data System (ADS)

Fox, C.; Lewicki, J. P.; Abdulla, H. A.; Burdige, D.; Magen, C.; Chanton, J.; Komada, T.

2014-12-01

Dissolved organic matter (DOM) is a key intermediate in microbial remineralization of organic matter, but only a small percentage of this complex pool has been fully characterized. We present the results of a novel approach to the characterization of DOM in whole porewater samples from the anoxic sediments of the Santa Barbara Basin, California Borderland, using solution state nuclear magnetic resonance (NMR) techniques. Profiles of porewater DOM were obtained by 1H NMR from 95 to 435 cm sediment depth. 1H NMR spectra of each whole porewater sample showed continuous, broad regions from ~0.5 to ~4.5 ppm, indicative of significant signal overlap inherent to complex mixtures, superimposed on a few highly resolved peaks. The individual samples consist of a broad range of chemical environments with varying relative abundances that show a near linear trend with depth. The normalized spectral data were analyzed by principal component analysis to resolve variations in chemical composition of DOM as a function of depth. In addition to detecting the major components such as carbohydrates, cyclic aliphatics and aromatics, our results demonstrate a negative correlation between carbohydrates concurrent with a relative increase in levels of aliphatics. Furthermore, we have identified a decrease in the abundance of alkenes coupled with an increase in a broad region from ~1.9 to ~3.2 ppm, likely corresponding to signals from carboxylic-rich alicyclic molecules. In both trends, the greatest variation occurs between 115 and 135 cm, which straddles the sulfate-methane transition zone (~125 cm), potentially highlighting a region of relatively high DOM transformation. Our work has also identified thiol species which are thought to be formed by dissolved (inorganic) sulfide incorporation into porewater DOM compounds. The implications of these results with respect to carbon cycling in anaerobic sediments will be discussed.

Survival of Acetate in Biodegraded Stream Water DOM: New Insights Based on NMR Spectroscopy

NASA Astrophysics Data System (ADS)

Whitty, S.; Waggoner, D. C.; Bowen, J. C.; Cory, R. M.; Kaplan, L.; Hatcher, P.

2017-12-01

DOM is a complex chemical mixture of high- (HMW) and low-molecular-weight (LMW) organic molecules that serve as the primary energy sources for heterotrophic bacteria in freshwater environments. However, there are still large uncertainties on the composition of DOM that is labile and thus rapidly metabolized. The current thinking is that labile DOM is primarily composed of monosaccharides, amino acids, and other LMW organic acids such as formic, acetic, or propionic among others, although some humic substances also are biologically labile. To test the contribution of LMW organic acids to the labile fraction of DOM, freshwater samples were collected from five streams within the Rio Tempisquito watershed in Costa Rica and subjected to differing degrees of biodegradation using a series of plug-flow bioreactors with residence times ranging from 0.5-150 min. Varying the residence times of bioreactors allows for separation and identification of labile from less labile to more recalcitrant DOM. The stream water fed into the bioreactors had DOC concentrations that ranged from 0.7-1.2 ppm C and the GF/F-filtered stream water as well as the bioreactor effluents were analyzed directly without pre-treatment using proton nuclear magnetic resonance spectroscopy (1H NMR). Small molecules dominated the 1H NMR spectra with the greatest changes, as a function of bioreactor residence time, in the carbohydrate, terminal methyl, and long-chain methylene structures. In contrast, acetate remained relatively constant after 150 min of bioreactor residence time, thus raising the question of why this inherently labile volatile fatty acid was not consumed by stream microbes colonizing bioreactors that otherwise metabolized approximately 35% of the total dissolved organic carbon present in the stream water. We suggest that acetate may resist biodegradation because it is complexed strongly with inorganic cations.

[FTIR and 13C NMR Analysis of Dissolved Organic Matter (DOM) in the Treatment Process of Tannery Wastewater].

PubMed

Fan, Chun-hui; Zhang, Ying-chao; Tang, Ze-heng; Wang, Jia-hong

2015-05-01

Nowadays, the wastewater quantity discharged yearly from tannery industry is around 0. 2 billion t in China. The contaminants of tannery wastewater include macromolecular organic matters, such as grease, fur scraps and collagen, and the alkaline wastewater appears to be of high content of salt and COD. The quality of tannery wastewater is monitored strictly among all kinds of industry wastewater. In the treatment process of tannery wastewater, the quality of inlet and outlet water is generally analyzed. In fact, the transformation behavior of contaminants should be additionally checked to optimize the treatment conditions. Dissolved organic matter (DOM) is commonly existed in water-bodies and helpful to understand the physicochemical characteristics, while the related work should be further studied on tannery wastewater. The approaches of elemental analysis, thermal gravimetric analysis (TG), Fourier infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C NMR) were used to reveal the characteristics of DOM in the treatment process of tannery wastewater. The results showed the carbon content of DOM samples increased gradually, atomic ratios of H/C increased firstly and then decreased, indicating the organic matters were decomposed into chain structures firstly, finally forming the component hard to degraded. The pyrolysis process of DOM mainly proceeded in the regions of 110~530 °C (aliphatic compound, protein, etc. ) and 530~800 °C (aromatic ring, single bond of C-C, etc. ). The functional groups of DOM included -OH, -NH2, C=O and so on, and the aromatic substances were detected, shown from FTIR figures, in the later period of the reaction, caused by the metabolism effect of micro-organism. The content of alkoxy-C increased to the maximum in the second biochemical pond, and the minimum content of aromatic-C appeared in the second biochemical pond, suggesting the transformation behavior of carbon functional groups. The investigation on DOM in tannery wastewater is significant to understand the purification mechanism of contaminants in tannery wastewater.

High-field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter

NASA Astrophysics Data System (ADS)

Hertkorn, N.; Harir, M.; Koch, B. P.; Michalke, B.; Schmitt-Kopplin, P.

2013-03-01

High-performance, non-target, high-resolution organic structural spectroscopy was applied to solid phase extracted marine dissolved organic matter (SPE-DOM) isolated from four different depths in the open South Atlantic Ocean off the Angola coast (3° E, 18° S; Angola Basin) and provided molecular level information with extraordinary coverage and resolution. Sampling was performed at depths of 5 m (Angola Current; near-surface photic zone), 48 m (Angola Current; fluorescence maximum), 200 m (still above Antarctic Intermediate Water, AAIW; upper mesopelagic zone) and 5446 m (North Atlantic Deep Water, NADW; abyssopelagic, ~30 m above seafloor) and produced SPE-DOM with near 40% carbon yield and beneficial nuclear magnetic resonance (NMR) relaxation properties, a crucial prerequisite for the acquisition of NMR spectra with excellent resolution. 1H and 13C NMR spectra of all four marine SPE-DOM showed smooth bulk envelopes, reflecting intrinsic averaging from massive signal overlap, with a few percent of visibly resolved signatures and variable abundances for all major chemical environments. The abundance of singly oxygenated aliphatics and acetate derivatives in 1H NMR spectra declined from surface to deep marine SPE-DOM, whereas C-based aliphatics and carboxyl-rich alicyclic molecules (CRAM) increased in abundance. Surface SPE-DOM contained fewer methyl esters than all other samples, likely a consequence of direct exposure to sunlight. Integration of 13C NMR spectra revealed continual increase of carboxylic acids and ketones from surface to depth, reflecting a progressive oxygenation, with concomitant decline of carbohydrate-related substructures. Aliphatic branching increased with depth, whereas the fraction of oxygenated aliphatics declined for methine, methylene and methyl carbon. Lipids in the oldest SPE-DOM at 5446 m showed a larger share of ethyl groups and methylene carbon than observed in the other samples. Two-dimensional NMR spectra showed exceptional resolution and depicted resolved molecular signatures in excess of a certain minimum abundance. Classical methyl groups terminating aliphatic chains represented ~15% of total methyl in all samples investigated. A noticeable fraction of methyl (~2%) was bound to olefinic carbon. Methyl ethers were abundant in surface marine SPE-DOM, and the chemical diversity of carbohydrates was larger than that of freshwater and soil DOM. In all samples, we identified sp2-hybridized carbon chemical environments with discrimination of isolated and conjugated olefins and α,β-unsaturated double bonds. Olefinic proton and carbon atoms were more abundant than aromatic ones; olefinic unsaturation in marine SPE-DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation. The abundance of furan, pyrrol and thiophene derivatives was marginal, whereas benzene derivatives, phenols and six-membered nitrogen heterocycles were prominent; a yet unassigned set of six-membered N-heterocycles with likely more than one single nitrogen occurred in all samples. Various key polycyclic aromatic hydrocarbon substructures suggested the presence of thermogenic organic matter at all water depths. Progressive NMR cross-peak attenuation from surface to deep marine SPE-DOM was particularly strong in COSY NMR spectra and indicated a continual disappearance of biosignatures as well as entropy gain from an ever increased molecular diversity. Nevertheless, a specific near-seafloor SPE-DOM signature of unsaturated molecules recognized in both NMR and Fourier transform ion cyclotron mass spectrometry (FTICR/MS) possibly originated from sediment leaching. The conformity of key NMR and FTICR/MS signatures suggested the presence of a large set of identical molecules throughout the entire ocean column even though the investigated water masses belonged to different oceanic regimes and currents. FTICR/MS showed abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing numbers of mass peaks and average mass from surface to bottom SPE-DOM. The proportion of CHO and CHNO negative ions increased from surface to depth, whereas CHOS and especially CHNOS molecular series markedly declined. While certain rather aliphatic CHOS and CHNOS ions were observed solely in the surface, deep marine SPE-DOM was enriched in unique unsaturated and rather oxygenated CHO and CHNO molecular series. With the exception of abyssopelagic SPE-DOM at 5446 m, which showed a peculiar CHOS chemistry of unsaturated carbon and reduced sulphur (black sulphur), CHO and CHNO molecular series contributed ~87% to total positive electrospray ionization FTICR mass peak integral, with a near constant ratio of CHNO / CHO molecular compositions near 1.13 ± 0.05. In case of all four marine SPE-DOM, remarkably disparate average elemental compositions as determined from either MS and NMR spectra were observed, caused by a pronounced ionization selectivity in electrospray ionization FTICR/MS. The study demonstrates that the exhaustive characterization of complex unknowns in marine DOM will enable a meaningful classification of individual marine biogeosignatures. Future in-depth functional biodiversity studies with a clear understanding of DOM structure and function might eventually lead to a novel, unified perception of biodiversity and biogeochemistry.

Sprinting performance on the Woodway Curve 3.0 is related to muscle architecture.

PubMed

Mangine, Gerald T; Fukuda, David H; Townsend, Jeremy R; Wells, Adam J; Gonzalez, Adam M; Jajtner, Adam R; Bohner, Jonathan D; LaMonica, Michael; Hoffman, Jay R; Fragala, Maren S; Stout, Jeffrey R

2015-01-01

To determine if unilateral measures of muscle architecture in the rectus femoris (RF) and vastus lateralis (VL) were related to (and predictive of) sprinting speed and unilateral (and bilateral) force (FRC) and power (POW) during a 30 s maximal sprint on the Woodway Curve 3.0 non-motorized treadmill. Twenty-eight healthy, physically active men (n = 14) and women (n = 14) (age = 22.9 ± 2.4 years; body mass = 77.1 ± 16.2 kg; height = 171.6 ± 11.2 cm; body-fa t = 19.4 ± 8.1%) completed one familiarization and one 30-s maximal sprint on the TM to obtain maximal sprinting speed, POW and FRC. Muscle thickness (MT), cross-sectional area (CSA) and echo intensity (ECHO) of the RF and VL in the dominant (DOM; determined by unilateral sprinting power) and non-dominant (ND) legs were measured via ultrasound. Pearson correlations indicated several significant (p < 0.05) relationships between sprinting performance [POW (peak, DOM and ND), FRC (peak, DOM, ND) and sprinting time] and muscle architecture. Stepwise regression indicated that POW(DOM) was predictive of ipsilateral RF (MT and CSA) and VL (CSA and ECHO), while POW(ND) was predictive of ipsilateral RF (MT and CSA) and VL (CSA); sprinting power/force asymmetry was not predictive of architecture asymmetry. Sprinting time was best predicted by peak power and peak force, though muscle quality (ECHO) and the bilateral percent difference in VL (CSA) were strong architectural predictors. Muscle architecture is related to (and predictive of) TM sprinting performance, while unilateral POW is predictive of ipsilateral architecture. However, the extent to which architecture and other factors (i.e. neuromuscular control and sprinting technique) affect TM performance remains unknown.

Effects of Dissolved Organic Matter Properties on Formation and Composition of Mineral-Organic Co-Precipitates at the Nanometer Scale

NASA Astrophysics Data System (ADS)

Possinger, A. R.; Zachman, M.; Lehmann, J.

2016-12-01

An important, yet largely overlooked case of soil organic carbon (SOC) stabilization through mineral-organic associations is the co-precipitation of dissolved organic matter (DOM) into mineral precipitates as they form. The contribution of co-precipitated DOM to the mineral-stabilized SOC pool is expected to be greatest in soil environments with frequent mineral dissolution and precipitation processes. Compared to surface adsorption, properties of mineral-organic co-precipitates are expected to differ at both the particle scale (e.g., total carbon (C) content and composition) and the molecular scale (e.g., impurities in mineral structure), with potential implications for stability and C turnover; additionally, these properties vary across C sources, amounts, and forms. Consequently, high-resolution visualization and characterization combined with bulk chemical measurements is needed to provide a more complete understanding of co-precipitate formation processes and properties, especially as a function of C co-precipitant characteristics. In this study, we evaluate the effect of model C compound and DOM chemical properties (e.g., iron-binding affinity) on the formation, structure, and chemical properties of ferrihydrite (Fh) (Fe3+3O2 •0.5H2O) co-precipitates. Salicylic acid (SA), sucrose and water-extractable DOM from coniferous or deciduous-dominated organic soils were either adsorbed to pre-formed Fh or co-precipitated with Fh. At a C/Fe ratio 10, the amount of co-precipitated C differed among all organic compounds, and for DOM, was more than 2X greater for co-precipitation than adsorption, suggesting a greater capacity for C retention. To probe the molecular-scale C spatial distribution of Fh-SA particles, we obtained Scanning Transmission Electron Microscopy with Electron Energy Loss Spectroscopy (STEM-EELS) maps at a nanometer-scale spatial pixel resolution. Additionally, we will present chemical characteristics of organic-Fh co-precipitates and adsorption complexes investigated in bulk using C Near-Edge X-ray Absorption Fine Structure (NEXAFS) and Fourier Transform Infrared (FT-IR) spectroscopy. Ultimately, these observations of model co-precipitation systems will be used to better interpret observations of putative co-precipitated OM in natural soils.

Changes in DOM Character and Composition during Spring Snow Melt in the Jemez River Basin Critical Zone Observatory.

NASA Astrophysics Data System (ADS)

Thompson, M.; Olshansky, Y.; Chorover, J.

2017-12-01

Dynamics of dissolved organic matter (DOM) in stream waters are important indicators of internal processes in the critical zone, such as decomposition and mobilization of soil organic matter, hydrologic flow paths, potential for metal mobilization and nutrient redistribution. Previous studies indicate that DOM concentration was highest during peak snow melt in the La Jara catchment located in the Jemez River Basin Critical Zone Observatory (Perdrial et al., 2014). We postulate that the molecular composition and character of DOM changes with the advance of spring snow melt. Water samples were collected from two flumes located at the outlets of the La Jara Creek and from a zero order basin within this catchment through the spring snowmelt from March 1 to May 15 2017. DOM concentration increased with stream discharge. Quantification of molecular changes was conducted using Fourier transform infrared spectroscopy (FTIR), which showed the variation in carboxyl abundance (wavenumbers 1680, 1600 and 1410 cm-1) correlated with dissolved organic carbon concentration, indicating that this component is relatively a constant fraction of the organic carbon exported through the stream during spring snowmelt. In contrast, amide vibrations (3550, 1640 and 670 cm-1) were shown to decrease with the advance of spring snowmelt. This trend further corresponded to a decrease in the ratio of carboxylic acid (above) to aromatic (1622, 1490, 955 cm-1) moieties, suggesting either a flush of compounds accumulated prior to spring snow melt, or increased decomposition of plant derived material in the soil that was then transported to the stream. Aliphatic components (2965, 2925 and 2865 cm-1) decreased from the beginning to the middle of sampling period, then showed an increase toward the end of snowmelt. O-Alkyl peak (1150 and 1073 cm-1) varied without a clear trend during the spring snowmelt. These changes in O-Alkyl and aliphatic compounds may be related to microbial derived compounds and indicate changes in microbial activity during the spring snowmelt. These results will be combined with concentration discharge analysis and data from fluorescence and UV-vis spectroscopy for evaluation and modeling of CZ processes dominated by spring snowmelt.

Tracking changes in composition and amount of dissolved organic matter throughout drinking water treatment plants by comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry.

PubMed

Li, Chunmei; Wang, Donghong; Xu, Xiong; Xu, Meijia; Wang, Zijian; Xiao, Ruiyang

2017-12-31

Dissolved organic matter (DOM) can affect the performance of water treatment processes and produce undesirable disinfection by-products during disinfection. Several studies have been undertaken on the structural characterization of DOM, but its fate during drinking water treatment processes is still not fully understood. In this work, the nontargeted screening method of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC×GC-qMS) was used to reveal the detailed changes of different chemical classes of compounds in DOM during conventional and advanced drinking water treatment processes at three drinking water treatment plants in China. The results showed that when the dissolved organic carbon removal was low, shifts in the DOM composition could not be detected with the specific ultraviolet absorbance at 254nm, but the changes were clear in the three-dimensional fluorescence excitation-emission matrix or GC×GC-qMS analyses. Coagulation-sedimentation processes selectively removed 37-59% of the nitrogenous compounds, alcohols and aromatic hydrocarbons but increased the concentrations of halogen-containing compounds by 17-26% because of the contact time with chlorine in this step. Filtration was less efficient at removing DOM but preferentially removed 21-60% of the acids. However, other organic matter would be released from the filter (e.g., nitrogenous compounds, acids, and aromatic hydrocarbons). Biological activated carbon (BAC) treatment removed most of the compounds produced from ozonation, particularly ketones, alcohols, halogen-containing compounds and acids. However, it should be noted that certain highly polar or high molecular weight compounds not identified in this study might be released from the BAC bed. After the whole treatment processes, the concentrations of nitrogenous compounds, alcohols, alkenes, aromatic hydrocarbons and ketones were decreased more by the advanced treatment processes than by the conventional treatment processes. Alcohol and ketone removals were probably related to the reduction in protein-like materials. Alkane removal was probably related to the reduction in fulvic acid-like and humic acid-like materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Latitude and pH driven trends in the molecular composition of DOM across a north south transect along the Yenisei River

NASA Astrophysics Data System (ADS)

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2013-12-01

We used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) to identify the molecular composition of dissolved organic matter (DOM) collected from different ecosystems along a transect crossing Siberia’s northern and middle Taiga. This information is urgently needed to help elucidate global carbon cycling and export through Russian rivers. In total, we analyzed DOM samples from eleven Yenisei tributaries and seven bogs. Freeze-dried and re-dissolved DOM was desalted via solid phase extraction (SPE) and eluted in methanol for ESI-FT-ICR-MS measurements. We recorded 15209 different masses and identified 7382 molecular formulae in the mass range between m/z = 150 and 800. We utilized the relative FT-ICR-MS signal intensities of 3384 molecular formulae above a conservatively set limit of detection and summarized the molecular characteristics for each measurement using ten magnitude-weighted parameters ((O/C)w, (H/C)w, (N/C)w, (DBE)w, (DBE/C)w, (DBE/O)w, (DBE-O)w, (C#)w, (MW)w and (AI)w) for redundancy analysis. Consequently, we revealed that the molecular composition of DOM depends mainly on pH and geographical latitude. After applying variation partitioning to the peak data, we isolated molecular formulae that were strongly positive or negatively correlated with latitude and pH. We used the chemical information from 13 parameters (C#, H#, N#, O#, O/C, H/C, DBE, DBE/C, DBE/O, AI, N/C, DBE-O and MW) to characterize the extracted molecular formulae. Using latitude along the gradient representing climatic variation, we found a higher abundance of smaller molecules, nitrogen-containing compounds and unsaturated Cdbnd C functionalities at higher latitudes. As possible reasons for the different molecular characteristics occurring along this gradient, we suggested that the decomposition was temperature dependent resulting to a higher abundance of non-degraded lignin-derived phenolic substances. We demonstrated that bog samples, which were differentiated from river samples by their lower pH values, distinguish themselves by their higher unsaturation and molecular size. These molecular characteristics might suggest less phenol oxidase degradation occurs alongside a higher abundance of phenolic substances in bogs due to low pH and anoxic conditions. We concluded that heating at the higher latitudes will increase decomposition and feedback on the nitrogen cycle due to the increased mineralization of organic nitrogen compounds, although the peat system will be less affected due to pH inhibition.

Chemical characterization of fractions of dissolved humic substances from a marginal sea—a case from the Southern Yellow Sea

NASA Astrophysics Data System (ADS)

Zhang, Yaoling; Yang, Keli; Du, Jinzhou; Zhang, Fenfen; Dong, Yaping; Li, Wu

2018-03-01

Marine dissolved organic matter (DOM) is one of the largest dynamic pools of organic carbon in the global carbon cycle, yet DOM is still chemically poorly characterized. To better understand the origin, composition, and cycling of DOM in the China marginal sea, dissolved humic substances (DHS) were isolated from seawaters in two locations in the Southern Yellow Sea. The DHS were subdivided into fulvic acids (FAs), humic acids (HAs) and the XAD-4 fractions. Complementary analytical approaches were used to characterize the isolated DHS samples including stable carbon isotopic composition, Fourier transform infrared spectroscopy (FTIR), 13C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR), and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). The results demonstrated that both DHS samples encountered the influences from marine source, indicating that algal and microbial-derived materials are the predominant precursors for the studied samples. The three fractions of DHS showed different properties. FAs presented more aromatic features, whereas HAs contained more aliphatic lipids and proteinaceous materials. The XAD-4 fractions were enriched in 13C and contained more carbohydrates but less aromatic compounds. The lower molecular weight and higher heteroatom content and number of carboxyl groups for the XAD-4 fractions may give them considerable geochemical significance for aspects of trace metal species, bioavailability of pollutants, mineral weathering and water acidification in marine environments.

Quantifying fluxes and characterizing compositional changes of dissolved organic matter in aquatic systems in situ using combined acoustic and optical measurements

USGS Publications Warehouse

Downing, B.D.; Boss, E.; Bergamaschi, B.A.; Fleck, J.A.; Lionberger, M.A.; Ganju, N.K.; Schoellhamer, D.H.; Fujii, R.

2009-01-01

Studying the dynamics and geochemical behavior of dissolved and particulate organic material is difficult because concentration and composition may rapidly change in response to aperiodic as well as periodic physical and biological forcing. Here we describe a method useful for quantifying fluxes and analyzing dissolved organic matter (DOM) dynamics. The method uses coupled optical and acoustic measurements that provide robust quantitative estimates of concentrations and constituent characteristics needed to investigate processes and calculate fluxes of DOM in tidal and other lotic environments. Data were collected several times per hour for 2 weeks or more, with the frequency and duration limited only by power consumption and data storage capacity. We assessed the capabilities and limitations of the method using data from a winter deployment in a natural tidal wetland of the San Francisco Bay estuary. We used statistical correlation of in situ optical data with traditional laboratory analyses of discrete water samples to calibrate optical properties suited as proxies for DOM concentrations and characterizations. Coupled with measurements of flow velocity, we calculated long-term residual horizontal fluxes of DOC into and out from a tidal wetland. Subsampling the dataset provides an estimate for the maximum sampling interval beyond which the error in flux estimate is significantly increased.?? 2009, by the American Society of Limnology and Oceanography, Inc.

Photochemical alteration of dissolved organic matter and the subsequent effects on bacterial carbon cycling and diversity.

PubMed

Lønborg, Christian; Nieto-Cid, Mar; Hernando-Morales, Victor; Hernández-Ruiz, Marta; Teira, Eva; Álvarez-Salgado, Xosé Antón

2016-05-01

The impact of solar radiation on dissolved organic matter (DOM) derived from 3 different sources (seawater, eelgrass leaves and river water) and the effect on the bacterial carbon cycling and diversity were investigated. Seawater with DOM from the sources was first either kept in the dark or exposed to sunlight (4 days), after which a bacterial inoculum was added and incubated for 4 additional days. Sunlight exposure reduced the coloured DOM and carbon signals, which was followed by a production of inorganic nutrients. Bacterial carbon cycling was higher in the dark compared with the light treatment in seawater and river samples, while higher levels were found in the sunlight-exposed eelgrass experiment. Sunlight pre-exposure stimulated the bacterial growth efficiency in the seawater experiments, while no impact was found in the other experiments. We suggest that these responses are connected to differences in substrate composition and the production of free radicals. The bacterial community that developed in the dark and sunlight pre-treated samples differed in the seawater and river experiments. Our findings suggest that impact of sunlight exposure on the bacterial carbon transfer and diversity depends on the DOM source and on the sunlight-induced production of inorganic nutrients. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Variations of DOM quality in inflows of a drinking water reservoir: linking of van Krevelen diagrams with EEMF spectra by rank correlation.

PubMed

Herzsprung, Peter; von Tümpling, Wolf; Hertkorn, Norbert; Harir, Mourad; Büttner, Olaf; Bravidor, Jenny; Friese, Kurt; Schmitt-Kopplin, Philippe

2012-05-15

Elevated concentrations of dissolved organic matter (DOM) such as humic substances in raw water pose significant challenges during the processing of the commercial drinking water supplies. This is a relevant issue in Saxony, Central East Germany, and many other regions worldwide, where drinking water is produced from raw waters with noticeable presence of chromophoric DOM (CDOM), which is assumed to originate from forested watersheds in spring regions of the catchment area. For improved comprehension of DOM molecular composition, the seasonal and spatial variations of humic-like fluorescence and elemental formulas in the catchment area of the Muldenberg reservoir were recorded by excitation emission matrix fluorescence (EEMF) and ultrahigh-resolution mass spectrometry (FT-ICR-MS). The Spearman rank correlation was applied to link the EEMF intensities with exact molecular formulas and their corresponding relative mass peak abundances. Thereby, humic-like fluorescence could be allocated to the pool of oxygen-rich and relatively unsaturated components with stoichiometries similar to those of tannic acids, which are suspected to have a comparatively high disinfection byproduct formation potential associated with the chlorination of raw water. Analogous relationships were established for UV absorption at 254 nm (UV(254)) and dissolved organic carbon (DOC) and compared to the EEMF correlation.

Uncertainty analysis of the nonideal competitive adsorption-donnan model: effects of dissolved organic matter variability on predicted metal speciation in soil solution.

PubMed

Groenenberg, Jan E; Koopmans, Gerwin F; Comans, Rob N J

2010-02-15

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Proposal of a Method to Determine the Correlation between Total Suspended Solids and Dissolved Organic Matter in Water Bodies from Spectral Imaging and Artificial Neural Networks

PubMed Central

Kupssinskü, Lucas S.; T. Guimarães, Tainá; Koste, Emilie C.; da Silva, Juarez M.; de Souza, Laís V.; Oliverio, William F. M.; Jardim, Rogélio S.; Koch, Ismael É.; de Souza, Jonas G.; Mauad, Frederico F.

2018-01-01

Water quality monitoring through remote sensing with UAVs is best conducted using multispectral sensors; however, these sensors are expensive. We aimed to predict multispectral bands from a low-cost sensor (R, G, B bands) using artificial neural networks (ANN). We studied a lake located on the campus of Unisinos University, Brazil, using a low-cost sensor mounted on a UAV. Simultaneously, we collected water samples during the UAV flight to determine total suspended solids (TSS) and dissolved organic matter (DOM). We correlated the three bands predicted with TSS and DOM. The results show that the ANN validation process predicted the three bands of the multispectral sensor using the three bands of the low-cost sensor with a low average error of 19%. The correlations with TSS and DOM resulted in R2 values of greater than 0.60, consistent with literature values. PMID:29315219

The Photodegradation of Ibuprofen and Dissolved Organic Matter in Lake Superior and St. Louis River Water

PubMed Central

Moynan, Angela B.

2012-01-01

Abstract Ibuprofen can enter bodies of water via waste water treatment. The question was what effect does photodegradation have on ibuprofen and dissolved organic matter (DOM) in Lake Superior (oligiotrophic) and St. Louis (tannic stained) River water? Ibuprofen concentrations of 15,000, 30,000, and 60,000 μg/L were made from lake, river, and distilled water, as well as additional distilled concentrations of 7,500 and 120,000 μg/L. Half of the eighty-four trial cups were placed in an ultraviolet light cabinet and half of the set were placed in a dark cabinet for three days. After the exposure period, a UV-Vis was performed to measure change in molar mass and the summed absorbance of colored dissolved organic matter (CDOM). It appears that ibuprofen decreases in molar mass after exposure to light in distilled and lake water with 15,000 μg/L of ibuprofen. Surprisingly, the molar mass of DOM in river water increases after UV exposure. Possibly, this occurred because the river water has such a high molar mass of DOM and was not filtered. Microbial biomass could also have contributed to this increase. Ibuprofen entering bodies of water via the waste water treatment system appears to be affected by UV light exposure, but in different ways. PMID:23244688

Ground-fire effects on the composition of dissolved and total organic matter in forest floor and soil solutions from Scots pine forests in Germany: new insights from solid state 13C NMR analysis

NASA Astrophysics Data System (ADS)

Näthe, Kerstin; Michalzik, Beate; Levia, Delphis; Steffens, Markus

2016-04-01

Fires represent an ecosystem disturbance and are recognized to seriously pertubate the nutrient budgets of forested ecosystems. While the effects of fires on chemical, biological, and physical soil properties have been intensively studied, especially in Mediterranean areas and North America, few investigations examined the effects of fire-induced alterations in the water-bound fluxes and the chemical composition of dissolved and particulate organic carbon and nitrogen (DOC, POC, DN, PN). The exclusion of the particulate organic matter fraction (0.45 μm < POM < 500 μm) potentially results in misleading inferences and budgeting gaps when studying the effects of fires on nutrient and energy fluxes. To our best knowledge, this is the first known study to present fire-induced changes on the composition of dissolved and total organic matter (DOM, TOM) in forest floor (FF) and soil solutions (A, B horizon) from Scots pine forests in Germany. In relation to control sites, we test the effects of low-severity fires on: (1) the composition of DOM and TOM in forest floor and soil solutions; and (2) the translocated amount of particulate in relation to DOC and DN into the subsoil. The project aims to uncover the mechanisms of water-bound organic matter transport along an ecosystem profile and its compositional changes following a fire disturbance. Forest floor and soil solutions were fortnightly sampled from March to December 2014 on fire-manipulated and control plots in a Scots pine forest in Central Germany. Shortly after the experimental duff fire in April 2014 pooled solutions samples were taken for solid-state 13C NMR spectroscopy to characterize DOM (filtered solution < 0.8μm pore size) and TOM in unfiltered solutions. Independent from fire manipulation, the composition of TOM was generally less aromatic (aromaticity index [%] according to Hatcher et al., 1981) with values between 18 (FF) - 25% (B horizon) than the DOM fraction with 23 (FF) - 27% (B horizon). For DOM in FF solution, fire manipulation caused an increase in aromaticity from 23 to 27% compared to the control, due to an increase of the aryl-C and a decrease of the O-alkyl-C and alkyl-C signal. Fire effects were leveled out in the mineral soil. For TOM, fire effects became notable only in the A horizon, exhibiting a decrease in aromaticity from 22 to 18% compared to the control, due to increased O-alkyl-C and diminished aryl-C proportions. Compared to the control, fire only caused minor DOC release rates (< 10%) in the FF and mineral soil, while DN in the FF was significantly mobilized (+ 40%) by fire exhibiting annual values of 33 at the control sites compared to 46 kg DN ha-1 at the fire treated sites. Compared to the control, fire events did not significantly enhance the proportion of POC and PN in the total C and N amounts exhibiting values between 10 and 20%. To fully understand the quality and amount of translocated organic C and N compounds within soils under both ambient as well as fire environments, dissolved and particulate size fractions need to be considered.

Fluorescence spectroscopy for field surveillance of THM formation precursors to increase sustainable drinking water treatment for the water industry

NASA Astrophysics Data System (ADS)

Stutter, Marc; Cooper, Pat; Wyness, Adam; Allan, Richard; Weir, Paul; Frogbrook, Zoe; Haffey, Mark

2017-04-01

Our understanding of the composition and diversity of dissolved organic matter (DOM) in natural waters is improving rapidly with techniques such as fluorescence spectroscopy. For the water industry issues of the reaction of DOM and different processes used to reduce microbial contamination in water for public supply are a pressing concern. A range of processes can be used but the common disinfection by free chlorine can react with DOM to produce a group of substances referred to as disinfection by-products (DBPs) that have been linked to health concerns. Hence, management at water treatment works aims to remove DOM prior to the disinfection reaction or change the treatment method. Both are costly financially and in terms of process chemical, such as coagulents that work variably with different DOM forms. Hence, enabling methods of catchment management, which have long been associated with tackling other forms of pollution (e.g. N, P) through source-pathway-receptor concepts, are options for the water industry where catchment raw water source management is a possible sustainable addition to conventional treatment. This presentation looks at the requirements and ongoing work to inform source water management options using bench-top fluorescence excitation-emission spectroscopy and hand-held sensors to detect DBP precursors, namely trihalomethanes (THMs), in complex multi-source environments. We start by introducing the forms of DOM discernible in the fluorescence excitation-emission matrix, how these have been ascribed to different compounds by previous studies and what wavelengths are available for in-situ detection. We then discuss methodology issues for sample storage and standard materials. Then we draw on results from a national set of Scottish catchments and a small catchment study to evaluate relationships between THM compounds from standard assay and GC-MS detection against spectral DOM surrogates, including catchment hydrochemical and spatial data covariates. This is supported by laboratory batch work on potential synergistic interactions for THM formation in mixtures of DOM types from isolated humic substances and amino-acid compounds; where the latter can provide markers for anthropogenic pollution sources such as wastewater and farm effluents. Finally, we conclude on some of the potential for these techniques for catchment raw source water management. We present a circular-sustainability argument whereby the broad range of DOM combinations detectable by fluorescence techniques allows consideration of catchment C-source markers of potential THM formation resulting from disinfection and of the microbial contaminants necessitating the disinfection treatment.

The Removal of Terrestrial Dissolved Organic Matter in Coastal Regions by Photo-Flocculation Process

NASA Astrophysics Data System (ADS)

Abdulla, H. A.; Mopper, K.

2015-12-01

The fate of terrestrial dissolved organic matter (tDOM) as it moves to open ocean was the focus of many studies for the last three decades, most of these studies were focused on three major removal processes: 1) Photochemical mineralization of tDOM (conversion to inorganic forms); 2) Microbial oxidation; and 3) Mixing-induced flocculation. Based on recent estimations, the combination of theses removal processes accounts for ~20-35% of the loss of tDOM in estuaries and coastal regions; which is far from closing the gap between the riverine fluxes of tDOM and the amount of tDOM detected in the open ocean. In a preliminary experiment to determine if photo-flocculation indeed occurs at pH values and ionic strengths found in estuaries. A 0.1-μm filtered riverine was diluted 1:1 with artificial seawater and MilliQ water to yield final salinities ranging from 0 - 15; the pH of the saline samples was ranged from 6-8. Photo-flocculation was observed for all salinities, with particles organic carbon (POC) values ranged from 3.2 to 8.5% of the original DOC. Interestingly, the composition of the Photo-flocculated particles in the saline samples was markedly different from the zero salinity samples as shown in their FT-IR spectra. The photo-flocculated particles that formed in the saline samples appear to be rich in carbohydrate and amide functionalities (protein-like), while containing insignificant deprotonated carboxylate. While the flocs that formed in freshwater (salinity zero) are richer in deprotonated carboxyl groups, and relatively depleted in carbohydrate functionality.

Influence of solar radiation on DOM release from resuspended Florida Bay sediments

NASA Astrophysics Data System (ADS)

Shank, G. C.; Evans, A.; Jaffé, R.; Yamashita, Y.

2009-12-01

This study investigated dissolved organic matter (DOM) release from resuspended Florida Bay sediments under dark and sunlit conditions. Much of Florida Bay (located between Everglades and Florida Keys) is very shallow (< 2 m) so sediment resuspension events have the potential to substantially impact the concentration and composition of DOM in the water column. For our study, sediments were collected at several sites across Florida Bay and ranged from 3-11 percent organic carbon (by weight). Sediments were resuspended in oligotrophic seawater for 48 hours in 1 L quartz flasks in the dark and under simulated solar radiation (SunTest XLS+) at concentrations of 100 mg L-1 and 1 g L-1 (wet weight). Final solutions were analyzed for DOC, chromophoric dissolved organic matter (CDOM), and Excitation Emission Matrix (EEM) fluorescence. Results showed little to no DOC increases in the resuspensions performed under dark conditions, but substantial release of DOM in irradiated resuspensions, especially at high sediment concentrations where DOC increases ranged from 100-500%. The sediments also released substantial quantities of CDOM to solution under irradiated conditions. The magnitude of DOC increases in irradiated resuspensions were well-correlated with the amount of particulate organic carbon (POC) added. Data from EEM-PARAFAC analyses suggests the photochemically produced DOM was comprised of desorbed humic material with a smaller fraction from microbial mediated processes. Our study provides evidence that sediment resuspension episodes in shallow sunlit waters such as Florida Bay have the potential to provide an important source of organic carbon to overlying waters.

Changes in optical characteristics of surface microlayers in the Peruvian upwelling region hint to photochemically and microbially-mediated DOM turnover

NASA Astrophysics Data System (ADS)

Engel, A.; Galgani, L.

2016-02-01

The coastal upwelling system off Peru is characterized by high biological activity and associated subsurface oxygen minimum zone, leading to an enhanced emission of atmospheric trace gases. High biological productivity in the water column may promote the establishment of enriched organic surface films, key environments for processes regulating gas fluxes across the water-air interface. During M91 cruise to the Peruvian upwelling, we focused our attention on the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples in 38 stations determining DOC concentrations, amino acids composition, marine gels, CDOM and bacterial abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slopes (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources. Profound changes in spectral slope properties were observed suggesting smaller MW CDOM in the SML compared to underlying water. Microbial and photochemical degradation are likely the main drivers for organic matter cycling in the top layer of the ocean. Consequences on the formation of inorganic and organic species highly relevant for air-sea gas exchange and for climate dynamics will be discussed.

Vertical stratification of bacterial communities driven by multiple environmental factors in the waters (0-5000 m) off the Galician coast (NW Iberian margin)

NASA Astrophysics Data System (ADS)

Dobal-Amador, Vladimir; Nieto-Cid, Mar; Guerrero-Feijoo, Elisa; Hernando-Morales, Victor; Teira, Eva; Varela-Rozados, Marta M.

2016-08-01

The processes mediated by microbial planktonic communities occur along the entire water column, yet the microbial activity and composition have been studied mainly in surface waters. This research examined the vertical variation in bacterial abundance, activity and community composition and structure from surface down to 5000 m depth following a longitudinal transect off the Galician coast (NW Iberian margin, from 43°N, 9°W to 43°N, 15°W). Community activity and composition changed with depth. The leucine incorporation rates decreased from the euphotic layer to the bathypelagic waters by three orders of magnitude, whereas prokaryotic abundance decreased only by one order of magnitude. The relative abundance of SAR11 and Alteromonas, determined by catalyzed reported deposition fluorescence in situ hybridization (CARD-FISH), decreased with depth. Meanwhile, the contribution of SAR 202 and SAR324 was significantly higher in the deeper layers (i.e. NEADW, North East Atlantic Deep Water and LDW, Lower Deep Water) than in the euphotic zone. Bacterial community structure, assessed by Automated Ribosomal Intergenic Spacer Analysis (ARISA), was depth-specific. A distance based linear model (DistLM) revealed that the variability found in bacterial community structure was mainly explained by temperature nitrate, phosphate, dissolved organic matter (DOM) fluorescence, prokaryotic abundance, leucine incorporation and to a lesser extent salinity, oxygen, CDOM absorbance and dissolved organic carbon concentration. Our results displayed a bacterial community structure shaped not only by depth-related physicochemical features but also by DOM quality, indicating that different prokaryotic taxa have the potential to metabolize particular DOM sources.

The effects of dissolved organic matter and feeding on bioconcentration and oxidative stress of ethylhexyl dimethyl p-aminobenzoate (OD-PABA) to crucian carp (Carassius auratus).

PubMed

Ma, Binni; Lu, Guanghua; Yang, Haohan; Liu, Jianchao; Yan, Zhenhua; Nkoom, Matthew

2018-03-01

Bioconcentration of UV filters in organisms is an important indicator for the assessment of environmental hazards. However, bioconcentration testing rarely accounts for the influence of natural aquatic environmental factors. In order to better assess the ecological risk of organic UV filters (OUV-Fs) in an actual water environment, this study determined the influences of dissolved organic matter (DOM) (0, 1, 10, and 20 mg/L) and feeding (0, 0.5, 1, and 2% body weight/d) on bioconcentration of ethylhexyl dimethyl p-aminobenzoate (OD-PABA) in various tissues of crucian carp (Carassius auratus). Moreover, oxidative stress in the fish liver caused by the OD-PABA was also investigated by measuring activities of superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST), and levels of glutathione (GSH) and malondialdehyde (MDA). The bioconcentration of OD-PABA in the fish tissues was significantly decreased with the presence of DOM indicating a reduction of OD-PABA bioavailability caused by DOM. The bioconcentration factors (BCFs) decreased by 28.00~50.93% in the muscle, 72.67~96.74% in the gill, 37.84~87.72% in the liver, and 10.32~79.38% in the kidney at different DOM concentrations compared to those of the non-DOM treatments. Significant changes in SOD, CAT, GST, GSH, and MDA levels were found in the DOM- and OD-PABA-alone treatments. However, there were no significant differences in the SOD, CAT, GST, and MDA levels found when co-exposure to OD-PABA and DOM. Feeding led to lower OD-PABA concentrations in the fish tissues, and the concentrations were decreased with increasing feeding ratios. BCFs in various tissues reduced by 39.75~72.52% in the muscle, 56.86~79.73% in the gill, 66.41~87.50% in the liver, and 75.88~89.10% in the kidney, respectively. In the unfed treatments, the levels of SOD and MDA were significantly higher than those of the fed ones while GST and GSH levels were remarkably inhibited indicating the enhanced effect of starvation to oxidative stress. There was no markedly alternation of the biomarker levels observed between different fed treatments. In conclusion, our study indicated that both DOM and feeding reduced bioconcentration of OD-PABA and alleviated oxidative stress to some extent in the crucian carp.

Chemical properties of dissolved organic matter derived from sugarcane rind and the impacts on copper adsorption onto red soil.

PubMed

Hu, Sihai; Wu, Yaoguo; Yi, Na; Zhang, Shuai; Zhang, Yuanjing; Xin, Xu

2017-09-01

Dissolved organic matter (DOM), as the most active organic carbon in the soil, has a coherent affinity with heavy metals from inherent and exogenous sources. Although the important roles of DOM in the adsorption of heavy metals in soil have previously been demonstrated, the heterogeneity and variability of the chemical constitution of DOM impede the investigation of its effects on heavy metal adsorption onto soil under natural conditions. Fresh DOM (FDOM) and degraded DOM (DDOM) from sugarcane rind were prepared, and their chemical properties were measured by Fourier-transform infrared spectrometry (FTIR), excitation-emission matrix (EEM) fluorescence spectroscopes, nuclear magnetic resonance (NMR), and molecular weight distribution (MWD). They were also used in batch experiments to evaluate their effects on the adsorption of Cu(II) onto farmland red soil. Based on our results, the chemical structure and composition of DDOM greatly varied; compared with FDOM, the C/O ratio (from 24.0 to 9.6%) and fluorescence index (FI) (from 1.4 to 1.0) decreased, and high molecular weight (>10 kDa) compounds increased from 23.18 to 70.51%, while low molecular weight (<3 kDa) compounds decreased from 56.13 to 12.13%; aromaticity and humification degree were markedly enhanced. The discrepancy of FDOM and DDOM in terms of chemical properties greatly influenced Cu(II) adsorption onto red soil by affecting DOM-Cu(II) complex capacity. The FDOM inhibited the adsorption of Cu(II), while DDOM promoted adsorption, which was significantly influenced by soil pH. Maximum adsorption capacity (Q m ) was 0.92 and 5.76 mg g -1 in the presence of FDOM and DDOM, respectively. The adsorption process with DDOM could be better described by the Langmuir model, while that with FDOM was better described by the Freundlich model. The impacts caused by the dynamic changes of the chemical properties of DOM under natural conditions should therefore be considered in the risk assessment and remediation of soils contaminated with heavy metals.

A contribution to regional stratigraphic correlations of the Afro-Brazilian depression - The Dom João Stage (Brotas Group and equivalent units - Late Jurassic) in Northeastern Brazilian sedimentary basins

NASA Astrophysics Data System (ADS)

Kuchle, Juliano; Scherer, Claiton Marlon dos Santos; Born, Christian Correa; Alvarenga, Renata dos Santos; Adegas, Felipe

2011-04-01

The Dom João Stage comprises an interval with variable thickness between 100 and 1200 m, composed of fluvial, eolian and lacustrine deposits of Late Jurassic age, based mainly on the lacustrine ostracod fauna (although the top deposits may extend into the Early Cretaceous). These deposits comprise the so-called Afro-Brazilian Depression, initially characterized as containing the Brotas Group of the Recôncavo Basin (which includes the Aliança and the Sergi Formations) and subsequently extended into the Tucano, Jatobá, Camamu, Almada, Sergipe, Alagoas and Araripe Basins in northeastern Brazil, encompassing the study area of this paper. The large occurrence area of the Dom João Stage gives rise to discussions about the depositional connectivity between the basins, and the real extension of sedimentation. In the first studies of this stratigraphic interval, the Dom João Stage was strictly associated with the rift phase, as an initial stage (decades of 1960-70), but subsequent analyses considered the Dom João as an intracratonic basin or pre-rift phase - without any relation to the active mechanics of a tectonic syn-rift phase (decades of 1980-2000). The present work developed an evolutionary stratigraphic and tectonic model, based on the characterization of depositional sequences, internal flooding surfaces, depositional systems arrangement and paleoflow directions. Several outcrops on the onshore basins were used to build composite sections of each basin, comprising facies, architectural elements, depositional systems, stratigraphic and lithostratigraphic frameworks, and paleocurrents. In addition to that, over a hundred onshore and offshore exploration wells were used (only 21 of which are showed) to map the depositional sequences and generate correlation sections. These show the characteristics and relations of the Dom João Stage in each studied basin, and they were also extended to the Gabon Basin. The results indicate that there were two main phases during the Dom João Stage, in which distinctive sedimentary environments were developed, reflecting depositional system arrangements, paleoflow directions were diverse, and continuous or compartmented basins were developed.

Characterization of Organic Matter Sources within a Matrix of Land Use in Northeast Utah

NASA Astrophysics Data System (ADS)

Kelso, J. E.; Baker, M. A.

2017-12-01

Dynamics of organic matter (OM) sources in natural aquatic systems have been studied for decades, but urban studies have revealed additional, less studied, OM sources such as stormwater, lawn clippings, and wastewater effluent. Traditionally the OM pool in freshwater systems has been defined as a homogenous pool of varying size classes: course particulate, fine particulate and dissolved OM. Our goal was to identify and quantify the composition of fine particulate OM (FPOM), and dissolved OM (DOM) as derived from autochthonous, terrestrial, and potential anthropogenic sources. We hypothesized anthropogenic changes in land use have increased the proportion of autochthonous sources of OM. We sampled OM at 33 sites in four watersheds in northeast Utah that encompass a range of land uses. Stable isotopes of carbon, nitrogen, and deuterium were collected for all size classes of OM, and DOM was analyzed with a spectrofluorometer. Stable isotopes were used to estimate the proportion of autochthonous and terrestrial sources of OM. Fluorescence indices and a PARAFAC model were created from DOM excitation emission matrices (EEMs). FPOM appeared to be a mixture of autochthonous and terrestrial sources but overlap in endmember isotope values made quantifying the proportion of each source difficult. Higher deuterium values (-120 to -80‰) were associated with sites receiving wastewater effluent, while sites with agriculture, forest, and urban land use had lower deuterium isotope values (-200 to -110). DOM Excitation Emission Matrices were resolved into a 5-component PARAFAC model. The percent of protein-like DOM components tended to be higher in urban versus non-urban sites (mean 35%, S.D. 12% versus mean 25%, S.D. 15%). We concluded deuterium isotopes may be used as a tracer or wastewater effluent and DOM is composed of more labile, protein-like DOM with increased wastewater input. A greater understanding of the sources of OM can inform management and policy decisions aimed at mitigating the effects of OM pollution. For example, evaluating tradeoffs between mitigating the effects of OM inputs from cattle grazing versus building or improving waste water treatment facilities can be further explored.

Molecular characterization of macrophyte-derived dissolved organic matters and their implications for lakes

USDA-ARS?s Scientific Manuscript database

Chemical properties of whole organic matter (OM) and its dissolved organic matter (DOM) fraction from six dominant macrophytes in Lake Dianchi were comparatively characterized, and their environmental implications were discussed. Significant differences in chemical composition of the OM samples were...

Combining asymmetrical flow field-flow fractionation with on- and off-line fluorescence detection to examine biodegradation of riverine dissolved and particulate organic matter.

PubMed

Lee, Sang Tak; Yang, Boram; Kim, Jin-Yong; Park, Ji-Hyung; Moon, Myeong Hee

2015-08-28

This study demonstrated that asymmetrical flow field-flow fractionation (AF4) coupled with on-line UV and fluorescence detection (FLD) and off-line excitation-emission matrix (EEM) fluorescence spectroscopy can be employed to analyze the influence of microbial metabolic activity on the consumption and production of freshwater organic matter. With the AF4 system, organic matter is on-line enriched during a focusing/relaxation period, which is an essential process prior to separation. Size-fractionated chromophoric and fluorophoric organic materials were simultaneously monitored during the 30-min AF4 separation process. Two fractions of different sizes (dissolved organic matter (DOM) and particulate organic matter (POM)) of freshwater samples from three locations (up-, mid-, and downstream) along the Han River basin of Korea were incubated with the same inoculum for 14 days to analyze fraction-specific alterations in optical properties using AF4-UV-FLD. A comparison of AF4 fractograms obtained from pre- and post-incubation samples revealed that POM-derived DOM were more susceptible to microbial metabolic activity than was DOM. Preferential microbial consumption of protein-like DOM components concurred with enhanced peaks of chromophoric and humic-like fluorescent components, presumably formed as by-products of microbial processing. AF4-UV-FLD combined with off-line identification of microbially processed components using EEM fluorescence spectroscopy provides a powerful tool to study the relationship between microbial activity and composition as well as biodegradability of DOM and POM-derived DOM from different origins, especially for the analysis of chromophoric and fluorophoric organic matter that are consumed and produced by microbial metabolic activity. The proposed AF4 system can be applied to organic matter in freshwater samples having low concentration range (0.3-2.5ppm of total organic carbon) without a pre-concentration procedure. Copyright © 2015 Elsevier B.V. All rights reserved.

Changes in bacterial community metabolism and composition during the degradation of dissolved organic matter from the jellyfish Aurelia aurita in a Mediterranean coastal lagoon.

PubMed

Blanchet, Marine; Pringault, Olivier; Bouvy, Marc; Catala, Philippe; Oriol, Louise; Caparros, Jocelyne; Ortega-Retuerta, Eva; Intertaglia, Laurent; West, Nyree; Agis, Martin; Got, Patrice; Joux, Fabien

2015-09-01

Spatial increases and temporal shifts in outbreaks of gelatinous plankton have been observed over the past several decades in many estuarine and coastal ecosystems. The effects of these blooms on marine ecosystem functioning and particularly on the dynamics of the heterotrophic bacteria are still unclear. The response of the bacterial community from a Mediterranean coastal lagoon to the addition of dissolved organic matter (DOM) from the jellyfish Aurelia aurita, corresponding to an enrichment of dissolved organic carbon (DOC) by 1.4, was assessed for 22 days in microcosms (8 l). The high bioavailability of this material led to (i) a rapid mineralization of the DOC and dissolved organic nitrogen from the jellyfish and (ii) the accumulation of high concentrations of ammonium and orthophosphate in the water column. DOM from jellyfish greatly stimulated heterotrophic prokaryotic production and respiration rates during the first 2 days; then, these activities showed a continuous decay until reaching those measured in the control microcosms (lagoon water only) at the end of the experiment. Bacterial growth efficiency remained below 20%, indicating that most of the DOM was respired and a minor part was channeled to biomass production. Changes in bacterial diversity were assessed by tag pyrosequencing of partial bacterial 16S rRNA genes, DNA fingerprints, and a cultivation approach. While bacterial diversity in control microcosms showed little changes during the experiment, the addition of DOM from the jellyfish induced a rapid growth of Pseudoalteromonas and Vibrio species that were isolated. After 9 days, the bacterial community was dominated by Bacteroidetes, which appeared more adapted to metabolize high-molecular-weight DOM. At the end of the experiment, the bacterial community shifted toward a higher proportion of Alphaproteobacteria. Resilience of the bacterial community after the addition of DOM from the jellyfish was higher for metabolic functions than diversity, suggesting that jellyfish blooms can induce durable changes in the bacterial community structure in coastal lagoons.

Photochemical Transformation and Bacterial Utilization of Dissolved Organic Matter and Disinfection Byproduct Precursors from Foliar Litter

NASA Astrophysics Data System (ADS)

Chow, A. T.; Wong, P.; O'Geen, A. T.; Dahlgren, R. A.

2009-12-01

Foliar litter is an important terrestrial source of dissolved organic matter (DOM) in surface water. DOM is a public health concern since it is a precursor of carcinogenic disinfection byproducts (DBPs) during drinking water treatment. Chemical characterization of in-situ water samples for their impact on water treatment may be misleading because DOM characteristics can be altered from their original composition during downstream transport to water treatment plants. In this study, we collected leachate from four fresh litters and decomposed duffs from four dominant vegetation components of California oak woodlands: blue oak (Quercus douglassi), live oak (Quercus wislizenii), foothill pine (Pinus sabiniana), and annual grasses to evaluate their DOM degradability and the reactivity of altered DOM towards DBP formation. Samples were filtered through a sterilized membrane (0.2 micron) and exposed to natural sunlight and Escherichia coli K-12 independently for 14 days. Generally speaking, leachate from decomposed duff was relatively resistant towards biodegradation compared to that from fresh litter, but the former was more susceptible to photo-transformation. Photo-bleaching caused a 30% decrease in ultra-violet absorbance at 254 nm (UVA) but no significant changes in dissolved organic carbon (DOC) concentration. This apparent loss of aromatic carbon in DOM, in terms of specific UVA, did not result in a decrease of specific trihalomethane (THM) formation potential, although aromatic carbon is considered as a major reactive site for THM formation. In addition, there were significant increases (p < 0.05) of chloral hydrate after the 14-day exposure, suggesting that the photolytic products could be a precursor of chloral hydrate. In contrast, samples inoculated with E. coli did not show a significant effect on the DOC concentration, UVA or DBP formation, although the colony counts indicated a 2-log cell growth during the 14-day incubation. Results suggest photolysis is a major biogeochemical process altering terrestrial DOC in surface water.

DOMstudio: an integrated workflow for Digital Outcrop Model reconstruction and interpretation

NASA Astrophysics Data System (ADS)

Bistacchi, Andrea

2015-04-01

Different Remote Sensing technologies, including photogrammetry and LIDAR, allow collecting 3D dataset that can be used to create 3D digital representations of outcrop surfaces, called Digital Outcrop Models (DOM), or sometimes Virtual Outcrop Models (VOM). Irrespective of the Remote Sensing technique used, DOMs can be represented either by photorealistic point clouds (PC-DOM) or textured surfaces (TS-DOM). The first are datasets composed of millions of points with XYZ coordinates and RGB colour, whilst the latter are triangulated surfaces onto which images of the outcrop have been mapped or "textured" (applying a tech-nology originally developed for movies and videogames). Here we present a workflow that allows exploiting in an integrated and efficient, yet flexible way, both kinds of dataset: PC-DOMs and TS-DOMs. The workflow is composed of three main steps: (1) data collection and processing, (2) interpretation, and (3) modelling. Data collection can be performed with photogrammetry, LIDAR, or other techniques. The quality of photogrammetric datasets obtained with Structure From Motion (SFM) techniques has shown a tremendous improvement over the past few years, and this is becoming the more effective way to collect DOM datasets. The main advantages of photogrammetry over LIDAR are represented by the very simple and lightweight field equipment (a digital camera), and by the arbitrary spatial resolution, that can be increased simply getting closer to the out-crop or by using a different lens. It must be noted that concerns about the precision of close-range photogrammetric surveys, that were justified in the past, are no more a problem if modern software and acquisition schemas are applied. In any case, LIDAR is a well-tested technology and it is still very common. Irrespective of the data collection technology, the output will be a photorealistic point cloud and a collection of oriented photos, plus additional imagery in special projects (e.g. infrared images). This dataset can be used as-is (PC-DOM), or a 3D triangulated surface can be interpolated from the point cloud, and images can be used to associate a texture to this surface (TS-DOM). In the DOMstudio workflow we use both PC-DOMs and TS-DOMs. Particularly, the latter are obtained projecting the original images onto the triangulated surface, without any downsampling, thus retaining the original resolution and quality of images collected in the field. In the DOMstudio interpretation step, PC-DOM is considered the best option for fracture analysis in outcrops where facets corresponding to fractures are present. This allows obtaining orientation statistics (e.g. stereoplots, Fisher statistics, etc.) directly from a point cloud where, for each point, the unit vector normal to the outcrop surface has been calculated. A recent development in this kind of processing is represented by the possibility to automatically select (segment) subset point clouds representing single fracture surfaces, which can be used for studies on fracture length, spacing, etc., allowing to obtain parameters like the frequency-length distribution, P21, etc. PC-DOM interpretation can be combined or complemented, depending on the outcrop morphology, with an interpretation carried out on a TS-DOM in terms of traces, which are the linear intersection of "geological" surfaces (fractures, faults, bedding, etc.) with the outcrop surface. This kind of interpretation is very well suited for outcrops with smooth surfaces, and can be performed either by manual picking, or by applying image analysis techniques on the images associated with the DOM. In this case, a huge mass of data, with very high resolution, can be collected very effectively. If we consider applications like lithological or mineral map-ping, TS-DOM datasets are the only suitable support. Finally, the DOMstudio workflow produces output in formats that are compatible with all common geomodelling packages (e.g. Gocad/Skua, Petrel, Move), allowing to directly use the quantitative data collected on DOMs to generate and calibrate geological, structural, or geostatistical models. I will present examples of applications including hydrocarbon reservoir analogue studies, studies on fault zone architecture, lithological mapping on sedimentary and metamorphic rocks, and studies on the surface of planets and small bodies in the Solar System.

POM Pulses: Characterizing the Physical and Chemical Properties of Particulate Organic Matter (POM) Mobilized by Large Storm Events and its Influence on Receiving Fluvial Systems

NASA Astrophysics Data System (ADS)

Johnson, E. R.; Rowland, R. D.; Protokowicz, J.; Inamdar, S. P.; Kan, J.; Vargas, R.

2016-12-01

Extreme storm events have tremendous erosive energy which is capable of mobilizing vast amounts of material from watershed sources into fluvial systems. This complex mixture of sediment and particulate organic matter (POM) is a nutrient source, and has the potential to impact downstream water quality. The impact of POM on receiving aquatic systems can vary not only by the total amount exported but also by the various sources involved and the particle sizes of POM. This study examines the composition of POM in potential sources and within-event POM by: (1) determining the amount and quality of dissolved organic matter (DOM) that can be leached from coarse, medium and fine particle classes; (2) assessing the C and N content and isotopic character of within-event POM; and (3) coupling physical and chemical properties to evaluate storm event POM influence on stream water. Storm event POM samples and source sediments were collected from a forested headwater catchment (second order stream) in the Piedmont region of Maryland. Samples were sieved into three particle classes - coarse (2mm-1mm), medium (1mm-250µm) and fine (<250µm). Extractions were performed for three particle class sizes and the resulting fluorescent organic matter was analyzed. Carbon (C) and Nitrogen (N) amount, C:N ratio, and isotopic analysis of 13C and 15N were performed on solid state event and source material. Future work will include examination of microbial communities associated with POM particle size classes. Physical size class separation of within-event POM exhibited differences in C:N ratios, δ15N composition, and extracted DOM lability. Smaller size classes exhibited lower C:N ratios, more enriched δ15N and more recalcitrant properties in leached DOM. Source material had varying C:N ratios and contributions to leached DOM. These results indicate that both source and size class strongly influence the POM contribution to fluvial systems during large storm events.

Is the molecular diversity of marine dissolved organic matter already imprinted in the exometabolome of single strains?

NASA Astrophysics Data System (ADS)

Noriega-Ortega, B. E.; Wienhausen, G.; Dittmar, T.; Simon, M.; Niggemann, J.

2016-02-01

Dissolved organic matter (DOM) in the ocean, the marine geometabolome, is an extremely complex mixture composed of a wide variety of compounds. The molecular chemodiversity affects the function and turnover rate of DOM in the ocean. We hypothesize that the active microbial community essentially contributes to the complexity of the DOM pool through uptake and excretion of compounds. We tested this hypothesis in culture experiments with fully-sequenced strains of the Roseobacter clade. Bacteria of the Roseobacter clade are among the most abundant microbial players in the ocean. We studied the exometabolome of two representatives of the Roseobacter clade, Phaeobacter inhibens DSM 17395 and Dinoroseobacter shibae. The organisms were grown separately in cultures on defined single model substrates (acetate, succinate, glutamate, glucose). We used a non-targeted analytical approach via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the exometabolome at the molecular level, complemented by compound-specific analyses of free and combined amino acids and carbohydrates. The exometabolome composition varied between the tested strains, which released a different suite of compounds depending on the growth phase as well as on growth conditions (substrate). Both organisms exhibited a core exometabolome with compounds released when growing on either substrate and at all growth phases, and a variable exometabolome specific for different substrates and growth phases. However, only a small fraction of the exometabolites detected by FT-ICR-MS could be directly linked to the genome or transcriptome. We interpret these findings as evidence for the excretion of molecularly highly-diverse metabolic waste, whose composition is dependent on the metabolic state and genetic repertoire of the organisms. The molecular diversity of compounds excreted by a single strain is extraordinary and is likely the reason for the molecular diversity of natural DOM in the ocean.

Elucidation of riverine and lacustrine dissolved organic matter (DOM) composition using comprehensive GC×GC time-of-flight mass spectrometry (GC×GC-TOF-MS)

NASA Astrophysics Data System (ADS)

Ball, G. I.; Goldberg, S. J.; Aluwihare, L. I.

2012-12-01

Rivers and streams play a key role in mediating the transfer of organic carbon (both particulate and dissolved) from terrestrial to aquatic settings. Dissolved organic carbon represents the majority of the carbon pool in low alkalinity riverine and lacustrine waters, and its composition plays important roles, including affecting water clarity and stimulating heterotrophic productivity, which influences its rate of reconversion to CO2. Yet, the chemical complexity and heterogeneity of this reservoir have limited structural elucidation to primarily describing common bulk-level characteristics. Seasonal SPE-DOM samples from the Upper Truckee River, Lake Tahoe, and two surrounding lakes, as well as SPE-DOM isolated from two dissimilar California rivers, were first characterized using δ13C, δ15N, 1H-NMR, and then subjected to CuO oxidation followed by TMS derivatization and were analyzed using comprehensive GC×GC time-of-flight mass spectrometry (GC×GC-TOF-MS). Thousands of peaks were identified per sample. Simultaneous, orthogonal separation of components in two dimensions (on the basis of volatility and polarity) allowed for the identification of oxidation mixture components by both their MS spectra and, when MS spectra alone were insufficient for structural assignment and standards were absent, by the observed trajectories of homologues compound series assumed in 2-D retention-time space. Several homologous compound series were observed, including mid-to-long chain fatty acids, keto (ω-1) fatty acids, (α, ω)-dioic acids, and the resolution and identification of closely related isomers, such as the benzene di-, and tricarboxylic acids, were also facilitated by this method. Furthermore, in mixed samples containing two or more end-members, such as in lake DOM samples characterized by mixed terrestrial and algal OM sources, the intensity of the phenolic elution space, which includes the lignin phenols and lignin phenolic dimers, correlates with ancillary measurements indicative of terrestrial OM loading, such as increased 1H-NMR resonance intensities for methoxy and aromatic-linked hydrogens and lower δ13C values more consistent with C3 plant versus algal sources.igure 1: Oxidized and derivatized SPE-DOM isolated from the Upper Truckee River, South Lake Tahoe, CA, and visualized in two dimensions.

Sorption of Groundwater Dissolved Organic Carbon onto Minerals

NASA Astrophysics Data System (ADS)

Rutlidge, H.; Oudone, P.; McDonough, L.; Meredith, K.; Andersen, M. S.; O'Carrol, D. M.; Baker, A.

2017-12-01

Our understanding of groundwater organic matter (OM) as a carbon source or sink in the environmental carbon cycle is limited. The dynamics of groundwater OM is mainly governed by biological processing and its sorption to minerals. In saturated groundwaters, dissolved OM (DOM) represents one part of the groundwater organic carbon pool. Without consideration of the DOM sorption, it is not possible to quantify governing groundwater OM processes. This research explores the rate and extent of DOM sorption on different minerals. Groundwater DOM samples, and International Humic Substances Society (IHSS) standard solutions, were analysed. Each was mixed with a range of masses of iron coated quartz, clean quartz, and calcium carbonate, and shaken for 2 hours to reach equilibrium before being filtered through 0.2 μm for total dissolved organic carbon (DOC) and composition analysis by size-exclusion chromatography-organic carbon detection (LC-OCD). Sorption isotherms were constructed and groundwater DOM sorption were compared to the sorption of IHSS standards. Initial results suggest that for the IHSS standards, the operationally-defined humic substances fraction had the strongest sorption compared to the other LC-OCD fractions and total DOC. Some samples exhibited a small increase in the low molecular weight neutral (LMW-N) aqueous concentration with increasing humic substances sorption. This gradual increase observed could be the result of humic substances desorbing or their breakdown during the experiment. Further results comparing these IHSS standards with groundwater samples will be presented. In conjunction with complementary studies, these results can help provide more accurate prediction of whether groundwater OM is a carbon source or sink, which will enable the management of the groundwater resources as part of the carbon economy.

Photochemical Reactivity of Dissolved Organic Matter in Boreal Lakes

NASA Astrophysics Data System (ADS)

Gu, Y.; Vuorio, K.; Tiirola, M.; Perämäki, S.; Vahatalo, A.

2016-12-01

Boreal lakes are rich in dissolved organic matter (DOM) that terrestrially derived from forest soil and wetland, yet little is known about potential for photochemical transformation of aquatic DOM in boreal lakes. Transformation of chromophoric dissolved organic matter (CDOM) can decrease water color and enhance microbial mineralization, affecting primary production and respiration, which both affect the CO2 balance of the lakes. We used laboratory solar radiation exposure experiments with lake water samples collected from 54 lakes located in Finland and Sweden, representing different catchment composition and watershed location to assess photochemical reactivity of DOM. The pH of water samples ranged from 5.4 to 8.3, and the concentrations of dissolved iron (Fe) were between < 0.06 and 22 μmol L-1. The filtered water samples received simulated solar radiation corresponding to a daily dose of sunlight, and photomineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) was measured for determination of spectral apparent quantum yields (AQY). During irradiation, photobleaching decreased the absorption coefficients of CDOM at 330 nm between 4.9 and 79 m-1 by 0.5 to 11 m-1. Irradiation generated DIC from 2.8 to 79 μmol C L-1. The AQY at 330 nm ranged between 31 and 273 ×10-6 mol C mol photons-1 h-1, which was correlated positively with concentration of dissolved Fe, and negatively with pH. Further statistical analyze indicated that the interaction between pH and Fe may explain much of the photochemical reactivity of DOM in the examined lakes, and land cover concerns main catchment areas also can have impact on the photoreaction process. This study may suggest how environmental conditions regulate DOM photomineralization in boreal lakes.

Behavioral characterization of 2-O-desmethyl and 5-O-desmethyl metabolites of the phenylethylamine hallucinogen DOM.

PubMed

Eckler, J R; Chang-Fong, J; Rabin, R A; Smith, C; Teitler, M; Glennon, R A; Winter, J C

2003-07-01

The present investigation was undertaken to test the hypothesis that known metabolites of the phenylethylamine hallucinogen 1-(2,5-dimethoxy-4-methylphenyl)-2-aminopropane (DOM) are pharmacologically active. This hypothesis was tested by evaluating the ability of racemic DOM metabolites 2-O-desmethyl DOM (2-DM-DOM) and 5-O-desmethyl DOM (5-DM-DOM) to substitute for the stimulus properties of (+)lysergic acid diethylamide (LSD). The data indicate that both metabolites are active in LSD-trained subjects and are significantly inhibited by the selective 5-HT(2A) receptor antagonist M100907. Full generalization of LSD to both 2-DM-DOM and 5-DM-DOM occurred, and 5-DM-DOM was slightly more potent than 2-DM-DOM. Similarly, 5-DM-DOM had a slightly higher affinity than 2-DM-DOM for both 5-HT(2A) and 5-HT(2C) receptors. Additionally, it was of interest to determine if the formation of active metabolite(s) resulted in a temporal delay associated with maximal stimulus effects of DOM. We postulated that if metabolite formation resulted in the aforementioned delay, direct administration of the metabolites might result in maximally stable stimulus effects at an earlier pretreatment time. This hypothesis was tested by evaluating (1) the time point at which DOM produces the greatest degree of LSD-appropriate responding, (2) the involvement of 5-HT(2A) receptor in the stimulus effects of DOM at various pretreatment times by administration of M100907 and (3) the ability of 2-DM-DOM and 5-DM-DOM to substitute for the stimulus properties of LSD using either 15- or 75-min pretreatment time. The data indicate that (a) the DOM stimulus produces the greatest degree of LSD-appropriate responding at the 75-min time point in comparison with earlier pretreatment times and (b) the stimulus effects of DOM are differentially antagonized by M100907 and this effect is a function of DOM pretreatment time prior to testing. Both 2-DM-DOM and 5-DM-DOM were found to be most active, at all doses tested, using a 75-min versus a 15-min pretreatment time. The present data do not permit unequivocal acceptance or rejection of the hypothesis that active metabolites of (-)-DOM provide a full explanation of the observed discrepancy between brain levels of (-)-DOM and maximal stimulus effects.

Effects of changing redox conditions on the dynamics of dissolved organic matter and CO2 in paddy soils

NASA Astrophysics Data System (ADS)

Hanke, Alexander; Cao, Zhi Hong; Liu, Qin; Muhr, Jan; Kalbitz, Karsten

2010-05-01

The current knowledge about dissolved organic matter (DOM) dynamics in soils and its dependence on different C pools based mainly on observations and experiments in aerobic environments. We have only a limited understanding about the effects of changing redox conditions on production and composition of DOM although this fraction of soil organic matter is important for greenhouse gas emission and carbon storage in soils. In many ecosystems temporal and spatial changes of oxic and anoxic conditions are evident and might even increase in future. It is assumed that changing redox conditions are the key drivers of DOM dynamics in such ecosystems. More detailed we tested the following hypotheses: Anoxic conditions result in relative DOM accumulation due to less mineralization of already produced DOM Close relationship between DOM production and CO2 emission 14C signature of CO2 enables the identification of different C pools degraded at oxic and anoxic conditions We chose paddy soils as a model ecosystem because these soils are anoxic during the rice growing period and oxic during harvest and growth of other crops. Furthermore, paddy soils have oxic and anoxic horizons. Soils of a unique chronosequence of paddy soil evolution (50 to 2000 years, China) were studied in direct comparison to non-paddy soils of the same age. In these soils, exposed to different redox conditions over defined periods of times, the dynamics of DOM, CO2, 14C of the CO2 and other redox sensitive elements were followed in laboratory experiments. In the latter redox conditions were changed every 3 weeks from oxic to anoxic and vice versa. Besides analysis of the composition of the soil solution and the gas phase we determined differences in C pools being respired at oxic and anoxic conditions by 14C AMS of the CO2. The measured redox potentials of -50 mV to 250mV at anoxic conditions and 350 mV to 550 mV at oxic conditions were in the expected range and proofed the appropriate setting of the chosen incubation method. PH values varied between 5.5 and 7.5, where anoxic samples had higher values than oxic ones. We further observed only small DOC contents of less than 1mg per g C. Under anoxic conditions as well as among the non-paddy soils DOC production was slightly higher than their respective counterparts. However, we could not find large effects of the time of rice cultivation. Nevertheless, the 2000 year old paddy soil showed highest DOC and CO2 production. The increase of DOC and CO2 production was strongest when the oxic period disrupted the anoxic conditions. 14C data revealed that CO2 respired from the 700 year old paddy soil was much older than from the 2000 year old paddy soil independently from redox condition. Furthermore, C mineralized at anoxic conditions was older than at oxic ones. During the incubation experiment the C consumption shifted from older pools to younger ones. We conclude that DOM accumulated at anoxic conditions will be quickly mineralized at oxic conditions. The influence of soil development on the C dynamics was less important than expected, thus fresh organic matter seems to play a more decisive role. The unexpected large decomposition of old organic matter at anoxic conditions hints to changes in the microbial community involved.

Quantitative and Qualitative Prediction of Light Absorption by Colored Dissolved Organic Matter in the Coastal Zone

DTIC Science & Technology

2006-09-30

photochemical reactivity of CDOM, affecting its concentration and characteristics. The sampling strategy is coordinated with the Danish National...and DOP), stable isotopic composition of DOM, and lignin content (Osburn et al 2001). (Responsible project partner: NRL) This work package will

Singlet oxygen in the coupled photochemical and biochemical oxidation of dissolved organic matter.

PubMed

Cory, Rose M; McNeill, Kristopher; Cotner, James P; Amado, Andre; Purcell, Jeremiah M; Marshall, Alan G

2010-05-15

Dissolved organic matter (DOM) is a significant (>700 Pg) global C pool. Transport of terrestrial DOM to the inland waters and coastal zones represents the largest flux of reduced C from land to water (215 Tg yr(-1)) (Meybeck, M. Am. J. Sci. 1983, 282, 401-450). Oxidation of DOM by interdependent photochemical and biochemical processes largely controls the fate of DOM entering surface waters. Reactive oxygen species (ROS) have been hypothesized to play a significant role in the photooxidation of DOM, because they may oxidize the fraction of DOM that is inaccessible to direct photochemical degradation by sunlight. We followed the effects of photochemically produced singlet oxygen ((1)O(2)) on DOM by mass spectrometry with (18)O-labeled oxygen, to understand how (1)O(2)-mediated transformations of DOM may lead to altered DOM bioavailability. The photochemical oxygen uptake by DOM attributed to (1)O(2) increased with DOM concentration, yet it remained a minority contributor to photochemical oxygen uptake even at very high DOM concentrations. When DOM samples were exposed to (1)O(2)-generating conditions (Rose Bengal and visible light), increases were observed in DOM constituents with higher oxygen content and release of H(2)O(2) was detected. Differential effects of H(2)O(2) and (1)O(2)-treated DOM showed that (1)O(2)-treated DOM led to slower bacterial growth rates relative to unmodified DOM. Results of this study suggested that the net effect of the reactions between singlet oxygen and DOM may be production of partially oxidized substrates with correspondingly lower potential biological energy yield.

Molecular characterization of dissolved organic matter from subtropical wetlands: a comparative study through the analysis of optical properties, NMR and FTICR/MS

NASA Astrophysics Data System (ADS)

Hertkorn, Norbert; Harir, Mourad; Cawley, Kaelin M.; Schmitt-Kopplin, Philippe; Jaffé, Rudolf

2016-04-01

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

Whole-Body Vibration While Squatting and Delayed-Onset Muscle Soreness in Women.

PubMed

Dabbs, Nicole C; Black, Christopher D; Garner, John

2015-12-01

Research into alleviating muscle pain and symptoms in individuals after delayed-onset muscle soreness (DOMS) has been inconsistent and unsuccessful in demonstrating a useful recovery modality. To investigate the effects of short-term whole-body vibration (WBV) on DOMS over a 72-hour period after a high-intensity exercise protocol. Randomized controlled clinical trial. University laboratory. Thirty women volunteered to participate in 4 testing sessions and were assigned randomly to a WBV group (n = 16; age = 21.0 ± 1.9 years, height = 164.86 ± 6.73 cm, mass = 58.58 ± 9.32 kg) or a control group (n = 14; age = 22.00 ± 1.97 years, height = 166.65 ± 8.04 cm, mass = 58.69 ± 12.92 kg). Participants performed 4 sets to failure of single-legged split squats with 40% of their body weight to induce muscle soreness in the quadriceps. The WBV or control treatment was administered each day after DOMS. Unilateral pressure-pain threshold (PPT), range of motion (ROM), thigh circumference, and muscle-pain ratings of the quadriceps were collected before and for 3 days after high-intensity exercise. Each day, we collected 3 sets of measures, consisting of 1 measure before the WBV or control treatment protocol (pretreatment) and 2 sets of posttreatment measures. We observed no interactions for PPT, thigh circumference, and muscle pain (P > .05). An interaction was found for active ROM (P = .01), with the baseline pretreatment measure greater than the measures at baseline posttreatment 1 through 48 hours posttreatment 2 in the WBV group. For PPT, a main effect for time was revealed (P < .05), with the measure at baseline pretreatment greater than at 24 hours pretreatment and all other time points for the vastus medialis, greater than 24 hours pretreatment through 48 hours posttreatment 2 for the vastus lateralis, and greater than 24 hours pretreatment and 48 hours pretreatment for the rectus femoris. For dynamic muscle pain, we observed a main effect for time (P < .001), with the baseline pretreatment measure less than the measures at all other time points. No main effect for time was noted for thigh circumference (P = .24). No main effect for group was found for any variable (P > .05). The WBV treatment approach studied did not aid in alleviating DOMS after high-intensity exercise. Further research is needed in various populations.

Optical properties and bioavailability of dissolved organic matter along a flow-path continuum from soil pore waters to the Kolyma River, Siberia

NASA Astrophysics Data System (ADS)

Frey, K. E.; Sobczak, W. V.; Mann, P. J.; Holmes, R. M.

2015-08-01

The Kolyma River in Northeast Siberia is among the six largest arctic rivers and drains a region underlain by vast deposits of Holocene-aged peat and Pleistocene-aged loess known as yedoma, most of which is currently stored in ice-rich permafrost throughout the region. These peat and yedoma deposits are important sources of dissolved organic matter (DOM) to inland waters that in turn play a significant role in the transport and ultimate remineralization of organic carbon to CO2 and CH4 along the terrestrial flow-path continuum. The turnover and fate of terrigenous DOM during offshore transport will largely depend upon the composition and amount of carbon released to inland and coastal waters. Here, we measured the optical properties of chromophoric DOM (CDOM) from a geographically extensive collection of waters spanning soil pore waters, streams, rivers, and the Kolyma River mainstem throughout a ∼ 250 km transect of the northern Kolyma River basin. During the period of study, CDOM absorbance values were found to be robust proxies for the concentration of DOM, whereas additional CDOM parameters such as spectral slopes (S) were found to be useful indicators of DOM quality along the flow-path. In particular, CDOM absorption at 254 nm showed a strong relationship with dissolved organic carbon (DOC) concentrations across all water types (r2 = 0.958, p < 0.01). The spectral slope ratio (SR) of CDOM demonstrated statistically significant differences between all four water types and tracked changes in the concentration of bioavailable DOC, suggesting that this parameter may be suitable for clearly discriminating shifts in organic matter characteristics among water types along the full flow-path continuum across this landscape. The heterogeneity of environmental characteristics and extensive continuous permafrost of the Kolyma River basin combine to make this a critical region to investigate and monitor. With ongoing and future permafrost degradation, peat and yedoma deposits throughout the Northeast Siberian region will become more hydrologically active, providing greater amounts of DOM to fluvial networks and ultimately to the Arctic Ocean. The ability to rapidly and comprehensively monitor shifts in the quantity and quality of DOM across the landscape is therefore critical for understanding potential future feedbacks on the arctic carbon cycle.

Production and Reutilization of Fluorescent Dissolved Organic Matter by a Marine Bacterial Strain, Alteromonas macleodii

PubMed Central

Goto, Shuji; Tada, Yuya; Suzuki, Koji; Yamashita, Youhei

2017-01-01

The recalcitrant fraction of marine dissolved organic matter (DOM) plays an important role in carbon storage on the earth’s surface. Bacterial production of recalcitrant DOM (RDOM) has been proposed as a carbon sequestration process. It is still unclear whether bacterial physiology can affect RDOM production. In this study, we conducted a batch culture using the marine bacterial isolate Alteromonas macleodii, a ubiquitous gammaproteobacterium, to evaluate the linkage between bacterial growth and DOM production. Glucose (1 mmol C L-1) was used as the sole carbon source, and the bacterial number, the DOM concentration in terms of carbon, and the excitation–emission matrices (EEMs) of DOM were monitored during the 168-h incubation. The incubation period was partitioned into the exponential growth (0–24 h) and stationary phases (24–168 h) based on the growth curve. Although the DOM concentration decreased during the exponential growth phase due to glucose consumption, it remained stable during the stationary phase, corresponding to approximately 4% of the initial glucose in terms of carbon. Distinct fluorophores were not evident in the EEMs at the beginning of the incubation, but DOM produced by the strain exhibited five fluorescent peaks during exponential growth. Two fluorescent peaks were similar to protein-like fluorophores, while the others could be categorized as humic-like fluorophores. All fluorophores increased during the exponential growth phase. The tryptophan-like fluorophore decreased during the stationary phase, suggesting that the strain reused the large exopolymer. The tyrosine-like fluorophore seemed to be stable during the stationary phase, implying that the production of tyrosine-containing small peptides through the degradation of exopolymers was correlated with the reutilization of the tyrosine-like fluorophore. Two humic-like fluorophores that showed emission maxima at the longer wavelength (525 nm) increased during the stationary phase, while the other humic-like fluorophore, which had a shorter emission wavelength (400 nm) and was categorized as recalcitrant, was stable. These humic-like fluorophore behaviors during incubation indicated that the composition of bacterial humic-like fluorophores, which were unavailable to the strain, differed between growth phases. Our results suggest that bacterial physiology can affect RDOM production and accumulation in the ocean interior. PMID:28400762

Organic carbon and nitrogen export from a tropical dam-impacted floodplain system

NASA Astrophysics Data System (ADS)

Zurbrügg, R.; Suter, S.; Lehmann, M. F.; Wehrli, B.; Senn, D. B.

2013-01-01

Tropical floodplains play an important role in organic matter transport, storage, and transformation between headwaters and oceans. However, the fluxes and quality of organic carbon (OC) and organic nitrogen (ON) in tropical river-floodplain systems are not well constrained. We explored the quantity and characteristics of dissolved and particulate organic matter (DOM and POM, respectively) in the Kafue River flowing through the Kafue Flats (Zambia), a tropical river-floodplain system in the Zambezi River basin. During the flooding season, > 80% of the Kafue River water passed through the floodplain, mobilizing large quantities of OC and ON, which resulted in a net export of 69-119 kg OC km-2 d-1 and 3.8-4.7 kg ON km-2 d-1, 80% of which was in the dissolved form. The elemental C : N ratio of ~ 20, the comparatively high δ13C values of -25‰ to -21‰, and its spectroscopic properties (excitation-emission matrices) showed that DOM in the river was mainly of terrestrial origin. Despite a threefold increase in OC loads due to inputs from the floodplain, the characteristics of the riverine DOM remained relatively constant along the sampled 410-km river reach. This suggests that floodplain DOM displayed properties similar to those of DOM leaving the upstream reservoir and implied that the DOM produced in the reservoir was relatively short-lived. In contrast, the particulate fraction was 13C-depleted (-29‰) and had a C : N ratio of ~ 8, which indicated that POM originated from phytoplankton production in the reservoir and in the floodplain, rather than from plant debris or resuspended sediments. While the upstream dam had little effect on the DOM pool, terrestrial particles were retained, and POM from algal and microbial sources was released to the river. A nitrogen mass balance over the 2200 km2 flooded area revealed an annual deficit of 15 500-22 100 t N in the Kafue Flats. The N isotope budget suggests that these N losses are balanced by intense N-fixation. Our study shows that the Kafue Flats are a significant local source of OC and ON to downstream ecosystems and illustrates how the composition of riverine OM can be altered by dams and floodplains in tropical catchments.

Effect of dissolved organic matter source and character on microbial Hg methylation in Hg–S–DOM solutions

USGS Publications Warehouse

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

2013-01-01

Dissolved organic matter (DOM) is a key component of fate and transport models for most metals, including mercury (Hg). Utilizing a suite of diverse DOM isolates, we demonstrated that DOM character, in addition to concentration, influences inorganic Hg (Hg(II)i) bioavailability to Hg-methylating bacteria. Using a model Hg-methylating bacterium, Desulfovibrio desulfuricansND132, we evaluated Hg-DOM-sulfide bioavailability in washed-cell assays at environmentally relevant Hg/DOM ratios (∼1–8 ng Hg/mg C) and sulfide concentrations (1–1000 μM). All tested DOM isolates significantly enhanced Hg methylation above DOM-free controls (from ∼2 to >20-fold for 20 mg C/L DOM solutions), but high molecular weight/highly aromatic DOM isolates and/or those with high sulfur content were particularly effective at enhancing Hg methylation. Because these experiments were conducted under conditions of predicted supersaturation with respect to metacinnabar (β-HgS(s)), we attribute the DOM-dependent enhancement of Hg(II)i bioavailability to steric and specific chemical (e.g., DOM thiols) inhibition of β-HgS(s) growth and aggregation by DOM. Experiments examining the role of DOM across a wide sulfide gradient revealed that DOM only enhances Hg methylation under fairly low sulfide conditions (≲30 μM), conditions that favor HgS nanoparticle/cluster formation relative to dissolved HgS species.

PLA2G2A polymorphisms are associated with metabolic syndrome and type 2 diabetes mellitus. Results from the genetics of atherosclerotic disease Mexican study.

PubMed

Monroy-Muñoz, Irma Eloisa; Angeles-Martinez, Javier; Posadas-Sánchez, Rosalinda; Villarreal-Molina, Teresa; Alvarez-León, Edith; Flores-Dominguez, Carmina; Cardoso-Saldaña, Guillermo; Medina-Urrutia, Aida; Juárez-Rojas, Juan Gabriel; Posadas-Romero, Carlos; Alarcon, Gilberto Vargas

2017-10-01

The secretory phospholipase A 2 II A (sPLA 2 -IIA) encoded by PLA2G2A gene hydrolyzes phospholipids liberating free fatty acids (FFAs) and lysophospholipids. If lipolysis exceeds lipogenesis, the free fatty acids undergo a continuous release into circulation. A sustained excessive increase in this release contributes to metabolic disease. The aim of the present study was to evaluate the role of PLA2G2A gene polymorphisms as susceptibility markers for metabolic syndrome (MetS) and type 2 diabetes mellitus (T2DM) in Mexican population. Three PLA2G2A gene polymorphisms (rs876018, rs3753827 and rs11573156) were genotyped by 5' exonuclease TaqMan assays in a group of 338 patients with T2DM, 460 individuals with MetS and 366 healthy controls. Under codominant 1(codom1), dominant (dom) and additive (add) models adjusted by age, gender, body mass index (BMI), smoking habit, and hypertension, the rs876018T allele was associated with increased risk of MetS [Odds Ratio (OR)=1.66, P codom1 =0.005; OR=1.67, P dom =0.003; OR=1.49, P add =0.005] as compared to controls. On the other hand, under several models adjusted by the same variables, the rs3753827A (OR=1.52, P codom1 =0.039 and OR=1.49, P dom =0.039) and rs11573156C alleles (OR=6.46, P codom1 =0.013; OR=6.70, P codom2 =0.009; OR=6.65, P dom =0.009) were associated with increased risk of T2DM when compared with controls. In addition, the rs876018T allele was associated with hypercholesterolemia (P dom =0.017, P add =0.009) and risk of subclinical atherosclerosis (SA) (P dom =0.041) in MetS when compared with controls. Also, this allele was associated with SA in T2DM patients (P dom =0.007). The TAG haplotype was significantly associated with increased risk of MetS (OR=1.54, P=0.006). Results suggest that PLA2G2A polymorphisms are involved in the risk of developing MetS and T2D and are associated with SA in this group of patients. Copyright © 2016 Elsevier GmbH. All rights reserved.

Bacterial production and their role in the removal of dissolved organic matter from tributaries of drinking water reservoirs.

PubMed

Kamjunke, Norbert; Oosterwoud, Marieke R; Herzsprung, Peter; Tittel, Jörg

2016-04-01

Enhanced concentrations of dissolved organic matter (DOM) in freshwaters are an increasing problem in drinking water reservoirs. In this study we investigated bacterial DOM degradation rates in the tributaries of the reservoirs and tested the hypotheses that (1) DOM degradation is high enough to decrease DOM loads to reservoirs considerably, (2) DOM degradation is affected by stream hydrology, and (3) phosphorus addition may stimulate bacterial DOM degradation. Bacterial biomass production, which was used as a measure of DOM degradation, was highest in summer, and was usually lower at upstream than at downstream sites. An important proportion of bacterial production was realized in epilithic biofilms. Production of planktonic and biofilm bacteria was related to water temperature. Planktonic production weakly correlated to DOM quality and to total phosphorus concentration. Addition of soluble reactive phosphorus did not stimulate bacterial DOM degradation. Overall, DOM was considerably degraded in summer at low discharge levels, whereas degradation was negligible during flood events (when DOM load in reservoirs was high). The ratio of DOM degradation to total DOM release was negatively related to discharge. On annual average, only 0.6-12% of total DOM released by the catchments was degraded within the tributaries. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of dissolved organic matter on sorption and desorption of MCPA in ferralsol.

PubMed

Wu, Dongming; Yun, Yonghuan; Jiang, Lei; Wu, Chunyuan

2018-03-01

MCPA (4-chloro-2-methylphenoxyacetic acid) is an acidic herbicide, widely used in paddy fields. The presence of dissolved organic matter (DOM) modifies the sorption-desorption of herbicides in soils. In this study, effects of DOM on sorption- desorption of MCPA were tested using three typical ferralsol soil types from China: rhodic ferralsol, haplic ferralsol and paddy soil. DOM preparations were extracted from the paddy soil (DOM P ), from a compost mixture of cassava stems with chicken manure (DOM C ), and from rice straw (DOM R ). Sorption-desorption of MCPA in the tested soil types was shown to follow pseudo first-order kinetics, and the calculated isotherm data fitted well with a Freundlich equilibrium model in the range of the studied concentrations. MCPA was weakly sorbed by the soils, producing low Freundlich coefficient values (K f ) (0.854 to 4.237). The presence of DOM reduced the K f whereby DOM C had the strongest and DOM R the weakest effect. Presence of DOM also promoted MCPA desorption from the soils, again with DOM C having the strongest effect and DOM R the weakest. DOM coating changed the soil particle surface, as demonstrated by electron microscopy, and DOM also directly interacted with MCPA, as shown by Fourier-transform infrared spectroscopy. The experimental data were interpreted to suggest a competing sorption of DOM to ferralsol and an increased solubility of MCPA in the presence of DOM. The results indicate that the environmental risk of MCPA leaching to groundwater and surface flow is increased by presence of DOM, for instance as a result of organic fertilizer use. Copyright © 2017. Published by Elsevier B.V.

Exoenzyme activities as indicators of dissolved organic matter composition in the hyporheic zone of a floodplain river

Treesearch

Sandra M. Clinton; Rick T. Edwards; Stuart E.G. Findlay

2010-01-01

We measured the hyporheic microbial exoenzyme activities in a floodplain river to determine whether dissolved organic matter (DOM) bioavailability varied with overlying riparian vegetation patch structure or position along flowpaths. Particulate organic matter (POM), dissolved organic carbon (DOC), dissolved oxygen (DO), electrical conductivity and temperature were...

Feed intake and production parameters of lactating crossbred cows fed maize-based diets of stover, silage or quality protein silage.

PubMed

Gebrehawariat, Efrem; Tamir, Berhan; Tegegne, Azage

2010-12-01

Thirty-six Boran × Friesian dairy cows (392 ± 12 kg; mean ± SD) in early parity were used in a randomised complete block design. Cows were blocked by parity into three blocks of 12 animals and offered normal maize (NM) stover (T1), NM silage (T2) or quality protein maize (QPM) silage (T3) basal diets supplemented with a similar concentrate mix. Feed intake, body weight and condition changes and milk yield and composition were assessed. The daily intake of DM, OM, NDF and ADF for cows fed the NM stover-based diet was higher (P<0.05) than for the cows fed the NM silage and QPM silage-based diets. However, the daily intake of DOM (9.3 kg) and ME (140.8 MJ) for cows on QPM silage-based diet was higher (P<0.05) than for cows on NM stover-based diet (8.4 kg and 124.2 MJ) and NM silage-based diet (7.9 kg and 119.1 MJ). Body weight of cows was affected (P<0.05) by the diet, but diet had no effect (P>0.05) on body condition score, milk yield and milk composition. The digestible organic matter in the NM stover-based diet (724 g/kg DM) was lower (P<0.05) than that in the NM (770 g/kg DM) and QPM silage-based diet (762 g/kg DM). It was concluded that the performances of the cows on the NM silage and QPM silage diets were similar and were not superior to that of the NM stover-based diet.

Feed intake and production parameters of lactating crossbred cows fed maize-based diets of stover, silage or quality protein silage

PubMed Central

Gebrehawariat, Efrem; Tegegne, Azage

2010-01-01

Thirty-six Boran × Friesian dairy cows (392 ± 12 kg; mean ± SD) in early parity were used in a randomised complete block design. Cows were blocked by parity into three blocks of 12 animals and offered normal maize (NM) stover (T1), NM silage (T2) or quality protein maize (QPM) silage (T3) basal diets supplemented with a similar concentrate mix. Feed intake, body weight and condition changes and milk yield and composition were assessed. The daily intake of DM, OM, NDF and ADF for cows fed the NM stover-based diet was higher (P < 0.05) than for the cows fed the NM silage and QPM silage-based diets. However, the daily intake of DOM (9.3 kg) and ME (140.8 MJ) for cows on QPM silage-based diet was higher (P < 0.05) than for cows on NM stover-based diet (8.4 kg and 124.2 MJ) and NM silage-based diet (7.9 kg and 119.1 MJ). Body weight of cows was affected (P < 0.05) by the diet, but diet had no effect (P > 0.05) on body condition score, milk yield and milk composition. The digestible organic matter in the NM stover-based diet (724 g/kg DM) was lower (P < 0.05) than that in the NM (770 g/kg DM) and QPM silage-based diet (762 g/kg DM). It was concluded that the performances of the cows on the NM silage and QPM silage diets were similar and were not superior to that of the NM stover-based diet. PMID:20577806

Impacts of biochar addition on soil dissolved organic matter characteristics in a wheat-maize rotation system in Loess Plateau of China.

PubMed

Zhang, Afeng; Zhou, Xu; Li, Ming; Wu, Haiming

2017-11-01

Biochar amendment in soil has the potential to sequester carbon, improve soil quality and mitigate greenhouse gas (GHG) emission in agriculture, but the impact of biochar amendments on dissolved organic matter (DOM) properties of soils in the fertilized agro-ecosystem has received little research attention. This study performed a long-term field experiment to assess the influence of biochar amendments (different addition rate: 4 t ha -1 and 8 t ha -1 ) on DOM characteristics in soils in wheat-maize rotation system in Loess Plateau of China by exploiting fluorescence excitation-emission spectrophotometry and parallel factor analysis (EEM-PARAFAC). Our results showed that the content of soil DOM was significantly influenced by the addition of biochar, and the higher biochar addition markedly increased the mean concentration of dissolved organic carbon (DOC) (from 83.99 mg kg -1 to 144.27 mg kg -1 ) in soils under the same fertilizer application. Three identified fluorescent components (fulvic acid-like, humic acid-like and tryptophan-like) were found, and fluorescence intensity of those components (especially humic-like material) was enhanced with the increasing DOC in the biochar treatments but the composition of DOM was not changed. These findings would be beneficial to understand the biochar's effects and processes in decreasing GHG emissions from soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of Tillandsia usneoides (Spanish moss) water and leachate dynamics between urban and pristine barrier island maritime oak forests

NASA Astrophysics Data System (ADS)

Van Stan, J. T.; Stubbins, A.; Reichard, J. S.; Wright, K.; Jenkins, R. B.

2013-12-01

Epiphyte coverage on forest canopies can drastically alter the volume and chemical composition of rainwater reaching soils. Along subtropical and tropical coastlines Tillandisa usneoides L. (Spanish moss), in particular, can envelop urban and natural tree crowns. Several cities actively manage their 'moss' covered forest to enhance aesthetics in the most active tourist areas (e.g., Savannah GA, St. Augustine FL, Charleston SC). Since T. usneoides survives through atmospheric water and solute exchange from specialized trichomes (scales), we hypothesized that T. usneoides water storage dynamics and leachate chemistry may be altered by exposure to this active urban atmosphere. 30 samples of T. usneoides from managed forests around the tourist center of Savannah, Georgia, USA were collected to compare with 30 samples from the pristine maritime live oak (Quercus virginiana Mill.) forests of a nearby undeveloped barrier island (St. Catherines Island, Georgia, USA). Maximum water storage capacities were determined via submersion (for all 60 samples) along with dissolved ion (DI) and organic matter (DOM) concentrations (for 15 samples each) after simulated throughfall generation using milliQ ultrapurified water. Further, DOM quality was evaluated (for 15 samples each) using absorbance and fluorescence spectroscopy (EEMS). Results show significant alterations to water storage dynamics, DI, DOM, and DOM quality metrics under urban atmospheric conditions, suggesting modified C and water cycling in urban forest canopies that may, in turn, influence intrasystem nutrient cycles in urban catchment soils or streams via runoff.

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.

The nature of colored dissolved organic matter in the southern Canada Basin and East Siberian Sea

NASA Astrophysics Data System (ADS)

Guéguen, C.; McLaughlin, F. A.; Carmack, E. C.; Itoh, M.; Narita, H.; Nishino, S.

2012-12-01

Distributions of colored dissolved organic matter (CDOM) in the upper 400 m of the southern Canada Basin and East Siberian Sea were determined using an in situ WETStar fluorometer and fluorescence spectroscopy during cruises in 2008 as part of the Canada/US Joint Ocean Ice Study and Japan's International Polar Year program. Despite the low CDOM range (0.009-0.069 r.u.) observed in the upper 400 m of the study area, our results show that CDOM can be quantified from in situ DOM fluorescence sensor measurements. Unlike DOC concentrations, which are known to decrease with increasing depth, a pronounced mid-depth CDOM maximum was associated with the Pacific-derived winter water throughout our study area. Using parallel factor analysis (PARAFAC) to resolve dominant fluorophore components in fluorescence excitation-emission matrices (EEM), we identified three humic-like and two proteinaceous components. The nature and origin of these five fluorophores were investigated based on their fluorescent characteristics as well as their vertical and geographical distributions. The lowest terrestrial humic-like signals in the surface waters were mostly due to photochemical processes, whereas the highest microbial/marine humic-like signal revealed interactions with sediment during the formation of Pacific-origin haloclines over the Arctic shelves. The humic-like fluorophores dominated DOM fluorescence in the Westernmost region in the East Siberian Sea whereas the contribution of protein-like fluorophores was predominant elsewhere. The significant difference in CDOM composition between East and West of the 180° meridian suggests the presence of a front that divides our study area into the Eastern Chukchi—Beaufort and East Siberian sides. This indicates a change in water circulation, and that more than one DOM source affects our study area. Unlike proteinaceous material, the humic-like compounds varied significantly in the halocline. Ten to 20 percent enrichment was observed in terrestrially-derived DOM in the two Pacific-derived haloclines relative to the Atlantic-derived lower halocline. The application of PARAFAC modeling on fluorescent DOM is shown to be an important tool to investigate the dynamics and transport of allochthonous DOM in the Arctic Ocean.

Characterizing Low Molecular Weight Organic Matter in Arctic Polygonal Tundra Soils to Identify Biogeochemical Hotspots Using a Dual-Separation, High-Resolution Mass Spectrometry Approach

NASA Astrophysics Data System (ADS)

Ladd, M.; Wullschleger, S. D.; Iversen, C. M.; Hettich, R.

2016-12-01

Reliably modeling biogeochemical processes (e.g. decomposition, plant-microbial competition for nutrients) across spatial or temporal scales requires elucidating the chemical composition of low molecular weight (LMW) dissolved soil organic matter (DOM). Our understanding is limited, however, by the wide-ranging physicochemical properties and high fluxes of these compounds, posing major challenges in detection, isolation, and quantification. Here, we developed and evaluated a sensitive, non-targeted approach to characterize LMW DOM in the Arctic, a unique system that is warming at a rate twice that of the global average and may have significant feedbacks to global C and N cycles. Soil cores were collected from a continuous permafrost, polygonal tundra landscape near Barrow, Alaska (71° 16' N) and sectioned into 5 cm increments. Water and salt extracts from each section were filtered and injected onto C18 reversed-phase or zwitterionic-type hydrophilic interaction chromatography (ZIC-pHILIC) columns for separation. LMW DOM profiles were obtained using high-resolution mass spectrometry (HRMS), and unique features, known and unknown, were characterized by LC retention time, accurate mass (m/z), and molecular fragmentation pattern. Coupling two orthogonal chromatographic separations with HRMS enabled the characterization of hundreds of analytes in a single measurement providing enhanced, high-throughput coverage of LMW DOM from soil extracts. The complexity and relative/absolute intensities of LMW DOM features (e.g. organic acids, amino sugars, peptides) varied across polygon type (high- or low-centered), extract condition, and with depth, providing an information-rich, molecular signal of LMW DOM availability across scales. Comprehensively profiling this complex mixture of small molecules of both biotic and abiotic origin provides a chemical signature of biological function, allowing for more reliable predictions of how discrete, molecular-scale processes may control landscape dynamics. In the Arctic, this platform can be leveraged to identify biogeochemical hotspots to gain insight into to how warming temperatures will impact microbial dynamics and CO2 and CH4 fluxes from these systems.

Changes in the quality of chromophoric dissolved organic matter leached from senescent leaf litter during the early decomposition.

PubMed

Nishimura, Satoshi; Maie, Nagamitsu; Baba, Mitsuhisa; Sudo, Takahiro; Sugiura, Toshihiro; Shima, Eikichi

2012-01-01

Chromophoric dissolved organic matter (CDOM) leached from leaf litter is a major source of humus in mineral soil of forest ecosystems. While their functions and refractoriness depend on the physicochemical structure, there is little information on the quality of CDOM, especially for that leached in the very early stages of litter decomposition when a large amount of dissolved organic matter (DOM) is leached. This study aimed to better understand the variations/changes in the composition of CDOM leached from senescent leaf litter from two tree species during the early stage of decomposition. Leaf litter from a conifer tree (Japanese cedar, D. Don) and a deciduous broad-leaved tree (Konara oak, Thunb.) were incubated in columns using simulated rainfall events periodically for a total of 300 d at 20°C. The quality of CDOM was investigated based on the fluorescence properties by using a combination of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC). In addition, the phenolic composition of DOM was investigated at a molecular level by thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH). The EEM was statistically decomposed into eight fluorescence components (two tannin/peptide-like peaks, one protein-like peak, and five humic-like peaks). A significant contribution of tannin/peptide-like peaks was observed at the beginning of incubation, but these peaks decreased quickly and humic-like peaks increased within 1 mo of incubation. The composition of humic-like peaks was different between tree species and changed over the incubation period. Since tannin-derived phenolic compounds were detected in the DOM collected after 254 d of incubation on THM-GC-MS, it was suggested that tannins partially changed its structure, forming various humic-like peaks during the early decomposition. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

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 pooled then treated separately and the influence of preceding periods was tested. This hydrological division of time allowed us to identify climate effect on the topsoil DOM stores of the wetland and hillslope separately. Meteorological and hydro-pedological variables, like soil temperatures or duration of the water saturation in the organo-mineral horizons have been used to interpret the DOC concentrations and fluxes at the outlet within each period. The three hydrological periods contribute respectively to less than 17%, more than 63%, and less than 26% of the annual DOM exportation with flow weighted mean concentration of DOC of 9.5, 6.1, and 3.8 mg.L-1. Considering several DOM sources with different properties of depletion under climatic control, the main output of the work is to provide a modified conceptual model of the DOC dynamics.

Measurement of dissolved organic matter fluorescense in aquatic environments: An interlaboratory comparison

USGS Publications Warehouse

Murphy, Kathleen R.; Butler, Kenna D.; Spencer, Robert G. M.; Stedmon, Colin A.; Boehme, Jennifer R.; Aiken, George R.

2010-01-01

The fluorescent properties of dissolved organic matter (DOM) are often studied in order to infer DOM characteristics in aquatic environments, including source, quantity, composition, and behavior. While a potentially powerful technique, a single widely implemented standard method for correcting and presenting fluorescence measurements is lacking, leading to difficulties when comparing data collected by different research groups. This paper reports on a large-scale interlaboratory comparison in which natural samples and well-characterized fluorophores were analyzed in 20 laboratories in the U.S., Europe, and Australia. Shortcomings were evident in several areas, including data quality-assurance, the accuracy of spectral correction factors used to correct EEMs, and the treatment of optically dense samples. Data corrected by participants according to individual laboratory procedures were more variable than when corrected under a standard protocol. Wavelength dependency in measurement precision and accuracy were observed within and between instruments, even in corrected data. In an effort to reduce future occurrences of similar problems, algorithms for correcting and calibrating EEMs are described in detail, and MATLAB scripts for implementing the study's protocol are provided. Combined with the recent expansion of spectral fluorescence standards, this approach will serve to increase the intercomparability of DOM fluorescence studies.

Satellite-Derived Distributions, Inventories and Fluxes of Dissolved and Particulate Organic Matter Along the Northeastern U.S. Continental Margin

NASA Technical Reports Server (NTRS)

Mannino, A.; Hooker, S. B.; Hyde, K.; Novak, M. G.; Pan, X.; Friedrichs, M.; Cahill, B.; Wilkin, J.

2011-01-01

Estuaries and the coastal ocean experience a high degree of variability in the composition and concentration of particulate and dissolved organic matter (DOM) as a consequence of riverine and estuarine fluxes of terrigenous DOM, sediments, detritus and nutrients into coastal waters and associated phytoplankton blooms. Our approach integrates biogeochemical measurements, optical properties and remote sensing to examine the distributions and inventories of organic carbon in the U.S. Middle Atlantic Bight and Gulf of Maine. Algorithms developed to retrieve colored DOM (CDOM), Dissolved (DOC) and Particulate Organic Carbon (POC) from NASA's MODIS-Aqua and SeaWiFS satellite sensors are applied to quantify the distributions and inventories of DOC and POC. Horizontal fluxes of DOC and POC from the continental margin to the open ocean are estimated from SeaWiFS and MODIS-Aqua distributions of DOC and POC and horizontal divergence fluxes obtained from the Northeastern North Atlantic ROMS model. SeaWiFS and MODIS imagery reveal the importance of estuarine outflow to the export of CDOM and DOC to the coastal ocean and a net community production of DOC on the shelf.

Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids

USGS Publications Warehouse

Aiken, George R.; Hsu-Kim, Heileen; Ryan, Joseph N.

2011-01-01

We have known for decades that dissolved organic matter (DOM) plays a critical role in the biogeochemical cycling of trace metals and the mobility of colloidal particles in aquatic environments. In recent years, concerns about the ecological and human health effects of metal-based engineered nanoparticles released into natural waters have increased efforts to better define the nature of DOM interactions with metals and surfaces. Nanomaterials exhibit unique properties and enhanced reactivities that are not apparent in larger materials of the same composition1,2 or dissolved ions of metals that comprise the nanoparticles. These nanoparticle-specific properties generally result from the relatively large proportion of the atoms located at the surface, which leads to very high specific surface areas and a high proportion of crystal lattice imperfections relative to exposed surface area. Nanoscale colloids are ubiquitous in nature,2 and many engineered nanomaterials have analogs in the natural world. The properties of these materials, whether natural or manmade, are poorly understood, and new challenges have been presented in assessing their environmental fate. These challenges are particularly relevant in aquatic environments where interactions with DOM are key, albeit often overlooked, moderators of reactivity at the molecular and nanocolloidal scales.

Complexation of Arsenite with Humic Acid in the Presence of Ferric Iron

PubMed Central

Liu, Guangliang; Fernandez, Aymara; Cai, Yong

2011-01-01

In the presence of iron (Fe), dissolved organic matter (DOM) may bind considerable amounts of arsenic (As), through formation of Fe-bridged As-Fe-DOM complexes and surface complexation of As on DOM-stabilized Fe-colloids (collectively referred to as As-Fe-DOM complexation). However, direct (e.g., chromatographic and spectroscopic) evidence and fundamental kinetic and stability constants have been rarely reported for this As-Fe-DOM complexation. Using a size exclusion chromatography (SEC)-UV-inductively coupled plasma mass spectrometry (ICP-MS) technique, arsenite (AsIII)-Fe-DOM complexation was investigated after adding AsIII into the priorly prepared Fe-DOM. A series of evidence, including coelution of As, Fe, and DOM from the SEC column and coretention of As, Fe, and DOM by 3 kDa MWCO centrifugal filtration membrane, demonstrated the occurrence of AsIII-Fe-DOM complexation. The kinetic data of AsIII-Fe-DOM complexation were well described by a pseudo-first order rate equation (R2 = 0.95), with the rate constant (k′) being 0.17±0.04 1/h. Stability of AsIII-Fe-DOM complexation was characterized by apparent stability constant (Ks) derived from two-site ligand binding model, with log Ks ranging from 4.4±0.2 to 5.6±0.4. Considering the kinetics (within hours) and stability (similar to typical metal-humates) of AsIII-Fe-DOM complexation, this complexation needs to be included when evaluating As mobility in Fe and DOM rich environments. PMID:21322632

Contrasting Effects of Dissolved Organic Matter on Mercury Methylation by Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132.

PubMed

Zhao, Linduo; Chen, Hongmei; Lu, Xia; Lin, Hui; Christensen, Geoff A; Pierce, Eric M; Gu, Baohua

2017-09-19

Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. In this study, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under nonsulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hg via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. These strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting microbial Hg uptake and methylation. Additionally, DOM and glutathione greatly decreased Hg sorption by G. sulfurreducens PCA but showed little effect on D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. These observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.

Removal of triazine-based pollutants from water by carbon nanotubes: Impact of dissolved organic matter (DOM) and solution chemistry.

PubMed

Engel, Maya; Chefetz, Benny

2016-12-01

Adsorption of organic pollutants by carbon nanotubes (CNTs) in the environment or removal of pollutants during water purification require deep understanding of the impacts of the presence of dissolved organic matter (DOM). DOM is an integral part of environmental systems and plays a key role affecting the behavior of organic pollutants. In this study, the effects of solution chemistry (pH and ionic strength) and the presence of DOM on the removal of atrazine and lamotrigine by single-walled CNTs (SWCNTs) was investigated. The solubility of atrazine slightly decreased (∼5%) in the presence of DOM, whereas that of lamotrigine was significantly enhanced (by up to ∼70%). Simultaneous introduction of DOM and pollutant resulted in suppression of removal of both atrazine and lamotrigine, which was attributed to DOM-pollutant competition or blockage of adsorption sites by DOM. However the decrease in removal of lamotrigine was also a result of its complexation with DOM. Pre-introduction of DOM significantly reduced pollutant adsorption by the SWCNTs, whereas introduction of DOM after the pollutant resulted in the release of adsorbed atrazine and lamotrigine from the SWCNTs. These data imply that DOM exhibits higher affinity for the adsorption sites than the triazine-based pollutants. In the absence of DOM atrazine was a more effective competitor than lamotrigine for adsorption sites in SWCNTs. However, competition between pollutants in the presence of DOM revealed lamotrigine as the better competitor. Our findings help unravel the complex DOM-organic pollutant-CNT system and will aid in CNT-implementation in water-purification technologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tribological and structural properties of titanium nitride and titanium aluminum nitride coatings deposited with modulated pulsed power magnetron sputtering

NASA Astrophysics Data System (ADS)

Ward, Logan

The demand for economical high-performance materials has brought attention to the development of advanced coatings. Recent advances in high power magnetron sputtering (HPPMS) have shown to improve tribological properties of coatings. These coatings offer increased wear and oxidation resistance, which may facilitate the use of more economical materials in harsh applications. This study demonstrates the use of novel forms of HPPMS, namely modulated pulsed-power magnetron sputtering (MPPMS) and deep oscillation magnetron sputtering (DOMS), for depositing TiN and Ti1-xAlxN tribological coatings on commonly used alloys, such as Ti-6Al-4V and Inconel 718. Both technologies have been shown to offer unique plasma characteristics in the physical vapor deposition (PVD) process. High power pulses lead to a high degree of ionization compared to traditional direct-current magnetron sputtering (DCMS) and pulsed magnetron sputtering (PMS). Such a high degree of ionization was previously only achievable by cathodic arc deposition (CAD); however, CAD can lead to increased macroparticles that are unfavorable in high friction and corrosive environments. MPPMS, DOMS, and other HPPMS techniques offer unique plasma characteristics and have been shown to produce coatings with refined grain structure, improved density, hardness, adhesion, and wear resistance. Using DOMS and MPPMS, TiN and Ti1-xAlxN coatings were deposited using PMS to compare microstructures and tribological performance. For Ti1-xAlxN, two sputtering target compositions, Ti 0.5Al0.5 and Ti0.3Al0.7, were used to evaluate the effects of MPPMS on the coating's composition and tribological properties. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) were used to characterize microstructure and crystallographic texture. Several tribological properties were evaluated including: wear rate, coefficient of friction, adhesion, and nanohardness. Results show that substrate material can have a significant effect on adhesion and the mechanical response between the coating and substrate. Depending on deposition parameters and the selected material MPPMS and DOMS are promising alternatives to DCMS, PMS, and CAD.

A statistic-thermodynamic model for the DOM degradation in the estuary

NASA Astrophysics Data System (ADS)

Zheng, Quanan; Chen, Qin; Zhao, Haihong; Shi, Jiuxin; Cao, Yong; Wang, Dan

2008-03-01

This study aims to clarify the role of dissolved salts playing in the degradation process of terrestrial dissolved organic matter (DOM) at a scale of molecular movement. The molecular thermal movement is perpetual motion. In a multi-molecular system, this random motion also causes collision between the molecules. Seawater is a multi-molecular system consisting from water, salt, and terrestrial DOM molecules. This study attributes the DOM degradation in the estuary to the inelastic collision of DOM molecule with charged salt ions. From statistic-thermodynamic theories of molecular collision, the DOM degradation model and the DOM distribution model are derived. The models are validated by the field observations and satellite data. Thus, we conclude that the inelastic collision between the terrestrial DOM molecules and dissolved salt ions in seawater is a decisive dynamic mechanism for rapid loss of terrestrial DOM.

Is browning a trigger for dominance of harmful cyanobacteria species in lakes?

NASA Astrophysics Data System (ADS)

Freeman, E. C.; Creed, I. F.

2017-12-01

"Browning" is the increase of dissolved organic matter (DOM) loads into aquatic ecosystems. It is typified by an increase in the color of surface waters as well as an increase in iron (Fe) concentrations. Browning, has been observed in boreal and temperate lakes of the northern hemisphere. This phenomena has implications for freshwater ecosystems by shifting microbial community compositions, influencing the nutritional quality of autotrophs in terms of their stoichiometry, fatty acid composition, toxin production, and methylmercury concentration, and therefore, contaminant transfer through the anabolic food web. We hypothesize that browning of lake waters will increase the dominance of particular species of cyanobacteria with adaptations to lower light, mixotrophic tendencies, and specialized Fe-uptake mechanisms. Here, we present results from a high resolution real-time monitoring campaign of an Ontario lake during the growing season where the toxin-producing cyanobacteria Plantothrix Isothrix is the dominant species. We observe the changes in phytoplankton composition, Fe concentrations, and DOM. These observations are paired with a series of controlled in-lake bottle bioassay experiments that test the role of Fe in controlling the growth of Planktothix Isothrix. In a three-way factorial design, with additions of the macronutrients phosphorus and nitrogen, we explore the effects of Fe removal and addition on the phytoplankton community composition. Understanding the interaction between the effects of browning and toxin-producing phytoplankton gives insight into the dominance of cyanobacteria in a browner world, and the potential risks to aquatic ecosystems and the services they provide.

Atrazine removal from water by polycation-clay composites: effect of dissolved organic matter and comparison to activated carbon.

PubMed

Zadaka, Dikla; Nir, Shlomo; Radian, Adi; Mishael, Yael G

2009-02-01

Atrazine removal from water by two polycations pre-adsorbed on montmorillonite was studied. Batch experiments demonstrated that the most suitable composite poly (4-vinylpyridine-co-styrene)-montmorillonite (PVP-co-S90%-mont.) removed 90-99% of atrazine (0.5-28 ppm) within 20-40 min at 0.367% w/w. Calculations employing Langmuir's equation could simulate and predict the kinetics and final extents of atrazine adsorption. Column filter experiments (columns 20x1.6 cm) which included 2g of the PVP-co-S90%-mont. composite mixed with excess sand removed 93-96% of atrazine (800 ppb) for the first 800 pore volumes, whereas the same amount of granular activated carbon (GAC) removed 83-75%. In the presence of dissolved organic matter (DOM; 3.7 ppm) the efficiency of the GAC filter to remove atrazine decreased significantly (68-52% removal), whereas the corresponding efficiency of the PVP-co-S90%-mont. filter was only slightly influenced by DOM. At lower atrazine concentration (7 ppb) the PVP-co-S90%-mont. filter reduced even after 3000 pore volumes the emerging atrazine concentration below 3 ppb (USEPA standard). In the case of the GAC filter the emerging atrazine concentration was between 2.4 and 5.3 microg/L even for the first 100 pore volumes. Thus, the PVP-co-S90%-mont. composite is a new efficient material for the removal of atrazine from water.

Tracking the evolution of stream DOM source during storm events using end member mixing analysis based on DOM quality

NASA Astrophysics Data System (ADS)

Yang, Liyang; Chang, Soon-Woong; Shin, Hyun-Sang; Hur, Jin

2015-04-01

The source of river dissolved organic matter (DOM) during storm events has not been well constrained, which is critical in determining the quality and reactivity of DOM. This study assessed temporal changes in the contributions of four end members (weeds, leaf litter, soil, and groundwater), which exist in a small forested watershed (the Ehwa Brook, South Korea), to the stream DOM during two storm events, using end member mixing analysis (EMMA) based on spectroscopic properties of DOM. The instantaneous export fluxes of dissolved organic carbon (DOC), chromophoric DOM (CDOM), and fluorescent components were all enhanced during peak flows. The DOC concentration increased with the flow rate, while CDOM and humic-like fluorescent components were diluted around the peak flows. Leaf litter was dominant for the DOM source in event 2 with a higher rainfall, although there were temporal variations in the contributions of the four end members to the stream DOM for both events. The contribution of leaf litter peaked while that of deeper soils decreased to minima at peak flows. Our results demonstrated that EMMA based on DOM properties could be used to trace the DOM source, which is of fundamental importance for understanding the factors responsible for river DOM dynamics during storm events.

Contrasting Effects of Dissolved Organic Matter on Mercury Methylation by G. sulfurreducens PCA and D. desulfuricans ND132

DOE PAGES

Zhao, Linduo; Chen, Hongmei; Lu, Xia; ...

2017-08-14

Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial Hg methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. Here, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under non-sulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hgmore » via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. Furthermore, these strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting cell Hg uptake and methylation. Additionally, DOM and glutathione decreased Hg sorption by G. sulfurreducens PCA, but not by D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. Finally, these observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.« less

Pre-treatments, characteristics, and biogeochemical dynamics of dissolved organic matter in sediments: A review.

PubMed

Chen, Meilian; Hur, Jin

2015-08-01

Dissolved organic matter (DOM) in sediments, termed here sediment DOM, plays a variety of important roles in global biogeochemical cycling of carbon and nutrients as well as in the fate and transport of xenobiotics. Here we reviewed sediment DOM, including pore waters and water extractable organic matter from inland and coastal sediments, based on recent literature (from 1996 to 2014). Sampling, pre-treatment, and characterization methods for sediment DOM were summarized. The characteristics of sediment DOM have been compared along an inland to coastal ecosystems gradient and also with the overlying DOM in water column to distinguish the unique nature of it. Dissolved organic carbon (DOC) from inland sediment DOM was generally higher than coastal areas, while no notable differences were found for their aromaticity and apparent molecular weight. Fluorescence index (FI) revealed that mixed sources are dominant for inland sediment DOM, but marine end-member prevails for coastal sediment DOM. Many reports showed that sediments operate as a net source of DOC and chromophoric DOM (CDOM) to the water column. Sediment DOM has shown more enrichment of nitrogen- and sulfur-containing compounds in the elemental signature than the overlying DOM. Fluorescent fingerprint investigated by excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) further demonstrated the characteristics of sediment DOM lacking in the photo-oxidized and the intermediate components, which are typically present in the overlying surface water. In addition, the biogeochemical changes in sediment DOM and the subsequent environmental implications were discussed with the focus on the binding and the complexation properties with pollutants. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhanced Production of Bioethanol by Fermentation of Autohydrolyzed and C4mimOAc-Treated Sugarcane Bagasse Employing Various Yeast Strains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hashmi, Muzna; Shah, Aamer; Hameed, Abdul

Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial Hg methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. Here, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under non-sulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hgmore » via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. These strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting cell Hg uptake and methylation. Additionally, DOM and glutathione decreased Hg sorption by G. sulfurreducens PCA, but not by D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. Our observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.« less

Enhanced Production of Bioethanol by Fermentation of Autohydrolyzed and C4mimOAc-Treated Sugarcane Bagasse Employing Various Yeast Strains

DOE PAGES

Hashmi, Muzna; Shah, Aamer; Hameed, Abdul; ...

2017-08-01

Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial Hg methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. Here, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under non-sulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hgmore » via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. These strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting cell Hg uptake and methylation. Additionally, DOM and glutathione decreased Hg sorption by G. sulfurreducens PCA, but not by D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. Our observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.« less

Contrasting Effects of Dissolved Organic Matter on Mercury Methylation by G. sulfurreducens PCA and D. desulfuricans ND132

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Linduo; Chen, Hongmei; Lu, Xia

Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial Hg methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. Here, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under non-sulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hgmore » via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. Furthermore, these strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting cell Hg uptake and methylation. Additionally, DOM and glutathione decreased Hg sorption by G. sulfurreducens PCA, but not by D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. Finally, these observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.« less

Changes in dissolved organic matter quality in a peatland and forest headwater stream as a function of seasonality and hydrologic conditions

NASA Astrophysics Data System (ADS)

Broder, Tanja; Knorr, Klaus-Holger; Biester, Harald

2017-04-01

Peatlands and peaty riparian zones are major sources of dissolved organic matter (DOM), but are poorly understood in terms of export dynamics and controls thereof. Thereby quality of DOM affects function and behavior of DOM in aquatic ecosystems, but DOM quality can also help to track DOM sources and their export dynamics under specific hydrologic preconditions. The objective of this study was to elucidate controls on temporal variability in DOM concentration and quality in stream water draining a bog and a forested peaty riparian zone, particularly considering drought and storm flow events. DOM quality was monitored using spectrofluorometric indices for aromaticity (SUVA254), apparent molecular size (SR) and precursor organic material (FI), as well as PARAFAC modeling of excitation emission matrices (EEMs). Indices for DOM quality exhibited major changes due to different hydrologic conditions, but patterns were also dependent on season. Stream water at the forested site with mineral, peaty soils generally exhibited higher variability in DOM concentrations and quality compared to the outflow of an ombrotrophic bog, where DOM was less susceptible to changes in hydrologic conditions. During snowmelt and spring events, near-surface protein-like DOM pools were exported. A microbial DOM fraction originating from groundwater and deep peat layers was increasing during drought, while a strongly microbially altered DOM fraction was also exported by discharge events with dry preconditions at the forested site. This might be due to accelerated microbial activity in the peaty riparian zone of the forested site under these preconditions. Our study demonstrated that DOM export dynamics are not only a passive mixing of different hydrological sources, but monitoring studies have to consider that DOM quality depends on hydrologic preconditions and season. Moreover, the forested peaty riparian zone generated the most variability in headwater DOM quantity and quality, as could be tracked by the used spectrofluorometric indices.

Ordered nanoporous silica as carriers for improved delivery of water insoluble drugs: a comparative study between three dimensional and two dimensional macroporous silica

PubMed Central

Wang, Ying; Zhao, Qinfu; Hu, Yanchen; Sun, Lizhang; Bai, Ling; Jiang, Tongying; Wang, Siling

2013-01-01

The goal of the present study was to compare the drug release properties and stability of the nanoporous silica with different pore architectures as a matrix for improved delivery of poorly soluble drugs. For this purpose, three dimensional ordered macroporous (3DOM) silica with 3D continuous and interconnected macropores of different sizes (200 nm and 500 nm) and classic mesoporous silica (ie, Mobil Composition of Matter [MCM]-41 and Santa Barbara Amorphous [SBA]-15) with well-ordered two dimensional (2D) cylindrical mesopores were successfully fabricated and then loaded with the model drug indomethacin (IMC) via the solvent deposition method. Scanning electron microscopy (SEM), N2 adsorption, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were applied to systematically characterize all IMC-loaded nanoporous silica formulations, evidencing the successful inclusion of IMC into nanopores, the reduced crystallinity, and finally accelerated dissolution of IMC. It was worth mentioning that, in comparison to 2D mesoporous silica, 3DOM silica displayed a more rapid release profile, which may be ascribed to the 3D interconnected pore networks and the highly accessible surface areas. The results obtained from the stability test indicated that the amorphous state of IMC entrapped in the 2D mesoporous silica (SBA-15 and MCM-41) has a better physical stability than in that of 3DOM silica. Moreover, the dissolution rate and stability of IMC loaded in 3DOM silica was closely related to the pore size of macroporous silica. The colorimetric 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and Cell Counting Kit (CCK)-8 assays in combination with direct morphology observations demonstrated the good biocompatibility of nanoporous silica, especially for 3DOM silica and SBA-15. The present work encourages further study of the drug release properties and stability of drug entrapped in different pore architecture of silica in order to realize their potential in oral drug delivery. PMID:24174875

Evaluating fluorescence spectroscopy as a tool to characterize cyanobacteria intracellular organic matter upon simulated release and oxidation in natural water.

PubMed

Korak, Julie A; Wert, Eric C; Rosario-Ortiz, Fernando L

2015-01-01

Intracellular organic matter (IOM) from cyanobacteria may be released into natural waters following cell death in aquatic ecosystems and during oxidation processes in drinking water treatment plants. Fluorescence spectroscopy was evaluated to identify the presence of IOM from three cyanobacteria species during simulated release into natural water and following oxidation processes (i.e. ozone, free chlorine, chloramine, chlorine dioxide). Peak picking and the fluorescence index (FI) were explored to determine which IOM components (e.g., pigments) provide unique and persistent fluorescence signatures with minimal interferences from the background dissolved organic matter (DOM) found in Colorado River water (CRW). When IOM was added to ultrapure water, the fluorescence signature of the three cyanobacteria species showed similarities to each other. Each IOM exhibited a strong protein-like fluorescence and fluorescence at Ex 370 nm and Em 460 nm (FDOM), where commercial fluorescence sensors monitor. All species also had strong phycobiliprotein fluorescence (i.e. phycocyanin or phycoerythrin) in the higher excitation range (500-650 nm). All three IOM isolates had FI values greater than 2. When IOM was added to CRW, phycobiliprotein fluorescence was quenched through interactions between IOM and CRW-DOM. Mixing IOM and CRW demonstrated that protein-like and FDOM intensity responses were not a simple superposition of the starting material intensities, indicating that interactions between IOM and CRW-DOM fluorescing moieties were important. Fluorescence intensity in all regions decreased with exposure to ozone, free chlorine, and chlorine dioxide, but the FI still indicated compositional differences compared to CRW-DOM. The phycobiliproteins in IOM are not promising as a surrogate for IOM release, because their fluorescence intensity is quenched by interactions with DOM and decreased during oxidation processes. Increases in both FDOM intensity and FI are viable qualitative indicators of IOM release in natural waters and following oxidation and may provide a more robust real-time indication of the presence of IOM than conventional dissolved organic carbon or UV absorbance measurements.

Partial coupling and differential regulation of biologically and photo-chemically labile dissolved organic carbon across boreal aquatic networks

NASA Astrophysics Data System (ADS)

Lapierre, J.-F.; del Giorgio, P. A.

2014-05-01

Despite the rapidly increasing volume of research on the biological and photochemical degradation of DOC in aquatic environments, little is known on the large-scale patterns in biologically and photo-chemically degradable DOC (Bd-DOC and Pd-DOC, respectively) in continental watersheds, and on the links that exist between these two key properties that greatly influence the flow of carbon from continents to oceans. Here we explore the patterns of Bd- and Pd-DOC across hundreds of boreal lakes, rivers and wetlands spanning a large range of system trophy and terrestrial influence, and compared the drivers of these two reactive pools of DOC at the landscape level. Using standardized incubations of natural waters, we found that the concentrations of Bd- and Pd-DOC co-varied across all systems studied but were nevertheless related to different pools of dissolved organic matter (DOM, identified by fluorescence analyses) in ambient waters. A combination of nutrients and protein-like DOM explained nearly half of the variation in Bd-DOC, whereas Pd-DOC was exclusively predicted by DOM optical properties, consistent with the photochemical degradability of specific fluorescent DOM (FDOM) pools that we experimentally determined. The concentrations of colored DOM (CDOM), a proxy of terrestrial influence, almost entirely accounted for the observed relationship between FDOM and the concentrations of both Bd- and Pd-DOC. The concentrations of CDOM and of the putative bio-labile fluorescence component shifted from complete decoupling in clear-water environments to strong coupling in browner streams and wetlands. This suggests a baseline autochthonous Bd-DOC pool fuelled by internal production that is gradually overwhelmed by land-derived Bd-DOC as terrestrial influence increases across landscape gradients. The importance of land as a major source of both biologically and photo-chemically degradable DOC for continental watersheds resulted in a partial coupling of those carbon pools in natural freshwaters, despite fundamental contrasts in terms of their composition and regulation.

Is DOM driver of the microbial carrying capacity in pristine porous groundwater ecosystems? - lab-scale experiments in 2D sediment flow-through microcosms

NASA Astrophysics Data System (ADS)

Hofmann, Roland; Griebler, Christian

2017-04-01

Groundwater ecosystems are an essential resource for drinking water and at the same time constitute fascinating habitats subject to increasing (anthropogenic) disturbances. In our research, we look for ways to qualitatively and quantitatively access, and predict the resistance and resilience (potential) of groundwater ecosystems in consequence of selected disturbances. As a central goal we hope to identify and quantify the underlying biological and ecological key drivers of the microbial Carrying Capacity (mCC) - an ecological concept established in macro-ecology - we assume directly connected to the ecosystem's productivity and the resistance and resilience of aquifers. We further hypothesize, that the ecosystems' mCC is a result of available energy and constitutes a promising proxy for the potential of groundwater ecosystems to withstand impacts and recover from it. In a first approach we studied the dynamics of the microbial standing stock (biomass) and growth (productivity) productivity of a natural groundwater microbial community in parallel 2-D sediment flow-through systems. Selected zones of the model aquifers were disturbed by elevated DOM concentrations. Both the 'mobile' (free floating) and 'sessile' (sediment attached) microbial components were followed over time in terms of biomass, growth, and specific activities (ATP, carbon use efficiency) and taxonomic composition. Sediment regions supplied with elevated concentrations of natural DOM showed increased biomass, activities and taxonomic richness with the sediment community, while differences in the mobile microbial were marginal. Specifically, the carbon use efficiency was significantly increased in the DOM amended sediment zones. In contrast, the microbial community that received the mainly refractory natural background DOM was able to metabolize polymers more efficiently in substrate use tests (ECOLOG), seen as an adaptation to the energy-poor subsurface. Quasi-stationary conditions were reached in the model aquifers only after several weeks. The quantitative link between microbial productivity and mCC is currently evaluated.

Production and Composition of Dissolved Black Carbon from Various Biochars and Environmentally-aged Charcoals

NASA Astrophysics Data System (ADS)

Bostick, K. W.; Zimmerman, A. R.; Hatcher, P.; Mitra, S.; Wozniak, A. S.

2016-12-01

Pyrogenic organic matter, or black carbon (BC), is the solid carbonaceous product of biomass pyrolysis. While solid BC represents a long-lived portion of the C cycle, it releases pyrogenic dissolved organic matter (py-DOM) which may be more susceptible to mineralization and transformation. This py-DOM may impact environmental and public health and likely controls exchange between terrestrial and aquatic BC pools. Benzene polycarboxylic acids (BPCAs), produced by acid digestion of samples, are used as molecular markers for pyrogenic organic matter. Yet, we currently have a poor understanding of the controls on the production of py-DOM and its yield of BPCA compounds. In response, aqueous leaching time series experiments were carried out using a series of laboratory-made biochars and environmentally-aged charcoals. While non-charred oak biomass released 31.8 mg C/g (45% C loss), oak biochars prepared at low temperatures (250 and 400ºC), produced 9.9 and 2.6 mg C/g (11 and 2.3% C loss), respectively. Oak chars prepared at a higher temperatures (650ºC) leached only 1.85 mg C/g (1.5% C loss). In contrast, an environmentally-aged charcoal (30 y old cypress charcoal) leached 10.9% of its C. On average, 59% (ranging 38-80%) of oak pyrogenic DOC was converted into BPCAs, suggesting that oak py-DOM has a variably condensed aromatic proportion. However, much less BPCAs were generated by BC parent solids. In addition, trace amounts of BPCA were generated from non-pyrolyzed grass, oak wood, and compost leachates; these lend concern to the use of BPCAs as exclusive pyrogenic molecular markers. As expected, BPCA molecular distribution showed that condensation increased with pyrolysis temperature of solid biochars and their corresponding leachates. The comparison of these findings to 13C and 1H NMR spectra of charcoal parent solids and their leachates will further elucidate the chemistry and production mechanisms of py-DOM.

Biochars induced modification of dissolved organic matter (DOM) in soil and its impact on mobility and bioaccumulation of arsenic and cadmium.

PubMed

Li, Gang; Khan, Sardar; Ibrahim, Muhammad; Sun, Tian-Ran; Tang, Jian-Feng; Cotner, James B; Xu, Yao-Yang

2018-04-15

Biochar application has attracted great attention due to its diverse uses and benefits in the fields of environmental management and agriculture. Biochar modifies the composition of dissolved organic matter (DOM) in soil, which directly or indirectly controls the mobility of metal contaminants and their bioaccumulation. In this study, ten different hydrothermal biochars pyrolysed from mushroom waste (MSBC), soybean straw (SBBC), sewage sludge (SSBC), peanut shells (PNBC) and rice straw (RSBC) at two pyrolysis temperatures (200 °C and 350 °C) were used to investigate DOM changes in soil solution and their effects on metal availability and bioaccumulation. Biochar induced modification of soil DOM which was characterized by spectroscopic analysis of water soluble organic carbon, specific absorbance (SUVA 254 ), UV-vis absorption, spectral slope (S R ) and the absorption coefficient. Regarding rice plant growth, the biochar effects on biomass were greatly varied. Biochars (except for RSBC and MSBC) prepared at high temperature significantly (P ≤ 0.05) suppressed the availability of As and Cd in soil and their subsequent bioaccumulation in rice plants. The highest reduction (88%) in bioaccumulated As was observed in rice grown on soil amended with SBBC prepared at 350 °C (the highest temperature for hydrothermal technique). The addition of biochars (except RSBC and MSBC) prepared at high temperature markedly (p < 0.05) decreased AsIII (30-92%), while the effects on dimethylarsenic acid (DMA) and arsenate (AsV) concentrations were not significant except for SSBC350 (prepared at 350 °C) treatment. These results highlight the potential of biochar-DOM interactions as an important mechanism for suppressing the mobility and bioaccumulation of As and Cd in biochar-amended paddy agricultural systems. Copyright © 2018 Elsevier B.V. All rights reserved.

High field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter from the South Atlantic Ocean

NASA Astrophysics Data System (ADS)

Hertkorn, N.; Harir, M.; Koch, B. P.; Michalke, B.; Grill, P.; Schmitt-Kopplin, P.

2012-01-01

Non target high resolution organic structural spectroscopy of marine dissolved organic matter (DOM) isolated on 27 November 2008 by means of solid phase extraction (SPE) from four different depths in the South Atlantic Ocean off the Angola coast (3.1° E; -17.7° S; Angola basin) provided molecular level information of complex unknowns with unprecedented coverage and resolution. The sampling was intended to represent major characteristic oceanic regimes of general significance: 5 m (FISH; near surface photic zone), 48 m (FMAX; fluorescence maximum), 200 m (upper mesopelagic zone) and 5446 m (30 m above ground). 800 MHz proton (1H) nuclear magnetic resonance (NMR) 1H NMR, spectra were least affected by fast and differential transverse NMR relaxation and produced at first similar looking, rather smooth bulk NMR envelopes reflecting intrinsic averaging from massive signal overlap. Visibly resolved NMR signatures were most abundant in surface DOM but contributed at most a few percent to the total 1H NMR integral and were mainly limited to unsaturated and singly oxygenated carbon chemical environments. The relative abundance and variance of resolved signatures between samples was maximal in the aromatic region; in particular, the aromatic resolved NMR signature of the deep ocean sample at 5446 m was considerably different from that of all other samples. When scaled to equal total NMR integral, 1H NMR spectra of the four marine DOM samples revealed considerable variance in abundance for all major chemical environments across the entire range of chemical shift. Abundance of singly oxygenated CH units and acetate derivatives declined from surface to depth whereas aliphatics and carboxyl-rich alicyclic molecules (CRAM) derived molecules increased in abundance. Surface DOM contained a remarkably lesser abundance of methyl esters than all other marine DOM, likely a consequence of photodegradation from direct exposure to sunlight. All DOM showed similar overall 13C NMR resonance envelopes typical of an intricate mixture of natural organic matter with noticeable peaks of anomerics and C-aromatics carbon whereas oxygenated aromatics and ketones were of too low abundance to result in noticeable humps at the S/N ratio provided. Integration according to major substructure regimes revealed continual increase of carboxylic acids and ketones from surface to deep marine DOM, reflecting a progressive oxygenation of marine DOM, with concomitant decline of carbohydrate-related substructures. Isolation of marine DOM by means of SPE likely discriminated against carbohydrates but produced materials with beneficial NMR relaxation properties: a substantial fraction of dissolved organic molecules present allowed the acquisition of two-dimensional NMR spectra with exceptional resolution. JRES, COSY and HMBC NMR spectra were capable to depict resolved molecular signatures of compounds exceeding a certain minimum abundance. Here, JRES spectra suffered from limited resolution whereas HMBC spectra were constrained because of limited S/N ratio. Hence, COSY NMR spectra appeared best suited to depict organic complexity in marine DOM. The intensity and number of COSY cross peaks was found maximal for sample FMAX and conformed to about 1500 molecules recognizable in variable abundance. Surface DOM (FISH) produced a slightly (~25%) lesser number of cross peaks with remarkable positional accordance to FMAX (~80% conforming COSY cross peaks were found in FISH and FMAX). With increasing water depth, progressive attenuation of COSY cross peaks was caused by fast transverse NMR relaxation of yet unknown origin. However, most of the faint COSY cross peak positions of deep water DOM conformed to those observed in the surface DOM, suggesting the presence of a numerous set of identical molecules throughout the entire ocean column even if the investigated water masses belonged to different oceanic regimes and currents. Aliphatic chemical environments of methylene (CH2) and methyl (CH3) in marine DOM were nicely discriminated in DEPT HSQC NMR spectra. Classical methyl groups terminating aliphatic chains represented only ~15% of total methyl in all marine DOM investigated. Chemical shift anisotropy from carbonyl derivatives (i.e. most likely carboxylic acids) displaced aliphatic methyl 1H NMR resonances up to δH ~1.6 ppm, indicative of alicyclic geometry which furnishes more numerous short range connectivities for any given atom pairs. A noticeable fraction of methyl (~2%) was bound to olefinic carbon. The comparatively large abundance of methyl ethers in surface marine DOM contrasted with DOM of freshwater and soil origin. The chemical diversity of carbohydrates as indicated by H2CO-groups (δC ~ 62 ± 2 ppm) and anomerics (δC ~ 102 ± 7 ppm) exceeded that of freshwater and soil DOM considerably. HSQC NMR spectra were best suited to identify chemical environments of methin carbon (CH) and enabled discrimination of olefinic and aromatic cross peaks (δC > 110 ppm) and those of doubly oxygenated carbon (δC < 110 ppm). The abundance of olefinic protons exceeded that of aromatic protons; comparison of relative HSQC cross peak integrals indicated larger abundance of olefinic carbon than aromatic carbon in all marine DOM as well. A considerable fraction of olefins seemed isolated and likely sterically constrained as judged from small nJHH couplings associated with those olefins. High S/N ratio and fair resolution of TOCSY and HSQC cross peaks enabled unprecedented depiction of sp2-hybridized carbon chemical environments in marine DOM with discrimination of isolated and conjugated olefins as well as α, β-unsaturated double bonds. However, contributions from five-membered heterocycles (furan, pyrrol and thiophene derivatives) even if very unlikely from given elemental C/N and C/S ratios and upfield proton NMR chemical shift (δH < 6.5 ppm) could not yet been ruled out entirely. In addition to classical aromatic DOM, like benzene derivatives and phenols, six-membered nitrogen heterocycles were found prominent contributors to the downfield region of proton chemical shift (δH > 8 ppm). Specifically, a rather confined HSQC cross peak at δH/δC = 8.2/164 ppm indicated a limited set of nitrogen heterocycles with several nitrogen atoms in analogy to RNA derivatives present in all four marine DOM. Appreciable amounts of extended HSQC and TOCSY cross peaks derived from various key polycyclic aromatic hydrocarbon substructures suggested the presence of previously proposed but NMR invisible thermogenic organic matter (TMOC) in marine DOM at all water depths. Eventually, olefinic unsaturation in marine DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation of which a substantial fraction originates from an aged material which from the beginning was subjected to complex and less specific biogeochemical reactions like thermal decomposition. The variance in molecular mass as indicated from Fourier transform ion cyclotron resonance (FTICR) mass spectra was limited and could not satisfactorily explain the observed disparity in NMR transverse relaxation of the four marine DOM samples. Likewise, the presence of metal ions in isolated marine DOM remained near constant or declined from surface to depth for important paramagnetic ions like Mn, Cr, Fe, Co, Ni and Cu. Iron in particular, a strong complexing paramagnetic ion, was found most abundant by a considerable margin in surface (FISH) marine DOM for which well resolved COSY cross peaks were observed. Hence, facile relationships between metal content of isolated DOM (which does not reflect authentic marine DOM metal content) and transverse NMR relaxation were not observed. High field (12 T) negative electrospray ionization FTICR mass spectra showed at first view rather conforming mass spectra for all four DOM samples with abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing numbers of mass peaks from surface to bottom DOM and similar fractions (~50%) of assigned molecular compositions throughout all DOM samples. The average mass increased from surface to bottom DOM by about 10 Dalton. The limited variance of FTICR mass spectra probably resulted from a rather inherent conformity of marine DOM at the mandatory level of intrinsic averaging provided by FTICR mass spectrometry, when many isomers unavoidably project on single nominal mass peaks. In addition, averaging from ion suppression added to the accordance observed. The proportion of CHO and CHNO molecular series increased from surface to depth whereas CHOS and especially CHNOS molecular series markedly declined. The abundance of certain aromatic CHOS compounds declined with water depth. For future studies, COSY NMR spectra appear best suited to assess organic molecular complexity of marine DOM and to define individual DOM molecules of yet unknown structure and function. Non-target organic structural spectroscopy at the level demonstrated here covered nearly all carbon present in marine DOM. The exhaustive characterization of complex unknowns in marine DOM will reveal a meaningful assessment of individual marine biogeosignatures which carry the holistic memory of the oceanic water masses (Koch et al., 2011).

Are Longitudinal Patterns of Bacterial Community Composition and Dissolved Organic Matter Composition Linked Across a River Continuum? (Invited)

NASA Astrophysics Data System (ADS)

Mosher, J.; Kaplan, L. A.; Kan, J.; Findlay, R. H.; Podgorski, D. C.; McKenna, A. M.; Branan, T. L.; Griffith, C.

2013-12-01

The River Continuum Concept (RCC), an early meta-ecosystem idea, was developed without the benefit of new frontiers in molecular microbial ecology and ultra-high resolution mass spectrometry. We have applied technical advances in these areas to address a hypothesis implicit in the RCC that the upstream legacy of DOM processing contributes to the structure and function of downstream bacterial communities. DOM molecular structure and microbial community structure were measured across river networks within three distinct forested catchments. High-throughput pyrosequencing of bacterial 16S rRNA amplicons and phospholipid fatty acid analysis were used to characterize bacterial communities, and ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry characterized the molecular composition of stream water DOM. Total microbial biomass varied among river networks but showed a trend of decreasing biomass in sediment with increasing stream order. There were distinct shifts in bacterial community structure and a trend of decreasing richness was observed traveling downstream in both sediment and epilithic habitats. The bacterial richness in the first order stream sediment habitats was 7728 genera which decreased to 6597 genera in the second order sites and 4867 genera in the third order streams. The richness in the epilithic biofilm habitats was 2830 genera in the first order, 2322 genera in the second order and 1629 genera in the third order sites. Over 45% of the sediment biofilm genera and 37% of the epilithic genera were found in all three orders. In addition to shifts in bacterial richness, we observed a longitudinal shift in bacterial functional-types. In the sediment biofilms, Rhodoplanes spp. (containing rhodopsin pigment) and Bradyrhizobium spp. (nitrogen fixing bacteria) were predominately found in the heavily forested first order streams, while the cyanobacteria Limnothrix spp. was dominant in the second order streams. The third order streams had higher abundances of Sphingomonadaceae spp. and Nordella spp. (both Alphaproteobacteria). The cyanobacteria Chamaesiphon spp. was observed in highest abundance in the first and second order streams of the rock biofilm samples and the cyanobacteria Oscillatoria spp. was in highest abundance in the third order streams. Stream water samples from all orders had high lignin/tannin content and were enriched with carboxylic-rich alicyclic molecules (CRAM). There was an observable shift in in the molecular weight and relative abundance of the CRAM molecules with the CRAM molecules becoming less abundant and having lower molecular weight following the downstream gradient. Multivariate statistical analyses correlated the longitudinal patterns of changes in bacterial community structure to the DOM molecular structure and geochemical parameters across the river continuum.

An initial investigation into the organic matter biogeochemistry of the Congo River

USGS Publications Warehouse

Spencer, Robert G.M.; Hernes, Peter J.; Aufdenkampe, Anthony K.; Baker, Andy; Gulliver, Pauline; Stubbins, Aron; Aiken, George R.; Dyda, Rachael Y.; Butler, Kenna D.; Mwamba, Vincent L.; Mangangu, Arthur M.; Wabakanghanzi, Jose N.; Six, Johan

2012-01-01

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ13C, Δ14C, δ15N) and biochemical composition (lignin phenols) of coarse particulate (>63 μm; CPOM) and fine particulate (0.7–63 μm; FPOM) OM and DOC, δ13C, Δ14C and lignin phenol composition with respect to dissolved OM (14C = -62.2 ± -13.2‰, n = 5) compared to CPOM and DOM (mean Δ14C = 55.7 ± 30.6‰, n = 4 and 73.4 ± 16.1‰, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67–1.12 (mg(100 mg OC)-1)) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2–27.1) and Λ8 values (4.56–7.59 (mg(100 mg OC)-1)). In relation to CPOM, the aged FPOM fraction (320–580 ybp 14C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4–14.3), lower Λ8 (2.80–4.31 (mg(100 mg OC)-1)) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (~350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

Sorptive and desorptive fractionation of dissolved organic matter by mineral soil matrices.

PubMed

Oren, Adi; Chefetz, Benny

2012-01-01

Interactions of dissolved organic matter (DOM) with soil minerals, such as metal oxides and clays, involve various sorption mechanisms and may lead to sorptive fractionation of certain organic moieties. While sorption of DOM to soil minerals typically involves a degree of irreversibility, it is unclear which structural components of DOM correspond to the irreversibly bound fraction and which factors may be considered determinants. To assist in elucidating that, the current study aimed at investigating fractionation of DOM during sorption and desorption processes in soil. Batch DOM sorption and desorption experiments were conducted with organic matter poor, alkaline soils. Fourier-transform infrared (FTIR) and UV-Vis spectroscopy were used to analyze bulk DOM, sorbed DOM, and desorbed DOM fractions. Sorptive fractionation resulted mainly from the preferential uptake of aromatic, carboxylic, and phenolic moieties of DOM. Soil metal-oxide content positively affected DOM sorption and binding of some specific carboxylate and phenolate functional groups. Desorptive fractionation of DOM was expressed by the irreversible-binding nature of some carboxylic moieties, whereas other bound carboxylic moieties were readily desorbed. Inner-sphere, as opposed to outer-sphere, ligand-exchange complexation mechanisms may be responsible for these irreversible, as opposed to reversible, interactions, respectively. The interaction of aliphatic DOM constituents with soil, presumably through weak van der Waals forces, was minor and increased with increasing proportion of clay minerals in the soil. Revealing the nature of DOM-fractionation processes is of great importance to understanding carbon stabilization mechanisms in soils, as well as the overall fate of contaminants that might be associated with DOM. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Tracking senescence-induced patterns in leaf litter leachate using parallel factor analysis (PARAFAC) modeling and self-organizing maps

NASA Astrophysics Data System (ADS)

Wheeler, K. I.; Levia, D. F.; Hudson, J. E.

2017-09-01

In autumn, the dissolved organic matter (DOM) contribution of leaf litter leachate to streams in forested watersheds changes as trees undergo resorption, senescence, and leaf abscission. Despite its biogeochemical importance, little work has investigated how leaf litter leachate DOM changes throughout autumn and how any changes might differ interspecifically and intraspecifically. Since climate change is expected to cause vegetation migration, it is necessary to learn how changes in forest composition could affect DOM inputs via leaf litter leachate. We examined changes in leaf litter leachate fluorescent DOM (FDOM) from American beech (Fagus grandifolia Ehrh.) leaves in Maryland, Rhode Island, Vermont, and North Carolina and from yellow poplar (Liriodendron tulipifera L.) leaves from Maryland. FDOM in leachate samples was characterized by excitation-emission matrices (EEMs). A six-component parallel factor analysis (PARAFAC) model was created to identify components that accounted for the majority of the variation in the data set. Self-organizing maps (SOM) compared the PARAFAC component proportions of leachate samples. Phenophase and species exerted much stronger influence on the determination of a sample's SOM placement than geographic origin. As expected, FDOM from all trees transitioned from more protein-like components to more humic-like components with senescence. Percent greenness of sampled leaves and the proportion of tyrosine-like component 1 were found to be significantly different between the two genetic beech clusters, suggesting differences in photosynthesis and resorption. Our results highlight the need to account for interspecific and intraspecific variations in leaf litter leachate FDOM throughout autumn when examining the influence of allochthonous inputs to streams.

Occurrence and behaviors of fluorescence EEM-PARAFAC components in drinking water and wastewater treatment systems and their applications: a review.

PubMed

Yang, Liyang; Hur, Jin; Zhuang, Wane

2015-05-01

Fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) is a powerful tool for characterizing dissolved organic matter (DOM), and it is applied in a rapidly growing number of studies on drinking water and wastewater treatments. This paper presents an overview of recent findings about the occurrence and behavior of PARAFAC components in drinking water and wastewater treatments, as well as their feasibility for assessing the treatment performance and water quality including disinfection by-product formation potentials (DBPs FPs). A variety of humic-like, protein-like, and unique (e.g., pyrene-like) fluorescent components have been identified, providing valuable insights into the chemical composition of DOM and the effects of various treatment processes in engineered systems. Coagulation/flocculation-clarification preferentially removes humic-like components, and additional treatments such as biological activated carbon filtration, anion exchange, and UV irradiation can further remove DOM from drinking water. In contrast, biological treatments are more effective for protein-like components in wastewater treatments. PARAFAC components have been proven to be valuable as surrogates for conventional water quality parameter, to track the changes of organic matter quantity and quality in drinking water and wastewater treatments. They are also feasible for assessing formations of trihalomethanes and other DBPs and evaluating treatment system performance. Further studies of EEM-PARAFAC for assessing the effects of the raw water quality and variable treatment conditions on the removal of DOM, and the formation potentials of various emerging DBPs, are essential for optimizing the treatment processes to ensure treated water quality.

Seasonal variations in dissolved organic matter composition using absorbance and fluorescence spectroscopy in the Dardanelles Straits - North Aegean Sea mixing zone

NASA Astrophysics Data System (ADS)

Pitta, Elli; Zeri, Christina; Tzortziou, Maria; Mousdis, George; Scoullos, Michael

2017-10-01

The Dardanelles Straits - North Aegean Sea mixing zone is the area where the less saline waters of Black Sea origin supply organic material to the oligotrophic Mediterranean Sea. The objective of this work was to assess the seasonal dynamics of dissolved organic matter (DOM) in this region based on the optical properties (absorbance and fluorescence). By combining excitation-emission fluorescence with parallel factor analysis (EEM-PARAFAC), four fluorescent components were identified corresponding to three humic - like components and one amino acid - like. The latter was dominant during all seasons. Chromophoric DOM (CDOM) and dissolved organic carbon (DOC) were found to be strongly coupled only in early spring when conservative conditions prevailed and the two water masses present (Black Sea Waters - BSW and Levantine Waters - LW) could be identified by their absorption coefficients (a300) and spectral slopes S275-295. In summer and autumn the relationships collapsed. During summer two features appear to dominate the dynamics of CDOM: i) photodegradation that acts as an important sink for both the absorbing DOM and the terrestrially derived fluorescent humic substances and ii) the release of marine humic like fluorescent substances from bacterial transformation of DOM. Autumn results revealed a source of fluorescent CDOM of high molecular weight, which was independent of water mass sources and related to particle and sedimentary processes. The removal of the amino acid-like fluorescence during autumn provided evidence that although DOC was found to accumulate under low inorganic nutrient conditions, dissolved organic nitrogenous compounds could serve as bacterial substrate.

Capturing Hot Moments of Carbon Cycling in the Hyporheic Zone of an Intermittent Stream

NASA Astrophysics Data System (ADS)

Brandt, T.; Harjung, A.; Vieweg, M.; Butturini, A.; Schmidt, C.; Fleckenstein, J. H.; Sabater, F.

2016-12-01

Intermittent streams are increasingly recognized as a factor for underestimating potential CO2 emissions of aquatic ecosystems, because they are neglected during their dry phase. This can be partly attributed to poor understanding of dissolved organic matter (DOM) processing at highly reactive interfaces such as the hyporheic zone (HZ). Here, hydrological transitions drive rapid changes in the spatiotemporal distribution of dissolved oxygen (DO), thus creating hot moments of increased biogeochemical cycling. However, capturing these process-dynamics requires a continuous monitoring of hyporheic pore water at a sufficient temporal and spatial resolution. In order to investigate the transitions between the wet and dry phase, we used a combination of automated pore water sampling and in situ measurements. By combining conventional pumping approaches with recently developed technology we achieved a high resolution multi-scale, quasi continuous monitoring of relevant parameters of the carbon cycle. Our novel approach coupled continuous fluorescence DOM and infrared CO2 sensor measurements with spatially continuous vertical oxygen profiling in situ. A proof-of-concept application was established in a semi-pristine Mediterranean stream during the drying period in summer 2015. Previous sampling campaigns already identified the water level as a driver of DOM composition in the HZ. Once the surface flow switches to subsurface flow, the HZ becomes a sink for aromatic, high molecular weight compounds, while protein-like, autochthonous DOM gets released. Generally, we observed exponential increases in hyporheic CO2 from this point on, co-occurring with a sharp vertical DO gradient as a function of changing hydrological conditions.

ESI-FTICR-MS Molecular Characterization of DOM Degradation under Warming in Tundra Soils from Barrow, Alaska

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hongmei Chen; Ziming Yang; Rosalie Chu

This dataset provides the results of warming incubation of Arctic soils from trough areas of a high-center polygon at the Barrow Environmental Observatory (BEO) in northern Alaska, United States. The organic-rich soil (8-20 cm below ground surface) and the mineral-rich soil (22-45 cm below surface) were separated, and the thawed and homogenized subsamples from each soil were incubated at -2 degrees C or 8 degrees C for 122 days under anoxic conditions (headspace filled with N2). The extracted DOM from soil samples were analyzed by Fourier transform ion cyclotron resonance mass spectrometry coupled with electrospray ionization (ESI-FTICR-MS). Reported analytes includemore » soil water content, dissolved organic carbon, total organic carbon, MS peaks' m/z and intensities, and elemental composition of identified molecular formulas.« less

The balance model of oxygen enrichment of atmospheric air

NASA Astrophysics Data System (ADS)

Popov, Alexander

2013-04-01

The study of turnover of carbon and oxygen is an important line of scientific investigation. This line takes on special significance in conditions of soil degradation, which leads to the excess content of carbon dioxide and, as result, decrease of oxygen in the atmosphere. The aim of this article is a statement the balance model of oxygen enrichment of atmospheric air (ratio O/C) depending on consumption and assimilation by plants of dissolved organic matter (DOM) and the value of the oxidation-reduction potential (Eh). Basis of model was the following: green vascular plants are facultative heterotrophic organisms with symbiotic digestion and nutrition. According to the trophology viewpoint, the plant consumption of organic compounds broadens greatly a notion about the plant nutrition and ways of its regulation. In particular, beside the main known cycle of carbon: plant - litter - humus - carbon dioxide - plant, there is the second carbon cycle (turnover of organic compounds): plant - litter - humus - DOM - plant. The biogeochemical meaning of consumption of organic compounds by plants is that plants build the structural and functional blocks of biological macromolecules in their bodies. It provides receiving of a certain "energy payoff" by plants, which leads to increase of plant biomass by both an inclusion of allochthonous organic molecules in plant tissues, and positive effect of organic compounds on plant metabolic processes. One more of powerful ecological consequence of a heterotrophic nutrition of green plants is oxygen enrichment of atmospheric air. As the organic molecules in the second biological cycle of carbon are built in plants without considerable chemical change, the atmospheric air is enriched on that amount of oxygen, which would be required on oxidation of the organic molecules absorbed by plants, in result. It was accepted that: plant-soil system was climax, the plant community was grassy, initial contents of carbon in phytomass was accepted as 1, annually from 60 to 100 % of the plant litter could arrive to the soil; coefficients of humification of both plant litter and DOM were 0.1 (10 %); DOM is formed as a result of hydrolytic destruction of plant litter, newly formed humic substances (HS) and humus; coefficient of possible absorption of DOM by plants - 0.1 (10 %); it was considered that all organic compounds affiliated into DOM had positive physiological effect on green plants; it was accepted that 1 % DOM absorbed by plants increases phytomass on 10 % (for example, at the expense of photosynthesis acceleration); Eh value was changed from 300 to 800 mV; depending on Eh (i) the coefficient of plant litter oxidation was in the range from 0.75 (75 %) to 0.8 (90 %), coefficient of oxidation of DOM and newly formed HS - from 0.85 (85 %) to 0.9 (90 %), and coefficient of humus oxidation from 0 (0 %) to 0.05 (5 %), and (ii) coefficient of hydrolytic destruction of plant litter and newly formed HS was in the range from 0.12 (12 %) to 0.07 (7 %), and coefficient of humus hydrolytic destruction from 0,05 (5 %) to 0 (0 %), accordingly; all dependences were quasilinear. The following conclusions have been made based on the modeling: (i) both phytomass and oxygen content in atmospheric air were increased with increase of DOM part absorbed by green vascular plants; (ii) the abundance of humus was increased with increase of DOM consumption by green plant (on 5 % at all Eh values) too; (iii) the increase of Eh with 300 to 800 mV led to reduction of oxygen in atmospheric air and to quadruple decrease of the abundance of humus.

Photoreduction of Hg(II) and photodemethylation of methylmercury: the key role of thiol sites on dissolved organic matter

USGS Publications Warehouse

Jeremiason, Jeffrey D.; Portner, Joshua C.; Aiken, George R.; Hiranaka, Amber J.; Dvorak, Michelle T.; Tran, Khuyen T.; Latch, Douglas E.

2015-01-01

This study examined the kinetics of photoreduction of Hg(II) and photodemethylation of methylmercury (MeHg+) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg(II) and MeHg+ are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg(II) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg+ bound to DOM. UV spectra of Hg(II) and MeHg+ bound to thiol containing molecules demonstrate that the Hg(II)–S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg+–S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg+ and Hg(II); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg+ than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg(II) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg+. Utilizing the difference in photodemethylation rates measured for MeHg+ attached to DOM or thiol ligands, the binding constant for MeHg+ attached to thiol groups on DOM was estimated to be 1016.7.

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.

Effects of wastewater treatment plant effluent inputs on planktonic metabolic rates and microbial community composition in the Baltic Sea

NASA Astrophysics Data System (ADS)

Vaquer-Sunyer, Raquel; Reader, Heather E.; Muthusamy, Saraladevi; Lindh, Markus V.; Pinhassi, Jarone; Conley, Daniel J.; Kritzberg, Emma S.

2016-08-01

The Baltic Sea is the world's largest area suffering from eutrophication-driven hypoxia. Low oxygen levels are threatening its biodiversity and ecosystem functioning. The main causes for eutrophication-driven hypoxia are high nutrient loadings and global warming. Wastewater treatment plants (WWTP) contribute to eutrophication as they are important sources of nitrogen to coastal areas. Here, we evaluated the effects of wastewater treatment plant effluent inputs on Baltic Sea planktonic communities in four experiments. We tested for effects of effluent inputs on chlorophyll a content, bacterial community composition, and metabolic rates: gross primary production (GPP), net community production (NCP), community respiration (CR) and bacterial production (BP). Nitrogen-rich dissolved organic matter (DOM) inputs from effluents increased bacterial production and decreased primary production and community respiration. Nutrient amendments and seasonally variable environmental conditions lead to lower alpha-diversity and shifts in bacterial community composition (e.g. increased abundance of a few cyanobacterial populations in the summer experiment), concomitant with changes in metabolic rates. An increase in BP and decrease in CR could be caused by high lability of the DOM that can support secondary bacterial production, without an increase in respiration. Increases in bacterial production and simultaneous decreases of primary production lead to more carbon being consumed in the microbial loop, and may shift the ecosystem towards heterotrophy.

Partitioning of the pesticide trifluralin between dissolved organic matter and water using automated SPME-GC/MS.

PubMed

Caupos, Emilie; Touffet, Arnaud; Mazellier, Patrick; Croue, Jean-Philippe

2015-03-01

Solid-phase microextraction (SPME) was used to determine the equilibrium association constant for a pesticide, trifluralin (TFR), with dissolved organic matter (DOM). After optimization of the SPME method for the analysis of TFR, partition coefficients (K DOM) with three different sources of DOM were determined in buffered solutions at pH 7. Commercial humic acids and DOM fractions isolated from two surface waters were used. The values of log K DOM varied from 4.3 to 5.8, depending on the nature of the organic material. A good correlation was established between log K DOM and DOM properties (as measured with the H/O atomic ratio and UV absorbance), in agreement with literature data. This is consistent with the effect of polarity and aromaticity for governing DOM-pollutant associations, regardless of the origin of DOM. This association phenomenon is relevant to better understand the behavior of pesticides in the environment since it controls part of pesticide leaching and fate in aquatic systems.

Copper(II) binding by dissolved organic matter: Importance of the copper-to-dissolved organic matter ratio and implications for the Biotic Ligand Model

USGS Publications Warehouse

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

2012-01-01

The ratio of copper to dissolved organic matter (DOM) is known to affect the strength of copper binding by DOM, but previous methods to determine the Cu2+–DOM binding strength have generally not measured binding constants over the same Cu:DOM ratios. In this study, we used a competitive ligand exchange–solid-phase extraction (CLE-SPE) method to determine conditional stability constants for Cu2+–DOM binding at pH 6.6 and 0.01 M ionic strength over a range of Cu:DOM ratios that bridge the detection windows of copper-ion-selective electrode and voltammetry measurements. As the Cu:DOM ratio increased from 0.0005 to 0.1 mg of Cu/mg of DOM, the measured conditional binding constant (cKCuDOM) decreased from 1011.5 to 105.6 M–1. A comparison of the binding constants measured by CLE-SPE with those measured by copper-ion-selective electrode and voltammetry demonstrates that the Cu:DOM ratio is an important factor controlling Cu2+–DOM binding strength even for DOM isolates of different types and different sources and for whole water samples. The results were modeled with Visual MINTEQ and compared to results from the biotic ligand model (BLM). The BLM was found to over-estimate Cu2+ at low total copper concentrations and under-estimate Cu2+ at high total copper concentrations.

Carotenoids are the likely precursor of a significant fraction of marine dissolved organic matter

PubMed Central

Arakawa, Neal; Aluwihare, Lihini I.; Simpson, Andre J.; Soong, Ronald; Stephens, Brandon M.; Lane-Coplen, Daniel

2017-01-01

The ocean’s biota sequester atmospheric carbon dioxide (CO2) in part by producing dissolved organic matter (DOM) that persists in the ocean for millennia. This long-term accumulation of carbon may be facilitated by abiotic and biotic production of chemical structures that resist degradation, consequently contributing disproportionately to refractory DOM. Compounds that are selectively preserved in seawater were identified in solid-phase extracted DOM (PPL-DOM) using comprehensive gas chromatography (GC) coupled to mass spectrometry (MS). These molecules contained cyclic head groups that were linked to isoprenoid tails, and their overall structures closely resembled carotenoid degradation products (CDP). The origin of these compounds in PPL-DOM was further confirmed with an in vitro β-carotene photooxidation experiment that generated water-soluble CDP with similar structural characteristics. The molecular-level identification linked at least 10% of PPL-DOM carbon, and thus 4% of total DOM carbon, to CDP. Nuclear magnetic resonance spectra of experimental CDP and environmental PPL-DOM overlapped considerably, which indicated that even a greater proportion of PPL-DOM was likely composed of CDP. The CDP-rich DOM fraction was depleted in radiocarbon (14C age > 1500 years), a finding that supports the possible long-term accumulation of CDP in seawater. By linking a specific class of widespread biochemicals to refractory DOM, this work provides a foundation for future studies that aim to examine how persistent DOM forms in the ocean. PMID:28959723

Dom34 Links Translation to Protein O-mannosylation

PubMed Central

van Wijlick, Lasse; Geissen, René; Hilbig, Jessica S.; Lagadec, Quentin; Cantero, Pilar D.; Juchimiuk, Mateusz; Kluge, Sven; Wickert, Stephan; Alepuz, Paula; Ernst, Joachim F.

2016-01-01

In eukaryotes, Dom34 upregulates translation by securing levels of activatable ribosomal subunits. We found that in the yeast Saccharomyces cerevisiae and the human fungal pathogen Candida albicans, Dom34 interacts genetically with Pmt1, a major isoform of protein O-mannosyltransferase. In C. albicans, lack of Dom34 exacerbated defective phenotypes of pmt1 mutants, while they were ameliorated by Dom34 overproduction that enhanced Pmt1 protein but not PMT1 transcript levels. Translational effects of Dom34 required the 5′-UTR of the PMT1 transcript, which bound recombinant Dom34 directly at a CA/AC-rich sequence and regulated in vitro translation. Polysomal profiling revealed that Dom34 stimulates general translation moderately, but that it is especially required for translation of transcripts encoding Pmt isoforms 1, 4 and 6. Because defective protein N- or O-glycosylation upregulates transcription of PMT genes, it appears that Dom34-mediated specific translational upregulation of the PMT transcripts optimizes cellular responses to glycostress. Its translational function as an RNA binding protein acting at the 5′-UTR of specific transcripts adds another facet to the known ribosome-releasing functions of Dom34 at the 3′-UTR of transcripts. PMID:27768707

Dom34 Links Translation to Protein O-mannosylation.

PubMed

van Wijlick, Lasse; Geissen, René; Hilbig, Jessica S; Lagadec, Quentin; Cantero, Pilar D; Pfeifer, Eugen; Juchimiuk, Mateusz; Kluge, Sven; Wickert, Stephan; Alepuz, Paula; Ernst, Joachim F

2016-10-01

In eukaryotes, Dom34 upregulates translation by securing levels of activatable ribosomal subunits. We found that in the yeast Saccharomyces cerevisiae and the human fungal pathogen Candida albicans, Dom34 interacts genetically with Pmt1, a major isoform of protein O-mannosyltransferase. In C. albicans, lack of Dom34 exacerbated defective phenotypes of pmt1 mutants, while they were ameliorated by Dom34 overproduction that enhanced Pmt1 protein but not PMT1 transcript levels. Translational effects of Dom34 required the 5'-UTR of the PMT1 transcript, which bound recombinant Dom34 directly at a CA/AC-rich sequence and regulated in vitro translation. Polysomal profiling revealed that Dom34 stimulates general translation moderately, but that it is especially required for translation of transcripts encoding Pmt isoforms 1, 4 and 6. Because defective protein N- or O-glycosylation upregulates transcription of PMT genes, it appears that Dom34-mediated specific translational upregulation of the PMT transcripts optimizes cellular responses to glycostress. Its translational function as an RNA binding protein acting at the 5'-UTR of specific transcripts adds another facet to the known ribosome-releasing functions of Dom34 at the 3'-UTR of transcripts.

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

USGS Publications Warehouse

Leenheer, Jerry A.; Reddy, Michael M.

2008-01-01

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Seasonal organic matter dynamics in the Great Barrier Reef lagoon: Contribution of carbohydrates and proteins

NASA Astrophysics Data System (ADS)

Lønborg, Christian; Doyle, Jason; Furnas, Miles; Menendez, Patricia; Benthuysen, Jessica A.; Carreira, Cátia

2017-04-01

Organic matter (OM) plays a fundamental role in sustaining the high productivity of coral reef ecosystems. Carbohydrates and proteins constitute two of the major chemical classes identified in the OM pool and are used as indicators of bioavailability due to their fast turn-over. We conducted three cruises across the southern shelf of the Great Barrier Reef (GBR) during the early dry, late dry and wet seasons in 2009-2010 to 1) assess the relative bioavailability of particulate (POM) and dissolved (DOM) organic matter, 2) track the temporal and spatial variability in the carbohydrate and protein contribution to the OM pool, and 3) assess factors influencing protein and carbohydrate fractions of the OM pool. Generally, higher concentrations of particulate carbohydrates were found during the wet season, while similar concentrations of particulate protein were found during the three seasons. Both the dissolved carbohydrates and proteins had highest levels during the early dry season and lowest during the wet season, suggesting seasonal variations in the chemical composition of the DOM pool. Spatially, carbohydrates showed higher concentrations at the inshore stations, while no clear spatial pattern was found for the protein concentrations. On average carbohydrates and proteins accounted for a similar fraction (13±5 and 12±6% respectively) of POM, while carbohydrates accounted for a smaller fraction of the DOM than the proteins (6±3 and 13±10%). This suggests that the POM bioavailability was similar between seasons, while the DOM bioavailability varied seasonally with highest levels during the early dry season. This demonstrates that carbohydrates and proteins in the GBR have temporal and spatial variations. Our statistical analysis showed that 1) both carbohydrates and proteins were related with the POM and DOM C:N:P stoichiometry, demonstrating that both bulk estimates (stoichiometry) and specific compounds (CHO and Prot) provide useful measures of OM bioavailability in the GBR and 2) the carbohydrates and proteins levels were controlled by the amount of nutrients and POM, which in this system is mainly of plankton origin. Overall this study shows that the POM and DOM pools contain highly bioavailable compounds and that carbohydrate and proteins could play an important role in sustaining the productivity of the GBR.

Hydrological Controls on Dissolved Organic Matter Quality and Export in a Coastal River System in Southeastern USA

NASA Astrophysics Data System (ADS)

Bhattacharya, R.; Osburn, C. L.

2017-12-01

Dissolved organic matter (DOM) exported from river catchments can influence the biogeochemical processes in coastal environments with implications for water quality and carbon budget. High flow conditions are responsible for most DOM export ("pulses") from watersheds, and these events reduce DOM transformation and production by "shunting" DOM from river networks into coastal waters: the Pulse-Shunt Concept (PSC). Subsequently, the source and quality of DOM is also expected to change as a function of river flow. Here, we used stream dissolved organic carbon concentrations ([DOC]) along with DOM optical properties, such as absorbance at 350 nm (a350) and fluorescence excitation and emission matrices modeled by parallel factor analysis (PARAFAC), to characterize DOM source, quality and fluxes under variable flow conditions for the Neuse River, a coastal river system in the southeastern US. Observations were made at a flow gauged station above head of tide periodically between Aug 2011 and Feb 2013, which captured low flow periods in summer and several high flow events including Hurricane Irene. [DOC] and a350 were correlated and varied positively with river flow, implying that a large portion of the DOM was colored, humic and flow-mobilized. During high flow conditions, PARAFAC results demonstrated the higher influx of terrestrial humic DOM, and lower in-stream phytoplankton production or microbial degradation. However, during low flow, DOM transformation and production increased in response to higher residence times and elevated productivity. Further, 70% of the DOC was exported by above average flows, where 3-4 fold increases in DOC fluxes were observed during episodic events, consistent with PSC. These results imply that storms dramatically affects DOM export to coastal waters, whereby high river flow caused by episodic events primarily shunt terrestrial DOM to coastal waters, whereas low flow promotes in-stream DOM transformation and amendment with microbial DOM.

Temporal Changes in Photochemically Labile DOM and Implications for Carbon Budgets in Peatland Aquatic Systems

NASA Astrophysics Data System (ADS)

Pickard, A.

2015-12-01

Aquatic systems in peatland catchments are subject to high loading of dissolved organic matter (DOM) from surrounding terrestrial environments. However the significance of photochemical transformation of DOM in peatland carbon budgets remains poorly constrained. In this study UV irradiation experiments were conducted on water samples collected over one year from two contrasting systems in Scotland: a stream draining a peatland with high levels of DOM and a reservoir draining a peat catchment with low levels of DOM. Further samples were collected from the high DOM system during two storm events. After experimental exposure, optical and chemical analyses were employed to determine photochemical lability of the DOM pool. At both sites irradiation-induced decreases in dissolved organic carbon (DOC) as a percentage of the total carbon pool were greatest in winter, suggesting that DOM was depleted in photo-reactive molecules in summer. Seasonal variability in DOC was high at the stream site and was positively correlated with CO₂ and CO photoproduction (r2 = 0.81 and 0.83, respectively; p<0.05). Lignin phenol analyses indicate considerable contribution of peat to the DOM pool at the stream site, particularly during summer. Whilst DOC concentrations did not vary greatly during storm events, UV-Vis absorbance indicators did, signifying changing DOM source material from activation of different hydrological pathways. The most photo-reactive DOM occurred 5-10 hours after peak discharge, suggesting that storms replenish photochemically labile DOM in headwater streams. Conservative estimates using data from this study suggest that up to 7% of the DOM pool of peatland streams can be lost (primarily as CO₂ and CO) upon exposure to 8 hours of environmentally representative UV irradiation. Further investigation in field campaigns under natural UV exposure are underway to assess the importance of photodegradation of DOM as a loss pathway of carbon based gases from aquatic systems.

Dynamics of dissolved organic matter (DOM) in a typical inland lake of the Three Gorges Reservoir area: Fluorescent properties and their implications for dissolved mercury species.

PubMed

Jiang, Tao; Chen, Xueshuang; Wang, Dingyong; Liang, Jian; Bai, Weiyang; Zhang, Cheng; Wang, Qilei; Wei, Shiqiang

2018-01-15

Dissolved organic matter (DOM) plays an important environmental and ecological role in inland aquatic systems, including lakes. In this study, using fluorescence analysis, we investigated the seasonal dynamics of DOM characteristics in Changshou Lake, which is a typical inland lake in the Three Gorges Reservoir (TGR) area. We also discuss the environmental implications of DOM for mercury (Hg) dynamics. Based on the origins of two end-members, the variations in DOM observed in this study in Changshou Lake suggest that hydrological processes (e.g., terrestrial inputs resulting from runoff and humic-like component residences) and biological activities (e.g., microbial and algae growth) are the two main principal components controlling the seasonal dynamics of DOM characteristics. Furthermore, the dynamics of dissolved Hg co-varied with variations in DOM properties, rather than with dissolved organic carbon (DOC) concentrations. This indicates that the previously reported simple correlations between DOC and Hg were not comprehensive and may lead to misunderstanding the interactions between DOM and Hg. Therefore, we recommend that when using DOM-Hg correlations to evaluate the role of DOM in the environmental fate of Hg, especially in field investigations of the spatial and temporal distribution of Hg, the properties of DOM must be taken into account. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mixing and photoreactivity of dissolved organic matter in the Nelson/Hayes estuarine system (Hudson Bay, Canada)

NASA Astrophysics Data System (ADS)

Guéguen, C.; Mokhtar, M.; Perroud, A.; McCullough, G.; Papakyriakou, T.

2016-09-01

This work presents the results of a 4-year study (2009-2012) investigating the mixing and photoreactivity of dissolved organic matter (DOM) in the Nelson/Hayes estuary (Hudson Bay). Dissolved organic carbon (DOC), colored DOM, and humic-like DOM decreased with increasing salinity (r2 = 0.70-0.84). Removal of DOM was noticeable at low to mid salinity range, likely due to degradation and/or adsorption to particles. DOM photobleaching rates (i.e., decrease in DOM signal resulting from exposure to solar radiation) ranged from 0.005 to 0.030 h- 1, corresponding to half-lives of 4.9-9.9 days. Dissolved organic matter from the Nelson and Hayes Rivers was more photoreactive than from the estuary where the photodegradation of terrestrial DOM decreased with increasing salinity. Coincident with the loss of CDOM absorption was an increase in spectral slope S, suggesting a decrease in DOM molecular weight. Marked differences in photoreactivity of protein- and humic-like DOM were observed with highly humidified material being the most photosensitive. Information generated by our study will provide a valuable data set for better understanding the impacts of future hydroelectric development and climate change on DOM biogeochemical dynamics in the Nelson/Hayes estuary and coastal domain. This study will constitute a reference on terrestrial DOM fate prior to building additional generating capacity on the Nelson River.

Roxarsone binding to soil-derived dissolved organic matter: Insights from multi-spectroscopic techniques.

PubMed

Fu, Qing-Long; He, Jian-Zhou; Blaney, Lee; Zhou, Dong-Mei

2016-07-01

The fate and transport of roxarsone (ROX), a widely used organoarsenic feed additive, in soil is significantly influenced by the ubiquitous presence of soil-derived dissolved organic matter (DOM). In this study, fluorescence quenching titration and two-dimensional correlation spectroscopy (2D-COS) were employed to study ROX binding to DOM. Binding mechanisms were revealed by fluorescence lifetime measurement and Fourier transform infrared spectroscopy (FTIR). Humic- and protein-like fluorophores were identified in the excitation-emission matrix and synchronous fluorescence spectra of DOM. The conditional stability constant (log KC) for ROX binding to DOM was found to be 5.06, indicating that ROX was strongly bound to DOM. The binding order of ROX to DOM fluorophores revealed by 2D-COS followed the sequence of protein-like fluorophore ≈ the longer wavelength excited humic-like (L-humic-like) fluorophore > the shorter wavelength excited humic-like (S-humic-like) fluorophore. 2D-COS resolved issues with peak overlapping and allowed further exploration of the interaction between ROX and DOM. Results of fluorescence lifetime and FTIR spectra demonstrated that ROX interacted with DOM through the hydroxyl, amide II, carboxyl, aliphatic CH, and NO2 groups, yielding stable DOM-ROX complexes. The strong interaction between ROX and DOM implies that DOM plays an important role in the environmental fate of ROX in soil. Copyright © 2016 Elsevier Ltd. All rights reserved.

On the use of hydroxyl radical kinetics to assess the number-average molecular weight of dissolved organic matter.

PubMed

Appiani, Elena; Page, Sarah E; McNeill, Kristopher

2014-10-21

Dissolved organic matter (DOM) is involved in numerous environmental processes, and its molecular size is important in many of these processes, such as DOM bioavailability, DOM sorptive capacity, and the formation of disinfection byproducts during water treatment. The size and size distribution of the molecules composing DOM remains an open question. In this contribution, an indirect method to assess the average size of DOM is described, which is based on the reaction of hydroxyl radical (HO(•)) quenching by DOM. HO(•) is often assumed to be relatively unselective, reacting with nearly all organic molecules with similar rate constants. Literature values for HO(•) reaction with organic molecules were surveyed to assess the unselectivity of DOM and to determine a representative quenching rate constant (k(rep) = 5.6 × 10(9) M(-1) s(-1)). This value was used to assess the average molecular weight of various humic and fulvic acid isolates as model DOM, using literature HO(•) quenching constants, kC,DOM. The results obtained by this method were compared with previous estimates of average molecular weight. The average molecular weight (Mn) values obtained with this approach are lower than the Mn measured by other techniques such as size exclusion chromatography (SEC), vapor pressure osmometry (VPO), and flow field fractionation (FFF). This suggests that DOM is an especially good quencher for HO(•), reacting at rates close to the diffusion-control limit. It was further observed that humic acids generally react faster than fulvic acids. The high reactivity of humic acids toward HO(•) is in line with the antioxidant properties of DOM. The benefit of this method is that it provides a firm upper bound on the average molecular weight of DOM, based on the kinetic limits of the HO(•) reaction. The results indicate low average molecular weight values, which is most consistent with the recent understanding of DOM. A possible DOM size distribution is discussed to reconcile the small nature of DOM with the large-molecule behavior observed in other studies.

Modeling Effects of Lability on Microbial Uptake of DOM in River Reaches

NASA Astrophysics Data System (ADS)

Li, A.; Drummond, J. D.; Bowen, J. C.; Cory, R. M.; Kaplan, L.; Packman, A. I.

2017-12-01

Rivers are hotspots for biological degradation of dissolved organic matter (DOM), contributing to 1.8 petagrams of carbon emissions per year. DOM represents approximately 60% of the total mass of organic carbon transported within river networks, fueling stream ecosystem metabolism. Not all DOM is biodegradable, biodegradation rates vary based on lability, and lability decreases with reaction time. Fluorescent fractions of DOM (FDOM) are often used as proxies of DOM lability. Humic-like FDOM, previously considered recalcitrant and thought to contribute minimally to the biodegradable DOM pools, has recently been shown to contribute more than 50% to DOM uptake in bioreactor columns colonized by bacteria in stream water. Protein-like FDOM, a proxy for the biodegradable DOM pool, also contributes to the recalcitrant DOM pool in bioreactors. However, the contribution of different lability pools to DOM uptake at the reach scale remains elusive. Here we combine local-scale results from a bioreactor study and measures of stream geomorphology parameters to model reach-scale DOM uptake in White Clay Creek, a Pennsylvania piedmont stream with an intact, forested riparian zone and inputs from upland agriculture. Steady state modeling of a point-source, continuous injection of FDOM shows that humic-like FDOM contributes up to 80% of the total removal of FDOM at the reach scale, suggesting its importance to in-stream DOM uptake. Tryptophan-like FDOM, a protein-like FDOM, contributes to 80% of the remaining fraction of FDOM at the reach scale that incorporates longer timescales of transport and retention. This is consistent with recent local-scale findings that the lability of tryptophan-like FDOM decreases substantially with reaction time in bioreactors, such that it becomes much more recalcitrant as it travels downstream. Steady state modeling of a distributed source, continuous injection of FDOM shows that contributing sources distribute differently along the river reach for each FDOM component, due to their different uptake patterns. Thus, variations of DOM lability are important for estimating reach-scale microbial uptake and contributing sources of in-stream DOM.

Fluorescence excitation-emission matrix spectroscopy analysis of landfill leachate DOM in coagulation-flocculation process.

PubMed

Zhu, Guocheng; Wang, Chuang; Dong, Xingwei

2017-06-01

Landfill leachate contains a variety of organic matters, some of which can be excited and emit fluorescence signal. In order to degrade these organic matters, the pretreatment of the leachate is needed, which can improve the degradation performance of post-treatment process. Coagulation-flocculation is one of the important pretreatment processes to treat landfill leachate. Assessing the chemical compositions of landfill leachate is helpful in the understanding of their sources and fates as well as the mechanistic behaviors in the water environment. The present work aimed to use fluorescence excitation-emission matrix spectroscopy (EEMs) to characterize the chemical fractions of landfill leachate dissolved organic matter (DOM) in conjunction with parallel factor analysis (PARAFAC). Results showed that the DOM of landfill leachate tested in this study was identified resulting from microbial input, which included five typical characteristic peaks and four kinds of PARAFAC fractions. These fractions were mainly composed of hydrophobic macromolecule humic acid-like (HM-HA), hydrophilic intermediate molecular fulvic acid-like (HIM-FA), and hydrophilic small molecule protein-like substances (HSM-PS). HM-HA and HIM-FA were found to be easier to remove than HSM-PS. Further research on HSM-PS removal by coagulation-flocculation still needs to be improved.

Oligotrophic wetland sediments susceptible to shifts in microbiomes and mercury cycling with dissolved organic matter addition

PubMed Central

Gabor, Rachel S.; Schooler, Shon; McKnight, Diane M.; Knelman, Joseph E.

2018-01-01

Recent advances have allowed for greater investigation into microbial regulation of mercury toxicity in the environment. In wetlands in particular, dissolved organic matter (DOM) may influence methylmercury (MeHg) production both through chemical interactions and through substrate effects on microbiomes. We conducted microcosm experiments in two disparate wetland environments (oligotrophic unvegetated and high-C vegetated sediments) to examine the impacts of plant leachate and inorganic mercury loadings (20 mg/L HgCl2) on microbiomes and MeHg production in the St. Louis River Estuary. Our research reveals the greater relative capacity for mercury methylation in vegetated over unvegetated sediments. Further, our work shows how mercury cycling in oligotrophic unvegetated sediments may be susceptible to DOM inputs in the St. Louis River Estuary: unvegetated microcosms receiving leachate produced substantially more MeHg than unamended microcosms. We also demonstrate (1) changes in microbiome structure towards Clostridia, (2) metagenomic shifts toward fermentation, and (3) degradation of complex DOM; all of which coincide with elevated net MeHg production in unvegetated microcosms receiving leachate. Together, our work shows the influence of wetland vegetation in controlling MeHg production in the Great Lakes region and provides evidence that this may be due to both enhanced microbial activity as well as differences in microbiome composition. PMID:29632744

Investigating the effect of landfill leachates on the characteristics of dissolved organic matter in groundwater using excitation-emission matrix fluorescence spectra coupled with fluorescence regional integration and self-organizing map.

PubMed

He, Xiao-Song; Fan, Qin-Dong

2016-11-01

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation-emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as "free" molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.

Heat impact caused molecular level changes in solid and dissolved soil organic matter

NASA Astrophysics Data System (ADS)

Hofmann, Diana; Steffen, Bernhard; Eckhardt, Kai-Uwe; Leinweber, Peter

2015-04-01

The ubiquitous abundance of pyrolysed, highly aromatic organic matter, called "Black Carbon" (BC), in all environmental compartments became increasingly important in different fields of research beyond intensive investigated atmospheric aerosol due to climatic relevance. Its predominant high resistance to abiotic and biotic degradation resulted in turnover times from less than a century to several millennia. This recalcitrance led to the enrichment of BC in soils, accounting for 1-6% (European forest soils) to 60% (Chernozems) of total soil organic matter (SOM). Hence, soil BC acts an important sink in the global carbon cycle. In contrast, consequences for the nitrogen cycle up to date are rather inconsistently discussed. Soil related dissolved organic matter (DOM) is a major controlling factor in soil formation, an important pathway of organic matter transport and one of the largest active carbon reservoirs on earth, if considering oceans and other bodies of water. The aim of this study was to evaluate the effects of artificially simulated wildfire by thermal treatment on the molecular composition of water extractable soil organic matter (DOM). Soils from two outdoor lysimeters with different management history were investigated. Soil samples, non-heated and heated up to 350°C were analyzed for elemental composition (carbon, nitrogen and sulfur) and for bulk molecular composition by Pyrolysis-Field Ionization Mass Spectrometry (Py-FIMS) and synchrotron-based X-ray Absorption Near-Edge Spectroscopy (XANES) at the C- and N K-edges. DOM-samples obtained by hot water extraction, desalting and concentration by solid phase extraction were subsequently analyzed by flow injection analysis in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR-MS), equipped with an ESI source and a 7 T supra-conducting magnet (LTQ-FT Ultra, ThermoFisher Scientific). This technique is the key technique for the analysis of complex samples due to its outstanding mass resolution (used 400.000 at m/z 400 Da) and mass accuracy (≤ 1 ppm), simultaneously providing molecular level details of thousands of compounds. The characteristics and differences of the FTICR-MS spectra with as many as ten or more peaks at each nominal mass are discussed: heated samples showed considerable higher intensities of even numbered peaks. An in-house developed, automated post processing was used for further exploitation of the data with the aim of an unambiguous assignment of as many peaks as possible. Obtained mass lists were transformed for sorting and preparation/ interpretation of graphics like Kendrick and van Krevelen plots. The heat-treated solid samples show decreasing C/N ratios and the formation cyclic and N-heterocyclic compounds in good agreement among the various methods (Py-FIMS and C- and N-XANES). Detailed insight into the hot-water extracts by FTICR-MS showed clear qualitative as well as quantitative changes in the number and the intensity of nitrogen and nitrogen + sulfur containing compounds, respectively, which generally became enriched under soil heating. This demonstrates for the first time, that not only the bulk SOM is affected in structure by heat impact but also the more mobile DOM. We assume, that heat impact volatilizes and oxidizes parts of the organic substances is as expected but another part of the substances incorporates (further) nitrogen atom(s) similar to the generation of new compounds under the conditions of plasma etching in nitrogen atmosphere. This would explain to some extent, why soils are e.g. after fire clearing of vegetation are highly fertile for a short period (better plant acceptable compounds) but become more infertile in the long run, especially under tropical conditions with frequently heavy rain that would lead to an increased leaching of compounds with higher polarity.

High soil solution carbon and nitrogen concentrations in a drained Atlantic bog are reduced to natural levels by 10 years of rewetting

NASA Astrophysics Data System (ADS)

Frank, S.; Tiemeyer, B.; Gelbrecht, J.; Freibauer, A.

2014-04-01

Anthropogenic drainage of peatlands releases additional greenhouse gases to the atmosphere, and dissolved carbon (C) and nutrients to downstream ecosystems. Rewetting drained peatlands offers a possibility to reduce nitrogen (N) and C losses. In this study, we investigate the impact of drainage and rewetting on the cycling of dissolved C and N as well as on dissolved gases, over a period of 1 year and a period of 4 months. We chose four sites within one Atlantic bog complex: a near-natural site, two drained grasslands with different mean groundwater levels and a former peat cutting area rewetted 10 years ago. Our results clearly indicate that long-term drainage has increased the concentrations of dissolved organic carbon (DOC), ammonium, nitrate and dissolved organic nitrogen (DON) compared to the near-natural site. DON and ammonium contributed the most to the total dissolved nitrogen. Nitrate concentrations below the mean groundwater table were negligible. The concentrations of DOC and N species increased with drainage depth. In the deeply-drained grassland, with a mean annual water table of 45 cm below surface, DOC concentrations were twice as high as in the partially rewetted grassland with a mean annual water table of 28 cm below surface. The deeply drained grassland had some of the highest-ever observed DOC concentrations of 195.8 ± 77.3 mg L-1 with maximum values of >400 mg L-1. In general, dissolved organic matter (DOM) at the drained sites was enriched in aromatic moieties and showed a higher degradation status (lower DOC to DON ratio) compared to the near-natural site. At the drained sites, the C to N ratios of the uppermost peat layer were the same as of DOM in the peat profile. This suggests that the uppermost degraded peat layer is the main source of DOM. Nearly constant DOM quality through the profile furthermore indicated that DOM moving downwards through the drained sites remained largely biogeochemically unchanged. Unlike DOM concentration, DOM quality and dissolved N species distribution were similar in the two grasslands and thus unaffected by the drainage depth. Methane production during the winter months at the drained sites was limited to the subsoil, which was quasi-permanently water saturated. The recovery of the water table in the winter months led to the production of nitrous oxide around mean water table depth at the drained sites. The rewetted and the near-natural site had comparable DOM quantity and quality (DOC to DON ratio and aromaticity). 10 years after rewetting quasi-pristine biogeochemical conditions have been re-established under continuously water logged conditions in the former peat cut area. Only the elevated dissolved methane and ammonium concentrations reflected the former disturbance by drainage and peat extraction. Rewetting via polder technique seems to be an appropriate way to revitalize peatlands on longer timescales and to improve the water quality of downstream water bodies.

Dissolved Organic Matter Compositional Change and Biolability During Two Storm Runoff Events in a Small Agricultural Watershed

NASA Astrophysics Data System (ADS)

Eckard, Robert S.; Pellerin, Brian A.; Bergamaschi, Brian A.; Bachand, Philip A. M.; Bachand, Sandra M.; Spencer, Robert G. M.; Hernes, Peter J.

2017-10-01

Agricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and postharvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Storm water discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor analysis identified an 80% reduction in a protein-like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic-like, terrestrially sourced component (C4). Storm-driven releases tripled DOC concentration (from 2.8 to 8.7 mg L-1) during the first flush event in comparison to base flow and were terrestrially sourced, with an eightfold increase in vascular plant derived lignin phenols (23.0 to 185 μg L-1). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to storm water hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

Production and composition of pyrogenic dissolved organic matter from a logical series of laboratory-generated chars

NASA Astrophysics Data System (ADS)

Bostick, Kyle W.; Zimmerman, Andrew R.; Wozniak, Andrew. S.; Mitra, Siddhartha; Hatcher, Patrick G.

2018-04-01

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known of the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared to that of their parent solids. Over 17 daily leaching cycles, biochars made from oak at 250 to 650° C released decreasing amounts of C on both a weight (16.9 to 0.3%, respectively) and C yield basis (7.4 to 0.2% C, respectively). Aryl-C represented an estimated 32 to 82% of C in the parent solids (identified by 13C-NMR), but only 7 to 38% in the leachates (identified by 1H-NMR), though both increased with pyrolysis temperature. PyC, often operationally defined as condensed aromatic carbon (ConAC), was quantified using the benzenepolycarboxylic acid (BPCA) method. Tri- and tetra-carboxylated BPCAs were formed from non-pyrogenic reference materials, thus, only penta- and hexa-carboxylated BPCAs were used to derive a BPCA-C to ConAC conversion factor of 7.04. ConAC made up 24 to 57% of the pyrogenic solid C (excluding the 250 °C biochar), but only about 9 to 23% of their respective leachates' DOC, though both proportions generally increased with pyrolysis temperature. Weighted BPCA compound distributions, or the BPCA Aromatic Condensation (BACon) Index, indicate that ConAC cluster size increased in pyrogenic solids but not in leachates. Additional evidence presented suggests that both aromatic cluster size and O-containing functional group contents in the pyrogenic solid control pyC solubility. Overall, pyDOM was found to be compositionally dissimilar from its parent chars and contained a complex mixture of organic compound groups. Thus, it is expected that estimates of dissolved pyC production and export, made only by detection of ConAC, are too low by factors of 4 to 11.

The impact of solar radiation on the use of dissolved organic matter in two Ozark Streams: Possible role of photo-enhanced humification

NASA Astrophysics Data System (ADS)

Townsend, S. L.; Ziegler, S. E.

2005-05-01

The effect of solar radiation on dissolved organic matter (DOM) utilization was studied in two contrasting streams from June 2002 through October 2004. Moores Creek is an agricultural stream with elevated nutrient and dissolved organic carbon (DOC) concentrations. Huey Hollow is a forested stream with low nutrient and DOC concentrations. A series of experiments were conducted seasonally to assess how solar radiation influenced DOM utilization. Exposure of DOM to solar radiation significantly decreased its utilization during most seasons in both streams. Each stream experienced one seasonal period when exposure of DOM significantly increased bacterial production; during these periods, DOM appeared to be the least bioavailable and most photochemically reactive. Interestingly, in spring when bioavailability of DOM was lowest in Moores Creek solar radiation exposure further reduced DOM bioavailability. Elevated ammonium concentrations during this spring experiment suggest photochemically-enhanced humification may have been an important mechanism influencing DOM cycling. Bioassays using 15N-labeled ammonium indicated no significant effect of elevated ammonium on the utilization of DOM in either stream in fall 2004. Detection of elevated 15N in the DOM fractions, however, would reveal light stimulated humification under elevated ammonium concentrations not detected with the bioassay.

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. © 2014 SETAC.

Controls on the dynamics of dissolved organic matter in soils: A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalbitz, K.; Solinger, S.; Park, J.H.

Dissolved organic matter (DOM) in soils plays an important role in the biogeochemistry of carbon, nitrogen, and phosphorus, in pedogenesis, and in the transport of pollutants in soils. The aim of this review is to summarize the recent literature about controls on DOM concentrations and fluxes in soils. The authors focus on comparing results between laboratory and field investigations and on the differences between the dynamics of dissolved organic carbon (DOC), nitrogen (DON), and phosphorus (DOP). Both laboratory and field studies show that litter and humus are the most important DOM sources in soils. However, it is impossible to quantifymore » the individual contributions of each of these sources to DOM release. In addition, it is not clear how changes in the pool sizes of litter or humus may affect DOM release. High microbial activity, high fungal abundance, and any conditions that enhance mineralization all promote high DOM concentrations. However, under field conditions, hydrologic variability in soil horizons with high carbon contents may be more important than biotic controls. In subsoil horizons with low carbon contents, DOM may be adsorbed strongly to mineral surfaces, resulting in low DOM concentrations in the soil solution. There are strong indications that microbial degradation of DOM also controls the fate of DOM in the soil.« less

Comprehensive assessment of precursors, diagenesis, and reactivity to water treatment of dissolved and colloidal organic matter

USGS Publications Warehouse

Leenheer, J.A.

2004-01-01

A comprehensive isolation, fractionation, and characterization research approach was developed for dissolved and colloidal organic matter (DOM) in water, and it was applied to various surface- and groundwaters to assess DOM precursors, DOM diagenesis, and DOM reactivity to water treatment processes. Major precursors for natural DOM are amino sugars, condensed tannins, and terpenoids. Amino sugar colloids derived from bacterial cell walls are incompletely removed by drinking water treatment and foul reverse osmosis membranes, but are nearly quantitatively removed by soil/aquifer treatment. When chlorinated, amino sugars produce low yields of regulated disinfection by-products (DBFs) but they produce significant chlorine demand that is likely caused by chlorination of free amino groups. Condensed tannins are major precursors for "blackwater" DOM such as that found in the Suwannee River. This DOM produces high yields of DBPs upon chorination, and is efficiently removed by coagulation/flocculation treatment. Terpenoid-derived DOM appears to be biologically refractory, infiltrates readily into groundwater with little removal by soil/aquifer treatment, gives low DBF-yields upon chlorination and is poorly removed by coagulation/flocculation treatments. Peptides derived from proteins are major components of the base DOM fraction (10% or less of the mass of DOM), and this fraction produces large yields of haloacetonitriles upon chorination.

Study on substrate metabolism process of saline waste sludge and its biological hydrogen production potential.

PubMed

Zhang, Zengshuai; Guo, Liang; Li, Qianqian; Zhao, Yangguo; Gao, Mengchun; She, Zonglian

2017-07-01

With the increasing of high saline waste sludge production, the treatment and utilization of saline waste sludge attracted more and more attention. In this study, the biological hydrogen production from saline waste sludge after heating pretreatment was studied. The substrate metabolism process at different salinity condition was analyzed by the changes of soluble chemical oxygen demand (SCOD), carbohydrate and protein in extracellular polymeric substances (EPS), and dissolved organic matters (DOM). The excitation-emission matrix (EEM) with fluorescence regional integration (FRI) was also used to investigate the effect of salinity on EPS and DOM composition during hydrogen fermentation. The highest hydrogen yield of 23.6 mL H 2 /g VSS and hydrogen content of 77.6% were obtained at 0.0% salinity condition. The salinity could influence the hydrogen production and substrate metabolism of waste sludge.

Seasonal Variation of Eutrophication in Some Lakes of Danube Delta Biosphere Reserve.

PubMed

Török, Liliana; Török, Zsolt; Carstea, Elfrida M; Savastru, Dan

2017-01-01

  To understand the trophic state of lakes, this study aims to determine the dynamics of phytoplankton assemblages and the main factors that influence their seasonal variation. Sampling campaigns were carried out in three lakes from the Danube Delta Biosphere Reserve. Spectral analysis of specific phytoplankton pigments was applied as a diagnostic marker to establish the distribution and composition of phytoplankton taxonomic groups. Fluorescence spectroscopy was used to quantify changes in dissolved organic matter (DOM). The relative contribution of the main phytoplankton groups to the total phytoplankton biomass and the trend of development during succession of the seasons showed that cyanobacteria could raise potential ecological or human health problems. Moreover, fluorescence spectroscopy revealed that Cryptophyta and cyanobacteria were the main contributors to the protein-like components of DOM. It was concluded that fluorescence could be used to provide a qualitative evaluation of the eutrophication degree in Danube Delta lakes.

Electrochemically modified dissolved organic matter accelerates the combining photodegradation and biodegradation of 17α-ethinylestradiol in natural aquatic environment.

PubMed

He, Huan; Huang, Bin; Fu, Gen; Xiong, Dan; Xu, Zhixiang; Wu, Xinhao; Pan, Xuejun

2018-06-15

The photochemical conversion and microbial transformation of pollutants mediated by dissolved organic matter (DOM), including 17α-ethinylestradiol (EE2), are often accompanied in natural water. However, there are few studies to explore the connection and mechanism between the two processes. This research aims to investigate the mechanism of DOM after electrochemically modification mediated EE2 combining photodegradation and biodegradation in the environment and it want to explain the natural phenomena of DOM after electrochemical advanced treatment entering the water environment mediated EE2 natural degradation. The results showed that combining photodegradation with biodegradation rates of EE2 mediated by DOM and electrochemically modified DOM (E-DOM) were promoted obviously. The efficiency of EE2 biodegradation was shown to be strongly correlated with electron accepting capacity (EAC) of DOM. Electrochemical modification can increase the EAC of DOM leading to EE2 biodegradation accelerated, and it also can form more triplet-state DOM moieties to promote the EE2 photodegradation in irradiation conditions, due to the increasing of quinone-type structures in DOM. Moreover, cell polymeric secretion (CPS) secreted from the microorganism could be stimulated to an excited state by irradiation, and that also accelerated EE2 degradation. Photolysis combined with biochemical degradation yielded less toxic degradation products. This study shows that the emission of DOM in wastewater after electrochemical treatment could accelerate estrogen degradation and play a positive role on the pollutant transformation in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of quantity, quality, and contact time of dissolved organic matter on bioconcentration of benzo[a]pyrene in the nematode Caenorhabditis elegans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haitzer, M.; Hoess, S.; Burnison, B.K.

1999-03-01

Quantity and quality of dissolved organic matter (DOM) and the time allowed for DOM to interact with organic contaminants can influence their bioavailability. The authors studied the effect of natural aquatic DOM that had been in contact with benzo[a]pyrene (B[a]P) for 1 to 12 d on the bioconcentration of B[a]P in the nematode Caenorhabditis elegans. Dissolved organic matter quality and quantity was varied by using DOM from three different sources, each in three different concentrations. A model, based on the assumption that only freely dissolved B[a]P is bioavailable, was employed to estimate biologically determined partition coefficients [K{sub p}(biol.)]. Expressing themore » data for each combination of DOM source and contact time in a single K{sub p} (biol.) value allowed a direct comparison of the effects of different DOM qualities and contact times. The results show that the effect of DOM from a specific source was dependent on DOM quantity, but they also observed a distinct effect of DOM quality (represented by different sampling locations) on the bioconcentration of B[a]P. Contact time had no significant influence for the effects of two DOM sources on the bioconcentration of B[a]P. However, the third DOM source was significantly more effective with increased contact time, leading to lower B[a]P bioconcentration in the nematodes.« less

Association between arsenic and different-sized dissolved organic matter in the groundwater of black-foot disease area, Taiwan.

PubMed

Chen, Ting-Chien; Hseu, Zeng-Yei; Jean, Jiin-Shuh; Chou, Mon-Lin

2016-09-01

The formation of an arsenic (As)-dissolved organic matter (DOM) complex is important in driving the release of arsenic in groundwater. This study collected groundwater samples from a 20 m deep well throughout 2014 and separated each into three subsamples by ultrafiltration: high molecular weight-DOM (HDOM, 0.45 μm-10 kDa), medium molecular weight-DOM (MDOM, 10-1 kDa), and low molecular weight-DOM (LDOM, <1 kDa) solutions. The fractional DOM was measured with a three-dimensional excitation-emission matrix (EEM) via fluorescence spectroscopy. A fluorescence quenching method was used to calculate the apparent stability constant (Ks) between arsenic and the fractional DOM. Based on the EEM records, three fluorescence indicators were further calculated to characterize the DOM sources, including the fluorescence index (FI), the biological index (BI), and the humification index (HI). The experimental results indicated that arsenic in the groundwater was mainly partitioned into the MDOM and LDOM fractions. All fractional DOMs contained humic acid-like substances and were considered as microbial sources. LDOM had the highest humification degree and aromaticity, followed by MDOM and HDOM. The As and DOM association could be formed by a Fe-bridge, which was demonstrated by the Ks values and fourier transform infrared (FTIR) spectra of the DOM. The formation of AsFe-DOM complex was only significant in the MDOM and LDOM. Copyright © 2016 Elsevier Ltd. All rights reserved.

Temporal Dynamics in the Concentration, Flux, and Optical Properties of Tree-derived Dissolved Organic Matter (Tree-DOM) in an Epiphyte-laden Oak-cedar Forest.

NASA Astrophysics Data System (ADS)

Whitetree, A.; Van Stan, J. T., II; Wagner, S.; Guillemette, F.; Lewis, J.; Silva, L.; Stubbins, A.

2017-12-01

Studies on the fate and transport of dissolved organic matter (DOM) along the rainfall-to-discharge flow pathway typically begin in streams or soils, neglecting the initial enrichment of rainfall with DOM during contact with plant canopies. However, rain water can gather significant amounts of tree-derived DOM (tree-DOM) when it drains from the canopy, as throughfall, and down the stem, as stemflow. We examined the temporal variability of event-scale tree-DOM concentrations, yield, and optical (light absorbance and fluorescence) characteristics from an epiphyte-laden Quercus virginiana-Juniperus virginiana forest on Skidaway Island, Savannah, Georgia (USA). All tree-DOM fluxes were highly enriched compared to rainfall and epiphytes further increased concentrations. Stemflow DOC concentrations were greater than throughfall across study species, yet larger throughfall water yields produced greater DOC yields versus stemflow. Tree-DOM optical characteristics indicate it is aromatic-rich with FDOM dominated by humic-like fluorescence, containing 10-20% protein-like (tryptophan-like) fluorescence. Storm size was the only storm condition that strongly correlated with tree-DOM concentration and flux; however, throughfall and stemflow optical characteristics varied little across a wide range of storm conditions (from low magnitude events to intense tropical storms). Annual tree-DOM yields from the study forest (0.8-46 g-C m-2 yr-1) compared well to other yields along the rainfall-to- discharge flow pathway, exceeding DOM yields from some river watersheds.

Impact of Photooxidation and Biodegradation on the Fate of Oil Spilled During the Deepwater Horizon Incident: Advanced Stages of Weathering.

PubMed

Harriman, Brian H; Zito, Phoebe; Podgorski, David C; Tarr, Matthew A; Suflita, Joseph M

2017-07-05

While the biogeochemical forces influencing the weathering of spilled oil have been investigated for decades, the environmental fate and effects of "oxyhydrocarbons" in sand patties deposited on beaches are not well-known. We collected sand patties deposited in the swash zone on Gulf of Mexico beaches following the Deepwater Horizon oil spill. When sand patties were exposed to simulated sunlight, a larger concentration of dissolved organic carbon was leached into seawater than the corresponding dark controls. This result was consistent with the general ease of movement of seawater through the sand patties as shown with a 35 SO 4 2- radiotracer. Ultrahigh-resolution mass spectrometry, as well as optical measurements revealed that the chemical composition of dissolved organic matter (DOM) leached from the sand patties under dark and irradiated conditions were substantially different, but neither had a significant inhibitory influence on the endogenous rate of aerobic or anaerobic microbial respiratory activity. Rather, the dissolved organic photooxidation products stimulated significantly more microbial O 2 consumption (113 ± 4 μM) than either the dark (78 ± 2 μM) controls or the endogenous (38 μM ± 4) forms of DOM. The changes in the DOM quality and quantity were consistent with biodegradation as an explanation for the differences. These results confirm that sand patties undergo a gradual dissolution of DOM in both the dark and in the light, but photooxidation accelerates the production of water-soluble polar organic compounds that are relatively more amenable to aerobic biodegradation. As such, these processes represent previously unrecognized advanced weathering stages that are important in the ultimate transformation of spilled crude oil.

The Utility of CDOM for Improving the Resolution of Riverine DOM Fluxes and Biogeochemical Function

NASA Astrophysics Data System (ADS)

Spencer, R. G.; Aiken, G.; Mann, P. J.; Holmes, R. M.; Niggemann, J.; Dittmar, T.; Hernes, P.; Stubbins, A.

2014-12-01

A major historical limitation to geochemical studies assessing fluvial fluxes of dissolved organic matter (DOM) has been the issue of both temporal and spatial scaling. Examples will be presented from watersheds around the world highlighting how chromophoric dissolved organic matter (CDOM) measurements can be utilized as proxies for more intensive and expensive analytical analyses (e.g. molecular-level organic biomarkers). Utilizing these refined CDOM loads for terrigenous biomarkers results in improved temporal resolution and a significant change in flux estimates. Examining CDOM and dissolved organic carbon (DOC) flux data from an assortment of terrestrial biomes we establish a robust 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 a range of rivers are correlated to watershed percent wetland and 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. Finally, examples will be presented linking CDOM parameters to DOM composition and biogeochemical properties with the aim of providing measurements to improve the spatial and especially temporal resolution of the role DOM plays in fluvial networks.

Spatiotemporal Distribution, Sources, and Photobleaching Imprint of Dissolved Organic Matter in the Yangtze Estuary and Its Adjacent Sea Using Fluorescence and Parallel Factor Analysis

PubMed Central

Li, Penghui; Chen, Ling; Zhang, Wen; Huang, Qinghui

2015-01-01

To investigate the seasonal and interannual dynamics of dissolved organic matter (DOM) in the Yangtze Estuary, surface and bottom water samples in the Yangtze Estuary and its adjacent sea were collected and characterized using fluorescence excitation-emission matrices (EEMs) and parallel factor analysis (PARAFAC) in both dry and wet seasons in 2012 and 2013. Two protein-like components and three humic-like components were identified. Three humic-like components decreased linearly with increasing salinity (r>0.90, p<0.001), suggesting their distribution could primarily be controlled by physical mixing. By contrast, two protein-like components fell below the theoretical mixing line, largely due to microbial degradation and removal during mixing. Higher concentrations of humic-like components found in 2012 could be attributed to higher freshwater discharge relative to 2013. There was a lack of systematic patterns for three humic-like components between seasons and years, probably due to variations of other factors such as sources and characteristics. Highest concentrations of fluorescent components, observed in estuarine turbidity maximum (ETM) region, could be attributed to sediment resuspension and subsequent release of DOM, supported by higher concentrations of fluorescent components in bottom water than in surface water at two stations where sediments probably resuspended. Meanwhile, photobleaching could be reflected from the changes in the ratios between fluorescence intensity (Fmax) of humic-like components and chromophoric DOM (CDOM) absorption coefficient (a355) along the salinity gradient. This study demonstrates the abundance and composition of DOM in estuaries are controlled not only by hydrological conditions, but also by its sources, characteristics and related estuarine biogeochemical processes. PMID:26107640

Application of advanced characterization techniques to assess DOM treatability of micro-polluted and un-polluted drinking source waters in China.

PubMed

Wang, Dongsheng; Xing, Linan; Xie, Jiankun; Chow, Christopher W K; Xu, Zhizhen; Zhao, Yanmei; Drikas, Mary

2010-09-01

China has a very complex water supply system which relies on many rivers and lakes. As the population and economic development increases, water quality is greatly impacted by anthropogenic processes. This seriously affects the character of the dissolved organic matter (DOM) and imposes operational challenges to the water treatment facilities in terms of process optimization. The aim of this investigation was to compare selected drinking water sources (raw) with different DOM character, and the respective treated waters after coagulation, using simple organic characterization techniques to obtain a better understanding of the impact of source water quality on water treatment. Results from the analyses of selected water samples showed that the dissolved organic carbon (DOC) of polluted waters is generally higher than that of un-polluted waters, but the specific UV absorbance value has the opposite trend. After resolving the high performance size exclusion chromatography (HPSEC) peak components of source waters using peak fitting, the twelve waters studied can be divided into two main groups (micro-polluted and un-polluted) by using cluster analysis. The DOM removal efficiency (treatability) of these waters has been compared using four coagulants. For water sources allocated to the un-polluted group, traditional coagulants (Al(2)(SO(4))(3) and FeCl(3)) achieved better removal. High performance poly aluminum chloride, a new type of composite coagulant, performed very well and more efficiently for polluted waters. After peak fitting the HPSEC chromatogram of each of the treated waters, average removal efficiency of the profiles can be calculated and these correspond well with DOC and UV removal. This provides a convenient tool to assess coagulation removal and coagulant selection. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Evaluating oxidation-reduction properties of dissolved organic matter from Chinese milk vetch (Astragalus sinicus L.): a comprehensive multi-parametric study.

PubMed

Liu, Yong; Lou, Jun; Li, Fang-Bai; Xu, Jian-Ming; Yu, Xiong-Sheng; Zhu, Li-An; Wang, Feng

2014-08-01

Green manuring is a common practice in replenishment of soil organic matter and nutrients in rice paddy field. Owing to the complex interplay of multiple factors, the oxidation--reduction (redox) properties of dissolved organic matter (DOM) from green manure crops are presently not fully understood. In this study, a variety of surrogate parameters were used to evaluate the redox capacity and redox state of DOM derived from Chinese milk vetch (CMV, Astragalus sinicus L.) via microbial decomposition under continuously flooded (CF) and non-flooded (NF) conditions. Additionally, the correlation between the surrogate parameters of CMV-DOM and the kinetic parameters of relevant redox reactions was evaluated in a soil-water system containing CMV-DOM. Results showed that the redox properties of CMV-DOM were substantially different between the fresh and decomposed CMV-DOM treatments. Determination of the surrogate parameters via ultraviolet-visible/Fourier transform infrared absorption spectroscopy and gel permeation chromatography generally provided high-quality data for predicting the redox capacity of CMV-DOM, while the surrogate parameters determined by elemental analysis were suitable for predicting the redox state of CMV-DOM. Depending on the redox capacity and redox state of various moieties/components, NF-decomposed CMV-DOM could easily accelerate soil reduction by shuttling electrons to iron oxides, because it contained more reversible redox-active functional groups (e.g. quinone and hydroquinone pairs) than CF-decomposed CMV-DOM. This work demonstrates that a single index cannot interpret complex changes in multiple factors that jointly determine the redox reactivity of CMV-DOM. Thus, a multi-parametric study is needed for providing comprehensive information on the redox properties of green manure DOM.

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+)). Copyright © 2015 Elsevier Ltd. All rights reserved.

The effect of probe choice and solution conditions on the apparent photoreactivity of dissolved organic matter.

PubMed

Maizel, Andrew C; Remucal, Christina K

2017-08-16

Excited triplet states of dissolved organic matter ( 3 DOM) are quantified directly with the species-specific probes trans,trans-hexadienoic acid (HDA) and 2,4,6-trimethylphenol (TMP), and indirectly with the singlet oxygen ( 1 O 2 ) probe furfuryl alcohol (FFA). Although previous work suggests that these probe compounds may be sensitive to solution conditions, including dissolved organic carbon concentration ([DOC]) and pH, and may quantify different 3 DOM subpopulations, the probes have not been systematically compared. Therefore, we quantify the apparent photoreactivity of diverse environmental waters using HDA, TMP, and FFA. By conducting experiments under ambient [DOC] and pH, with standardized [DOC] and pH, and with solid phase extraction isolates, we demonstrate that much of the apparent dissimilarity in photochemical measurements is attributable to solution conditions, rather than intrinsic differences in 3 DOM production. In general, apparent quantum yields (Φ 1 O 2 ≥ Φ 3 DOM,TMP ≫ Φ 3 DOM,HDA ) and pseudo-steady state concentrations ([ 1 O 2 ] ss > [ 3 DOM] ss,TMP > [ 3 DOM] ss,HDA ) show consistent relationships in all waters under standardized conditions. However, intrinsic differences in 3 DOM photoreactivity are apparent between DOM from diverse sources, as seen in the higher Φ 1 O 2 and lower Φ 3 DOM,TMP of wastewater effluents compared with oligotrophic lakes. Additionally, while conflicting trends in photoreactivity are observed under ambient conditions, all probes observe quantum yields increasing from surface wetlands to terrestrially influenced waters to oligotrophic lakes under standardized conditions. This work elucidates how probe selection and solution conditions influence the apparent photoreactivity of environmental waters and confirms that 3 DOM or 1 O 2 probes cannot be used interchangeably in waters that vary in [DOC], pH, or DOM source.

Source and Processes of Dissolved Organic Matter in a Bangladesh Groundwater

NASA Astrophysics Data System (ADS)

McKnight, D. M.; Simone, B. E.; Mladenov, N.; Zheng, Y.; Legg, T. M.; Nemergut, D.

2010-12-01

Arsenic contamination of groundwater is a global health crisis, especially in Bangladesh where an estimated 40 million people are at risk. The release of geogenic arsenic bound to sediments into groundwater is thought to be influenced by dissolved organic matter (DOM) through several biogeochemical processes. Abiotically, DOM can promote the release of sediment bound As through the formation of DOM-As complexes and competitive interactions between As and DOM for sorption sites on the sediment. Additionally, the labile portion of groundwater DOM can serve as an electron donor to support microbial growth and the more recalcitrant humic DOM may serve as an electron shuttle, facilitating the eventual reduction of ferric iron present as iron oxides in sediments and consequently the mobilization of sorbed As and organic material. The goal of this study is to understand the source of DOM in representative Bangladesh groundwaters and the DOM sorption processes that occur at depth. We report chemical characteristics of representative DOM from a surface water, a shallow low-As groundwater, mid-depth high-As groundwater from the Araihazar region of Bangladesh. The humic DOM from groundwater displayed a more terrestrial chemical signature, indicative of being derived from plant and soil precursor materials, while the surface water humic DOM had a more microbial signature, suggesting an anthropogenic influence. In terms of biogeochemical processes occurring in the groundwater system, there is evidence from a diverse set of chemical characteristics, ranging from 13C-NMR spectroscopy to the analysis of lignin phenols, for preferential sorption onto iron oxides influencing the chemistry and reactivity of humic DOM in high As groundwater in Bangladesh. Taken together, these results provide chemical evidence for anthropogenic influence and the importance of sorption reactions at depth controlling the water quality of high As groundwater in Bangladesh.

New insights on ecosystem mercury cycling revealed by stable isotopes of mercury in water flowing from a headwater peatland catchment

Treesearch

Glenn E. Woerndle; Martin Tsz-Ki Tsui; Stephen D. Sebestyen; Joel D. Blum; Xiangping Nie; Randall K. Kolka

2018-01-01

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a...

Partitioning of dissolved organic matter-bound mercury between a hydrophobic surface and polysulfide-rubber polymer.

PubMed

Kim, Eun-Ah; Luthy, Richard G

2011-11-01

This study investigated the role of dissolved organic matter on mercury partitioning between a hydrophobic surface (polyethylene, PE) and a reduced sulfur-rich surface (polysulfide rubber, PSR). Comparative sorption studies employed polyethylene and polyethylene coated with PSR for reactions with DOM-bound mercuric ions. These studies revealed that PSR enhanced the Hg-DOM removal from water when DOM was Suwannee River natural organic matter (NOM), fulvic acid (FA), or humic acid (HA), while the same amount of 1,3-propanedithiol-bound mercuric ion was removed by both PE and PSR-PE. The differences for Hg-DOM removal efficiencies between PE and PSR-PE varied depending on which DOM was bound to mercuric ion as suggested by the PE/water and PSR-PE/water partition coefficients for mercury. The surface concentrations of mercury on PE and PSR-PE with the same DOM measured by x-ray photoelectron spectroscopy were similar, which indicated the comparable amounts of immobilized mercury on PE and PSR-PE being exposed to the aqueous phase. With these observations, two major pathways for the immobilization reactions between PSR-PE and Hg-DOM were examined: 1) adsorption of Hg-DOM on PE by hydrophobic interactions between DOM and PE, and 2) addition reaction of Hg-DOM onto PSR by a complexation reaction between Hg and PSR. The percent contribution of each pathway was derived from a mass balance and the ratios among aqueous mercury, PE-bound Hg-DOM, and PSR-bound Hg-DOM concentrations. The results indicate strong binding of mercuric ion with both dissolved organic matter and PSR polymer. The FT-IR examination of Hg-preloaded-PSR-PEs after the reaction with DOM corroborated a strong interaction between mercuric ion and 1,3-propanedithiol compared to Hg-HA, Hg-FA, or Hg-NOM interactions. Copyright © 2011 Elsevier Ltd. All rights reserved.

Partitioning of dissolved organic matter-bound mercury between a hydrophobic surface and polysulfide-rubber polymer

PubMed Central

Kim, Eun-Ah

2011-01-01

This study investigated the role of dissolved organic matter on mercury partitioning between a hydrophobic surface (polyethylene, PE) and a reduced sulfur-rich surface (polysulfide rubber, PSR). Comparative sorption studies employed polyethylene and polyethylene coated with PSR for reactions with DOM-bound mercuric ions. These studies revealed that PSR enhanced the Hg-DOM removal from water when DOM was Suwannee River natural organic matter (NOM), fulvic acid (FA), or humic acid (HA), while the same amount of 1,3-propanedithiol-bound mercuric ion was removed by both PE and PSR-PE. The differences for Hg-DOM removal efficiencies between PE and PSR-PE varied depending on which DOM was bound to mercuric ion as suggested by the PE/water and PSR-PE/water partition coefficients for mercury. The surface concentrations of mercury on PE and PSR-PE with the same DOM measured by x-ray – photoelectron spectroscopy were similar, which indicated the comparable amounts of immobilized mercury on PE and PSR-PE being exposed to the aqueous phase. With these observations, two major pathways for the immobilization reactions between PSR-PE and Hg- DOM were examined: 1) adsorption of Hg-DOM on PE by hydrophobic interactions between DOM and PE, and 2) addition reaction of Hg-DOM onto PSR by a complexation reaction between Hg and PSR. The percent contribution of each pathway was derived from a mass balance and the ratios among aqueous mercury, PE-bound Hg-DOM, and PSR-bound Hg-DOM concentrations. The results indicate strong binding of mercuric ion with both dissolved organic matter and PSR polymer. The FT-IR examination of Hg-preloaded-PSR-PEs after the reaction with DOM corroborated a strong interaction between mercuric ion and 1,3-propanedithiol compared to Hg-HA, Hg-FA, or Hg-NOM interactions. PMID:21872900

Phototransformation of pesticides in prairie potholes: effect of dissolved organic matter in triplet-induced oxidation.

PubMed

Karpuzcu, M Ekrem; McCabe, Andrew J; Arnold, William A

2016-02-01

Photochemical reactions involving a variety of photosensitizers contribute to the abiotic transformation of pesticides in prairie pothole lakes (PPLs). Despite the fact that triplet excited state dissolved organic matter (DOM) enhances phototransformation of pesticides by acting as a photosensitizer, it may also decrease the overall phototransformation rate through various mechanisms. In this study, the effect of DOM on the phototransformation of four commonly applied pesticides in four different PPL waters was investigated under simulated sunlight using photoexcited benzophenone-4-carboxylate as the oxidant with DOM serving as an anti-oxidant. For atrazine and mesotrione, a decrease in phototransformation rates was observed, while phototransformations of metolachlor and isoproturon were not affected by DOM inhibition. Phototransformation rates and the extent of inhibition/enhancement by DOM varied spatially and temporally across the wetlands studied. Characterization of DOM from the sites and different seasons suggested that the DOM type and variations in the DOM structure are important factors controlling phototransformation rates of pesticides in PPLs.

Visually induced analgesia in a deep tissue experimental pain model: A randomised crossover experiment.

PubMed

van Selm, M J; Gibson, W I; Travers, M J; Moseley, G L; Hince, D; Wand, B M

2018-04-20

Visualizing one's own painful body part appears to have an effect on reported pain intensity. Furthermore, it seems that manipulating the size of the viewed image can determine the direction and extent of this phenomenon. When visual distortion has been applied to clinical populations, the analgesic effects have been in opposition to those observed in some experimental pain models. To help resolve this problem, we explored the effect of visualisation and magnification of the visual image on reported pain using a delayed onset muscle soreness (DOMS) pain model. We induced DOMS in the quadriceps of 20 healthy volunteers. Forty-eight hours later, participants performed a series of painful contractions of the DOMS-affected muscle under four randomised conditions: (1) Viewing the injured thigh; (2) Viewing the contralateral thigh; (3) Viewing a neutral object; and (4) Viewing the injured thigh through magnifying glasses. For each condition, participants rated their pain intensity during a series of painful contractions. We observed that direct visualisation of the injured thigh had no effect on pain intensity when compared to viewing the contralateral thigh or neutral object. However, magnification of the DOMS-affected leg during the performance of painful contractions caused participants to report more pain than when viewing the injured thigh normally. These results further demonstrate that the effect of visualisation varies between different pain conditions. These results may have implications for the integration of visual feedback into clinical practice. We present delayed onset muscle soreness as a model for exploring visually induced analgesia. Our findings suggest that this phenomenon is expressed differently in exogenous and endogenous experimental pain models. Further exploration may offer a potential pathway for the integration of visual analgesia into the management of clinical pain. © 2018 European Pain Federation - EFIC®.

Formation of nanocolloidal metacinnabar in mercury-DOM-sulfide systems

USGS Publications Warehouse

Gerbig, Chase A.; Kim, Christopher S.; Stegemeier, John P.; Ryan, Joseph N.; Aiken, George R.

2011-01-01

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM)−1) by combining solid phase extraction using C18 resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C18 resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury–sulfur bonds with a longer interatomic distance (2.51–2.53 Å) similar to the mercury–sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg–1) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form, and these species need to be considered when addressing mercury biogeochemistry.

Transformations of DOM in forested catchments: the pathways of DOM from litter and soil to river export

NASA Astrophysics Data System (ADS)

Lajtha, K.; Yano, Y.; Crow, S.; Kaushal, S.

2006-12-01

Although the quality and quantity of DOM ultimately derives from plant detritus and soils in watersheds, three is substantial alteration of DOM as it passes from litter through the terrestrial landscape. As DOM is generated from plant and microbial detritus and processing, different fractions may be lost via respiration, form quasi-stable soil organic matter, or be temporarily sorbed to soil minerals. We followed the fate of DOC and DON from forested plots with experimentally altered detritus loads to determine the relative roles of original plant litter chemistry and soil transformations. Our study site was the DIRT (Detrital Input and Removal Treatment) plots at the H.J. Andrews Experimental Forest in Oregon, where treatments include detrital additions (wood vs. needle litter), litter exclusion, and root exclusions. Fractionation of detritus leachate solutions demonstrated significant differences in DOC chemistry from different detrital sources. Root leachates produced high quantities of hydrophilic neutral DOC, a fraction rich in labile sugars and polysaccharides; young wood extracts produced higher quantities of weak hydrophobic acids and hydrophobic neutrals (longer chain hydrocarbons); older wood had lower quantities of most labile constituents but was rich in strong hydrophobic acids. Although laboratory extracts of different litter types showed differences in DOM chemistry, soil solutions collected just below the forest floor from the differing detrital treatments were remarkably uniform and poor in labile constituents, suggesting microbial equalization of DOM leachate in the field. DOM quality and concentrations changed significantly with passage through soil profiles. DOC concentrations decreased through the soil profile in all plots to a greater degree than did dissolved organic nitrogen (DON), most likely due to preferential sorption of high C:N hydrophobic dissolved organic matter (DOM) in upper horizons. Percent hydrophobic DOM decreased significantly with depth, and the remaining hydrophilic DOM had a much lower and narrower C:N ratio than hydrophobic DOM. We also hypothesize that protein-reactive polyphenols, or tannins, may contribute to the decreased lability of N-rich DOM in soil solutions and thus significantly influence the quality of DOM delivered to streams.

The effect of source material in determining the photoreactivity of DOM in peatland aquatic systems

NASA Astrophysics Data System (ADS)

Pickard, Amy; Heal, Kate; McLeod, Andy; Dinsmore, Kerry

2016-04-01

Aquatic systems draining peatlands receive a high loading of dissolved organic matter (DOM) from surrounding terrestrial environments. However the fate of aquatic DOM remains poorly constrained, in part due to lack of knowledge regarding the photoreactivity of DOM and how this changes as a function of variability in source material. In this study water samples were collected monthly for a 13-month period from two contrasting aquatic systems in Scotland: a stream draining a peatland with high DOM concentrations (33.3 ± 14.2 mg DOC L-1) and a reservoir draining a peat catchment with low DOM concentrations (4.16 ± 0.91 mg DOC L-1). Controlled UV irradiation laboratory experiments were conducted on samples filtered to 0.2 μm in order to assess the photoreactivity of the DOM, measured as the unit mass of DOC lost upon irradiation. Experiments took place over 8h in temperature controlled conditions, with unirradiated samples used as controls. After exposure, a range of analytical techniques were used to characterise the DOM to yield information about its source material and to determine how this was related to the observed photoreactivity. Lignin phenol analyses indicate considerable contribution of Sphagnum to DOM at the stream site, particularly during summer, as demonstrated by high P-hydroxy/Vanillyl phenol ratios (P/V). Low P/V ratios were correlated with increased photoreactivity, (Pearson's: -0.410; p = 0.15, n = 13), suggesting that DOM from woody lignin sources within the catchment was more photolabile. Photoreactivity was also negatively correlated with Fluorescence Index (FI) values (Pearson's: -0.555; p = 0.055, n = 13), where low FI values are understood to indicate greater contribution of terrestrially derived material to aquatic DOM. Excitation-emission matrices (EEMs) indicate that DOM at the stream site was primarily comprised of a humic-like peak (Ex/Em = 340, 380/460 nm). However, there was also contribution from a protein-like peak (Ex/Em = 290, 320/350 nm), which was present in samples with lower photoreactivity. DOM at the reservoir site was primarily composed of the same identified protein-like peak, which may account for the lower observed photoreactivity of these samples. Although total DOC concentration is the dominant control on photo-induced DOC losses in peatland aquatic systems, these results show that organic matter characterisation can be used to further comprehend changes to DOM photoreactivity. Increased understanding of DOM processing in aquatic freshwater systems will allow the fate of DOM to be more accurately determined.

Investigating the effect of hardness cations on coagulation: The aspect of neutralisation through Al(III)-dissolved organic matter (DOM) binding.

PubMed

Zhou, Yuxuan; Yan, Mingquan; Liu, Ruiping; Wang, Dongsheng; Qu, Jiuhui

2017-05-15

Hardness cations are ubiquitous and abundant in source water, while the effect of hardness on the performance of coagulation for dissolved organic matter (DOM) removal in water treatment remains unclear due to the limitation of methods that can characterise the subtle interactions between DOM, coagulant and hardness cations. This work quantified the competition between coagulant Al 3+ and hardness cations to bind onto DOM using absorbance spectroscopy acquired at different Al 3+ concentrations in the absence and presence of Ca 2+ or Mg 2+ . The results indicate that, in the presence of either Mg 2+ or Ca 2+ , an increasing depression of the binding of Al 3+ -DOM could be observed in the differential spectra of DOM with the increasing of Mg 2+ or Ca 2+ at a level of 10, 100 and 1000 μM, with the observation being more significant at higher pH from 6.5 to 8.5. The results of zeta potentials of DOM indicate that the competition of hardness cations results in the negative DOM being less efficiently neutralised by Al 3+ . This study demonstrates that the removal of DOM by coagulation would significantly deteriorate with the presence of hardness cations, which would compete with coagulant Al 3+ to neutralise the unsaturated sites in DOM. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fate of 14C-labeled dissolved organic matter in paddy and upland soils in responding to moisture.

PubMed

Chen, Xiangbi; Wang, Aihua; Li, Yang; Hu, Lening; Zheng, Hua; He, Xunyang; Ge, Tida; Wu, Jinshui; Kuzyakov, Yakov; Su, Yirong

2014-08-01

Soil organic matter (SOM) content in paddy soils is higher than that in upland soils in tropical and subtropical China. The dissolved organic matter (DOM) concentration, however, is lower in paddy soils. We hypothesize that soil moisture strongly controls the fate of DOM, and thereby leads to differences between the two agricultural soils under contrasting management regimens. A 100-day incubation experiment was conducted to trace the fate and biodegradability of DOM in paddy and upland soils under three moisture levels: 45%, 75%, and 105% of the water holding capacity (WHC). (14)C labeled DOM, extracted from the (14)C labeled rice plant material, was incubated in paddy and upland soils, and the mineralization to (14)CO2 and incorporation into microbial biomass were analyzed. Labile and refractory components of the initial (14)C labeled DOM and their respective half-lives were calculated by a double exponential model. During incubation, the mineralization of the initial (14)C labeled DOM in the paddy soils was more affected by moisture than in the upland soils. The amount of (14)C incorporated into the microbial biomass (2.4-11.0% of the initial DOM-(14)C activity) was less affected by moisture in the paddy soils than in the upland soils. At any of the moisture levels, 1) the mineralization of DOM to (14)CO2 within 100 days was 1.2-2.1-fold higher in the paddy soils (41.9-60.0% of the initial DOM-(14)C activity) than in the upland soils (28.7-35.7%), 2) (14)C activity remaining in solution was significantly lower in the paddy soils than in the upland soils, and 3) (14)C activity remaining in the same agricultural soil solution was not significantly different among the three moisture levels after 20 days. Therefore, moisture strongly controls DOM fate, but moisture was not the key factor in determining the lower DOM in the paddy soils than in the upland soils. The UV absorbance of DOM at 280 nm indicates less aromaticity of DOM from the paddy soils than from the upland soils. At any of the moisture levels, much more labile DOM was found in paddy soils (34.3-49.2% of the initial (14)C labeled DOM) compared with that in upland soils (19.4-23.9%). This demonstrates that the lower DOM content in the paddy soil compared with that in the upland soil is probably determined by the less complex components and structure of the DOM. Copyright © 2014 Elsevier B.V. All rights reserved.

'invisible' DOM in hourly-resolved headwater river records from Northern Amazonia

NASA Astrophysics Data System (ADS)

Pereira, R.; Bovolo, C.; Spencer, R. G.; Hernes, P. J.; Tipping, E.; Vieth-Hillebrand, A.; Chappell, N.; Lewis-Franklin, A.; Parkin, G.; Wagner, T.

2012-12-01

Global river networks annually process ~3 billion tonnes of organic carbon but only ~17% reaches the ocean. These estimates suggest rivers are not mere transportation pipes but biogeochemical reactors. Inland waters are therefore fundamental to the understanding of carbon and nutrient interactions between land and ocean. Within these global estimates, tropical rivers contribute ~two-thirds of the global dissolved organic matter flux to the ocean. Recent studies suggest that up to 50% of the CO2 outgassed from tropical rivers is derived from terrestrial organic matter and that the terrestrial-aquatic interface in river headwaters are hotspots of biochemical activity. However, to date, most tropical riverine studies focus on the main river stem or mouth and therefore the dynamics of tropical headwater organic matter cycling within the global carbon cycle are unknown. We present a geochemical and hydrological time-series (sub-hourly resolution) of river water DOC concentration, source and composition from a pristine lowland rainforest headwater of the Burro Burro River, a tributary of the Essequibo River, the 3rd largest river in S. America. We show that during and after a rainstorm event, DOC concentrations increase an order of magnitude (10 to 114mg/L) in less than 30 mins, far exceeding the entire seasonal DOC range measured in 2010 and 2011 (17-28mg/L). The source (δ13C-DOC) of DOC during the rainstorm event changes from microbial/aquatic (-21.9‰ to -25.7‰) at low/intermediate DOC concentration to C3 vegetation supply (-26.8‰ to -30.3‰) during peak DOC flushing. First radiocarbon data shows that riverine DOC is relatively young (106.8-110.9 %modern), however, tropical soils suggest a potential for organic matter to be preserved (360-1200 BP). The fundamental relationship between DOC and coloured dissolved organic matter (CDOM), measured as UV absorbance (SUVA254), holds only for low riverine DOC concentrations with proportionally high lignin contribution, whereas high levels in DOC are not explained by humic substances. Size exclusion chromatography confirms that the DOM pool is divided into two main fractions, humic substances and 'invisible' DOM, or 'iDOM'. The latter group includes non UV-absorbing organic compounds of mono- and oligosaccharides, alcohols, aldehydes, ketones and amino sugars. Our new records from Guyana show that whilst lignin phenols are present and closely track the UV absorbance (R2 = 0.97), it is iDOM that dominates the total DOC pool at peak concentrations (up to 84%). Notably, iDOM is still found in the main Burro Burro River (20-40%), indicating that iDOM has some potential to survive transport downstream. The results suggest that DOC could be significantly underestimated in tropical systems due to the observed decoupling of DOC, water colour (CDOM) and river flux related to large amounts of iDOM entering the river during rainstorm events and wet seasons. Furthermore, given that headwaters represent roughly 50-85% of the total area of tropical river catchments, it is likely that iDOM is a significant component of the terrestrial carbon and nutrient cycles. It is therefore necessary to conduct further field studies that will produce high resolution (temporal and spatial) geochemical records from a large number of tropical systems to better quantify the role of tropical inland waters in carbon and nutrient cycling.

Chemical and optical changes in freshwater dissolved organic matter exposed to solar radiation

USGS Publications Warehouse

Osburn, C.L.; Morris, D.P.; Thorn, K.A.; Moeller, R.E.

2001-01-01

We studied the chemical and optical changes in the dissolved organic matter (DOM) from two freshwater lakes and a Sphagnum bog after exposure to solar radiation. Stable carbon isotopes and solid-state 13C-NMR spectra of DOM were used together with optical and chemical data to interpret results from experimental exposures of DOM to sunlight and from seasonal observations of two lakes in northeastern Pennsylvania. Solar photochemical oxidation of humic-rich bog DOM to smaller LMW compounds and to DIC was inferred from losses of UV absorbance, optical indices of molecular weight and changes in DOM chemistry. Experimentally, we observed a 1.2??? enrichment in ??13C and a 47% loss in aromatic C functionality in bog DOM samples exposed to solar UVR. Similar results were observed in the surface waters of both lakes. In late summer hypolimnetic water in humic Lake Lacawac, we observed 3 to 4.5??? enrichments in ??13C and a 30% increase in aromatic C relative to early spring values during spring mixing. These changes coincided with increases in molecular weight and UV absorbance. Anaerobic conditions of the hypolimnion in Lake Lacawac suggest that microbial metabolism may be turning over allochthonous C introduced during spring mixing, as well as autochthonous C. This metabolic activity produces HMW DOM during the summer, which is photochemically labile and isotopically distinct from allochthonous DOM or autochthonous DOM. These results suggest both photooxidation of allochthonous DOM in the epilimnion and autotrophic production of DOM by bacteria in the hypolimnion cause seasonal trends in the UV absorbance of lakes.

Accumulation of humic-like and proteinaceous dissolved organic matter in zero-discharge aquaculture systems as revealed by fluorescence EEM spectroscopy.

PubMed

Yamin, G; Borisover, M; Cohen, E; van Rijn, J

2017-01-01

Recirculating aquaculture systems (RAS), offering many economic and fish husbandry benefits, are characterized by an accumulation of dissolved organic matter (DOM) and, specifically, humic substances (HS). As reported in a number of studies, HS may affect biological activity in both invertebrates and vertebrates. Given the accumulation of HS in RAS, it is therefore of great interest to characterize DOM and, specifically, its HS fraction in the RAS. The present study was aimed at characterizing long-term changes in fluorescent DOM composition in the culture water of RAS systems, which were operated in a novel, zero water exchange mode. Two such zero-discharge recirculating systems (ZDS) were examined: a freshwater system, stocked with hybrid tilapia (Oreochromis aureus x Oreochromis niloticus) and a marine system, stocked with gilthead seabream (Sparus aurata). Excitation-emission matrices (EEMs) of fluorescence, coupled with parallel factor analysis (PARAFAC), were used to characterize and quantify the different DOM components in the ZDS. In the culture water, one tryptophan-like and four HS-like components were identified. The fluorescence intensities of three of the HS-like components as well as the tryptophan-like component increased at comparable rates during ZDS operation while a much slower accumulation of these compounds was observed in a parallel operated, flow-through, freshwater aquarium. The ZDS examined in this study comprised a sludge digestion stage where a considerable accumulation of all fluorescent components was detected. A HS-like components and a tryptophan-like component in blood of tilapia from the freshwater ZDS were similar to components found in the culture water. Blood levels of both components were higher in fish cultured in the DOM-rich ZDS than in fish raised in the control, flow-through freshwater aquarium. Fluorescence of the HS-like component found in the fish blood increased also with time of ZDS operation. The finding that fish blood contains a HS-like fluorescent component may have important implications for the understanding of the physiological effects of HS in fish and the possible benefits of these substances in aquaculture. Copyright © 2016 Elsevier Ltd. All rights reserved.

Export of Dissolved Organic Carbon following Prescribed Fire on Forested Watersheds: Implications for Watershed Management for Drinking Water Supply

NASA Astrophysics Data System (ADS)

Zhang, W.; Olivares, C. I.; Uzun, H.; Erdem, C. U.; Trettin, C.; Liu, Y.; Robinson, E. R.; Karanfil, T.; Chow, A. T.

2016-12-01

Detrital material in forest watersheds is the major terrestrial source of dissolved organic matter (DOM) and disinfection byproduct (DBP) precursors in surface source waters, but it is also the fuel for forest fires. Prescribed fire, as a fuel reduction technique is intended to reduce the amount of forest detritus, and therefore the risk of wildfire. Accordingly, periodic prescribed fire can reduce the accumulation of detritus on forest floor and the amount of DOM export after forest treatments. To evaluate the effects of prescribed fire on water quality, we conducted a controlled study on a paired first-order watershed system that includes a 160 ha treatment watershed (WS77) and 200 ha control watershed (WS80) on the Santee Experimental Forest, near Charleston South Carolina. WS77 has been used for prescribed fire research since the 1960's, the current experimental burn occurred on April, 2016. WS80 has not been managed or burned for at least 55 years. Gauging stations were equipped with in-situ TOC sensors and flow-proportional water samplers for monitoring temporal trends on water quality. Water samples taken from the first runoff event from both watersheds including rising limb, peak discharge, and falling limb were used for detailed chemical characterizations including DOC and nutrient concentrations, coagulation efficiency, and DBP formation such as trihalomethanes (THMs) and halocacetic acids (HAAs) from chlorination as well as N-nitrosodimethylamine (NDMA) from chlorination, and chemical formula assignment on DOM using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) before and after chlorination and chloramination. Preliminary FT-ICR-MS data shows that DOM chemical compositions are different between raw samples collected from WS77 and WS80. Chlorination resulted in a shift toward lower molecular mass compared to the raw materials. While chloramination did not cause a drastic mass shift, such a treatment also produced DOM moieties that are significantly different from the raw material. Based on our understanding, this watershed-scale study is the first field-scale study to evaluate the effects of prescribed fire on treatability of drinking water supplies.

Changes in water extractable organic matter during incubation of forest floor material in the presence of quartz, goethite and gibbsite surfaces

NASA Astrophysics Data System (ADS)

Heckman, Katherine; Vazquez-Ortega, Angelica; Gao, Xiaodong; Chorover, Jon; Rasmussen, Craig

2011-08-01

The release of dissolved organic matter (DOM) from forest floor material constitutes a significant flux of C to the mineral soil in temperate forest ecosystems, with estimates on the order of 120-500 kg C ha -1 year -1. Interaction of DOM with minerals and metals results in sorptive fractionation and stabilization of OM within the soil profile. Iron and aluminum oxides, in particular, have a significant effect on the quantity and quality of DOM transported through forest soils due to their high surface area and the toxic effects of dissolved aluminum on microbial communities. We directly examined these interactions by incubating forest floor material, including native microbiota, for 154 days in the presence of (1) goethite (α-FeOOH), (2) gibbsite (γ-Al(OH) 3), and (3) quartz (α-SiO 2) sand (as a control). Changes in molecular and thermal properties of water extractable organic matter (WEOM, as a proxy for DOM) were evaluated. WEOM was harvested on days 5, 10, 20, 30, 60, 90, and 154, and examined by thermogravimetry/differential thermal analysis (TG/DTA) and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy. Results indicated significant differences in WEOM quality among treatments, though the way in which oxide surfaces influenced WEOM properties did not seem to change significantly with increasing incubation time. Dissolved organic C concentrations were significantly lower in WEOM from the oxide treatments in comparison to the control treatment. Incubation with goethite produced WEOM with mid-to-high-range thermal lability that was depleted in both protein and fatty acids relative to the control. The average enthalpy of WEOM from the goethite treatment was significantly higher than either the gibbsite or control treatment, suggesting that interaction with goethite surfaces increases the energy content of WEOM. Incubation with gibbsite produced WEOM rich in thermally recalcitrant and carboxyl-rich compounds in comparison to the control treatment. These data indicate that interaction of WEOM with oxide surfaces significantly influences the composition of WEOM and that oxides play an important role in determining the biogeochemistry of forest soil DOM.

Photo- and bio-reactivity patterns of dissolved organic matter from biomass and soil leachates and surface waters in a subtropical wetland.

PubMed

Chen, Meilian; Jaffé, Rudolf

2014-09-15

Dissolved organic carbon (DOC) measurements and optical properties were applied to assess the photo- and bio-reactivity of dissolved organic matter (DOM) from different sources, including biomass leaching, soil leaching and surface waters in a subtropical wetland ecosystem. Samples were exposed to light and/or dark incubated through controlled laboratory experiments. Changes in DOC, ultraviolet (UV-Vis) visible absorbance, and excitation-emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC) were performed to assess sample degradation. Degradation experiments showed that while significant amounts of DOC were consumed during bio-incubation for biomass leachates, a higher degree of bio-recalcitrance for soil leachate and particularly surface waters was displayed. Photo- and bio-humification transformations were suggested for sawgrass, mangrove, and seagrass leachates, as compared to substantial photo-degradation and very little to almost no change after bio-incubation for the other samples. During photo-degradation in most cases the EEM-PARAFAC components displayed photo-decay as compared to a few cases which featured photo-production. In contrast during bio-incubation most EEM-PARAFAC components proved to be mostly bio-refractory although some increases and decreases in abundance were also observed. Furthermore, the sequential photo- followed by bio-degradation showed, with some exceptions, a "priming effect" of light exposure on the bio-degradation of DOM, and the combination of these two processes resulted in a DOM composition more similar to that of the natural surface water for the different sub-environments. In addition, for leachate samples there was a general enrichment of one of the EEM-PARAFAC humic-like component (Ex/Em: <260(305)/416 nm) during photo-degradation and an enrichment of a microbial humc-like component (Ex/Em: <260(325)/406 nm and of a tryptophan-like component (Ex/Em: 300/342 nm) during the bio-degradation process. This study exemplifies the effectiveness of optical property and EEM-PARAFAC in the assessment of DOM reactivity and highlights the importance of the coupling of photo- and bio-degradation processes in DOM degradation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Using high frequency CDOM hyperspectral absorption to fingerprint river water sources

NASA Astrophysics Data System (ADS)

Beckler, J. S.; Kirkpatrick, G. J.; Dixon, L. K.; Milbrandt, E. C.

2016-12-01

Quantifying riverine carbon transfer from land to sea is complicated by variability in dissolved organic carbon (DOC), closely-related dissolved organic matter (DOM) and chromophoric dissolved organic matter (CDOM) concentrations, as well as in the composition of the freshwater end members of multiple drainage basins and seasons. Discrete measurements in estuaries have difficulty resolving convoluted upstream watershed dynamics. Optical measurements, however, can provide more continuous data regarding the molecular composition and concentration of the CDOM as it relates to river flow, tidal mixing, and salinity and may be used to fingerprint source waters. For the first time, long-term, hyperspectral CDOM measurements were obtained on filtered Caloosahatchee River estuarine waters using an in situ, long-pathlength spectrophotometric instrument, the Optical Phytoplankton Discriminator (OPD). Through a collaborative monitoring effort among partners within the Gulf of Mexico Coastal Ocean Observing System (GCOOS), ancillary measurements of fluorescent DOM (FDOM) and water quality parameters were also obtained from co-located instrumentation at high frequency. Optical properties demonstrated both short-term (hourly) tidal variations and long-term (daily - weekly) variations corresponding to changes in riverine flow and salinity. The optical properties of the river waters are demonstrated to be a dilution-adjusted linear combination of the optical properties of the source waters comprising the overall composition (e.g. Lake Okeechobee, watershed drainage basins, Gulf of Mexico). Overall, these techniques are promising as a tool to more accurately constrain the carbon flux to the ocean and to predict the optical quality of coastal waters.

Why dissolved organic matter (DOM) enhances photodegradation of methylmercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qian, Yun; Yin, Xiangping Lisa; Brooks, Scott C

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 degradationmore » 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.« less

Pan-Arctic Distribution of Bioavailable Dissolved Organic Matter and Linkages With Productivity in Ocean Margins

NASA Astrophysics Data System (ADS)

Shen, Yuan; Benner, Ronald; Kaiser, Karl; Fichot, Cédric G.; Whitledge, Terry E.

2018-02-01

Rapid environmental changes in the Arctic Ocean affect plankton productivity and the bioavailability of dissolved organic matter (DOM) that supports microbial food webs. We report concentrations of dissolved organic carbon (DOC) and yields of amino acids (indicators of labile DOM) in surface waters across major Arctic margins. Concentrations of DOC and bioavailability of DOM showed large pan-Arctic variability that corresponded to varying hydrological conditions and ecosystem productivity, respectively. Widespread hot spots of labile DOM were observed over productive inflow shelves (Chukchi and Barents Seas), in contrast to oligotrophic interior margins (Kara, Laptev, East Siberian, and Beaufort Seas). Amino acid yields in outflow gateways (Canadian Archipelago and Baffin Bay) indicated the prevalence of semilabile DOM in sea ice covered regions and sporadic production of labile DOM in ice-free waters. Comparing these observations with surface circulation patterns indicated varying shelf subsidies of bioavailable DOM to Arctic deep basins.

Insights into the redox components of dissolved organic matters during stabilization process.

PubMed

Yuan, Ying; Xi, Bei-Dou; He, Xiao-Song; Ma, Yan; Zhang, Hui; Li, Dan; Zhao, Xin-Yu

2018-05-01

The changes of dissolved organic matter (DOM) components during stabilization process play significant effects on its redox properties but are little reported. Composting is a stabilization process of DOM, during which both the components and electron transfer capacities (ETCs) of DOM change. The redox components within compost-derived DOM during the stabilization process are investigated in this study. The results show that compost-derived DOM contained protein-like, fulvic-like, and humic-like components. The protein-like component decreases during composting, whereas the fulvic- and humic-like components increase during the process. The electron-donating capacity (EDC), electron-accepting capacity (EAC), and ETC of compost-derived DOM all increase during composting but their correlations with the components presented significant difference. The humic-like components were the main functional component responsible for both EDC and ETC, whereas the protein- and fluvic-like components show negative effects with the EAC, EDC, and ETC, suggesting that the components within DOM have specific redox properties during the stabilization process. These findings are very meaningful for better understanding the geochemical behaviors of DOM in the environment.

Toxic metals (Ni2+, Pb2+, Hg2+) binding affinity of dissolved organic matter (DOM) derived from different ages municipal landfill leachate

NASA Astrophysics Data System (ADS)

Rikta, S. Y.; Tareq, Shafi M.; Uddin, M. Khabir

2018-03-01

Solid waste production is rapidly increasing in Bangladesh and landfill leachate is the consequence of the decomposition of this waste. These leachates contain heavy metals and significant amount of dissolved organic matter (DOM). DOM is known to have considerable role in heavy metals speciation. Hence, it is important to characterize DOM/leachate and evaluate toxic metals binding affinity of DOM. The objectives of this study were to characterize the DOM in landfill leachate through physico-chemical and optical analyses and to investigate the toxic metals (Ni2+, Pb2+ and Hg2+) binding affinity of three different ages (fresh sample L-1, young sample L-2 and mature sample L-3) DOM samples. Results suggested that leachate is a potential pollutant which contained very high organic pollutant load. Conditional stability constant (Log K) and percentages of fluorophores that correspond to metal binding (% f) values indicated that young DOM sample (L-2) had the highest binding affinity to all the three metals ions. In general, DOM samples showed the following order affinity to the metal ions; Ni2+ binding affinity: L-2 > L-3 > L-1, Pb2+ binding affinity: L-2 > L-3 > L-1 and Hg2+ binding affinity: L-2 > L-1 > L-3.

Spectroscopic study of interactions of lead (II) ions with dissolved organic matter: Evidence of preferential engagement of carboxylic groups

NASA Astrophysics Data System (ADS)

Lu, Yujuan; Yan, Mingquan; Korshin, Gregory V.

2017-09-01

The speciation, bioavailability and transport of Pb(II) in the environment are strongly affected by dissolved organic matter (DOM). Despite the importance of these interactions, the nature of Pb(II)-DOM binding is insufficiently attested. This study addressed this deficiency using the method of differential absorbance spectroscopy in combination with the non-ideal competitive adsorption (NICA)-Donnan model. Differential absorbance data allowed quantifying the interactions between Pb(II) and DOM in a wide range of pH values, ionic strengths and Pb(II) concentrations at an environmentally relevant DOM concentration (5 mg L-1). Changes of the slopes of the log-transformed absorbance spectra of DOM in the range of wavelength 242-262 and 350-400 nm were found to be predictive of the extent of Pb(II) bound by DOM carboxylic groups and of the total amount of DOM-bound Pb(II), respectively. The results also demonstrated the preferential involvement of DOM carboxylic groups in Pb(II) binding. The spectroscopic data allowed optimizing selected Pb(II)-DOM complexation constants used in the NICA-Donnan Model. This resulted in a markedly improved performance of that model when it was applied to interpret previously published Pb(II)-fulvic acid datasets.

Evaluating Activated Carbon Adsorption of Dissolved Organic Matter and Micropollutants Using Fluorescence Spectroscopy.

PubMed

Shimabuku, Kyle K; Kennedy, Anthony M; Mulhern, Riley E; Summers, R Scott

2017-03-07

Dissolved organic matter (DOM) negatively impacts granular activated carbon (GAC) adsorption of micropollutants and is a disinfection byproduct precursor. DOM from surface waters, wastewater effluent, and 1 kDa size fractions were adsorbed by GAC and characterized using fluorescence spectroscopy, UV-absorption, and size exclusion chromatography (SEC). Fluorescing DOM was preferentially adsorbed relative to UV-absorbing DOM. Humic-like fluorescence (peaks A and C) was selectively adsorbed relative to polyphenol-like fluorescence (peaks T and B) potentially due to size exclusion effects. In the surface waters and size fractions, peak C was preferentially removed relative to peak A, whereas the reverse was found in wastewater effluent, indicating that humic-like fluorescence is associated with different compounds depending on DOM source. Based on specific UV-absorption (SUVA), aromatic DOM was preferentially adsorbed. The fluorescence index (FI), if interpreted as an indicator of aromaticity, indicated the opposite but exhibited a strong relationship with average molecular weight, suggesting that FI might be a better indicator of DOM size than aromaticity. The influence of DOM intermolecular interactions on adsorption were minimal based on SEC analysis. Fluorescence parameters captured the impact of DOM size on the fouling of 2-methylisoborneol and warfarin adsorption and correlated with direct competition and pore blockage indicators.

Ecosystem consequences of changing inputs of terrestrial dissolved organic matter to lakes: current knowledge and future challenges

USGS Publications Warehouse

Solomon, Christopher T.; Jones, Stuart E.; Weidel, Brian C.; Buffam, Ishi; Fork, Megan L; Karlsson, Jan; Larsen, Soren; Lennon, Jay T.; Read, Jordan S.; Sadro, Steven; Saros, Jasmine E.

2015-01-01

Lake ecosystems and the services that they provide to people are profoundly influenced by dissolved organic matter derived from terrestrial plant tissues. These terrestrial dissolved organic matter (tDOM) inputs to lakes have changed substantially in recent decades, and will likely continue to change. In this paper, we first briefly review the substantial literature describing tDOM effects on lakes and ongoing changes in tDOM inputs. We then identify and provide examples of four major challenges which limit predictions about the implications of tDOM change for lakes, as follows: First, it is currently difficult to forecast future tDOM inputs for particular lakes or lake regions. Second, tDOM influences ecosystems via complex, interacting, physical-chemical-biological effects and our holistic understanding of those effects is still rudimentary. Third, non-linearities and thresholds in relationships between tDOM inputs and ecosystem processes have not been well described. Fourth, much understanding of tDOM effects is built on comparative studies across space that may not capture likely responses through time. We conclude by identifying research approaches that may be important for overcoming those challenges in order to provide policy- and management-relevant predictions about the implications of changing tDOM inputs for lakes.

Bioavailability of atrazine, pyrene and benzo[a]pyrene in European river waters

USGS Publications Warehouse

Akkanen, J.; Penttinen, S.; Haitzer, M.; Kukkonen, J.V.K.

2001-01-01

Thirteen river waters and one humic lake water were characterized. The effects of dissolved organic matter (DOM) on the bioavailability of atrazine, pyrene and benzo[a]pyrene (B[a]P) was evaluated. Binding of the chemicals by DOM was analyzed with the equilibrium dialysis technique. For each of the water samples, 24 h bioconcentration factors (BCFs) of the chemicals were measured in Daphnia magna. The relationship between DOM and other water characteristics (including conductivity, water hardness and pH), and bioavailability of the chemicals was studied by performing several statistical analyses, including multiple regression analyses, to determine how much of the variation of BCF values could be explained by the quantity and quality of DOM. The bioavailability of atrazine was not affected by DOM or any other water characteristics. Although equilibrium dialysis showed binding of pyrene to DOM, the bioavailability of pyrene was not significantly affected by DOM. The bioavailability of B[a]P was significantly affected by both the quality and quantity of DOM. Multiple regression analyses, using the quality (ABS270 and HbA%) and quantity of DOM as variables, explainedup to 70% of the variation in BCF of B[a]P in the waters studied. ?? 2001 Elsevier Science Ltd. All rights reserved.

Modelling the interactions between DOM and bacteria in marine ecosystems: state of the art and future prospective

NASA Astrophysics Data System (ADS)

polimene, Luca

2014-05-01

Marine dissolved organic matter (DOM) is the main source of carbon, nutrients and energy for marine prokaryotes, the most abundant life form in the oceans. Only a fraction of assimilated DOM is used by prokaryotes to synthesise new biomass (particulate organic matter, POM), while the rest is used for respiration or is excreted back into the environment as recalcitrant DOM (RDOM). The relative proportions of assimilated DOM that is distributed either to POM, respiration or RDOM is not constant but highly variable depending on the environmental conditions (e.g. nutrient availability, quality/quantity of DOM, temperature). This metabolic plasticity allows bacteria to shape the biogeochemistry of the surrounding waters by modulating three key carbon/energy fluxes fundamental for the functioning of the marine ecosystem: i) the transition from DOM to POM, ii) the remineralisation of carbon and nutrients, and iii) the transformation of labile DOM into recalcitrant DOM. The explicit representation of these processes (and their relative efficiency) in marine ecosystem models is a crucial (and challenging) issue which cannot be overlooked if we want to properly simulate marine biogeochemical cycles under present and climate changing conditions. This talk will provide an overview of how state of the art marine ecosystem models represent the interactions between DOM and bacteria, highlighting strengths and limits of the approaches currently used. A summary of future developments along with issues still open on the topic will also be presented and discussed.

Relationships between dissolved organic matter and discharge: New insights from in-situ measurements in a northern forested watershed

NASA Astrophysics Data System (ADS)

Pellerin, B. A.; Shanley, J. B.; Saraceno, J.; Aiken, G.; Sebestyen, S. D.; Bergamaschi, B. A.

2012-12-01

Quantifying the fundamental linkages between hydrology and dissolved organic matter (DOM) dynamics in streams and rivers is critical for understanding carbon loads, ecosystem food webs and metal transport. Accurately assessing this relationship is difficult, however, given that rapid changes in water flow paths and associated DOM sources are often not captured by traditional discrete sampling intervals of weeks to months. We explored DOM - discharge relationships at Sleepers River below a 40.5 hectare USGS research watershed in northern Vermont by making 30 minute chromophoric DOM fluorescence (FDOM) measurements in-situ since October 2008 along with periodic discrete sampling for dissolved organic carbon. There is a tight coupling between the timing of increases in FDOM and discharge at Sleepers during events, but the ratio of FDOM to discharge exhibited considerable variability across seasons and events, as did FDOM-discharge hysteresis (FDOM variously peaked 1-4 hours after streamflow). Discrete DOM quality indicators (spectral slope, fluorescence index, SUVA) indicate DOM was predominantly terrestrial at all but the lowest flows, highlighting the important role of DOM-rich terrestrial flow paths as the primary source of stream DOM. Our results suggest that changes in flow paths are likely to be the primary drivers of future changes in DOM transport from this site rather than changes in DOM quality. Overcoming significant challenges inherent in continuous sensor deployments in watersheds (e.g. ice cover, suspended particles, remote communication and power) will allow for new insights into watershed biogeochemistry.

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

DOE PAGES

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

2014-06-16

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

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

DOE PAGES

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

2015-01-12

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

Differences in dissolved organic matter lability between alpine glaciers and alpine rock glaciers of the American West

NASA Astrophysics Data System (ADS)

Hall, E.; Fegel, T. S., II; Baron, J.; Boot, C. M.

2015-12-01

While alpine glaciers in montane regions represent the largest flux of dissolved organic matter (DOM) from global ice melt no research has examined the bioavailability of DOM melted out of glacial ice in the western continental United States. Furthermore, rock glaciers are an order of magnitude more abundant than ice glaciers in U.S., yet are not included in budgets for perennial ice carbon stores. Our research aims to understand differences in the bioavailability of carbon from ice glaciers and rock glaciers along the Central Rocky Mountains of Colorado. Identical microbial communities were fed standardized amounts of DOM from four different ice glacier-rock glaciers pairs. Using laboratory incubations, paired with mass spectrometry based metabolomics and 16S gene sequencing; we were able to examine functional definitions of DOM lability in glacial ice. We hypothesized that even though DOM quantities are similar in the outputs of both glacial types in our study area, ice glacial DOM would be more bioavailable than DOM from rock glaciers due to higher proportions of byproducts from microbial metabolism than rock glacier DOM, which has higher amounts of "recalcitrant" plant material. Our results show that DOM from ice glaciers is more labile than DOM from geologically and geographically similar paired rock glaciers. Ice glacier DOM represents an important pool of labile carbon to headwater ecosystems of the Rocky Mountains. Metabolomic analysis shows numerous compounds from varying metabolite pathways, including byproducts of nitrification before and after incubation, meaning that, similar to large maritime glaciers in Alaska and Europe, subglacial environments in the mountain ranges of the United States are hotspots for biological activity and processing of organic carbon.

Urbanization and agriculture increase exports and differentially alter elemental stoichiometry of dissolved organic matter (DOM) from tropical catchments.

PubMed

Gücker, Björn; Silva, Ricky C S; Graeber, Daniel; Monteiro, José A F; Boëchat, Iola G

2016-04-15

Many tropical biomes are threatened by rapid land-use change, but its catchment-wide biogeochemical effects are poorly understood. The few previous studies on DOM in tropical catchments suggest that deforestation and subsequent land use increase stream water dissolved organic carbon (DOC) concentrations, but consistent effects on DOM elemental stoichiometry have not yet been reported. Here, we studied stream water DOC concentrations, catchment DOC exports, and DOM elemental stoichiometry in 20 tropical catchments at the Cerrado-Atlantic rainforest transition, dominated by natural vegetation, pasture, intensive agriculture, and urban land cover. Streams draining pasture could be distinguished from those draining natural catchments by their lower DOC concentrations, with lower DOM C:N and C:P ratios. Catchments with intensive agriculture had higher DOC exports and lower DOM C:P ratios than natural catchments. Finally, with the highest DOC concentrations and exports, as well as the highest DOM C:P and N:P ratios, but the lowest C:N ratios among all land-use types, urbanized catchments had the strongest effects on catchment DOM. Thus, urbanization may have alleviated N limitation of heterotrophic DOM decomposition, but increased P limitation. Land use-especially urbanization-also affected the seasonality of catchment biogeochemistry. While natural catchments exhibited high DOC exports and concentrations, with high DOM C:P ratios in the rainy season only, urbanized catchments had high values in these variables throughout the year. Our results suggest that urbanization and pastoral land use exerted the strongest impacts on DOM biogeochemistry in the investigated tropical catchments and should thus be important targets for management and mitigation efforts. Copyright © 2016 Elsevier B.V. All rights reserved.

Revealing Sources and Distribution Changes of Dissolved Organic Matter (DOM) in Pore Water of Sediment from the Yangtze Estuary

PubMed Central

Wang, Ying; Zhang, Di; Shen, Zhenyao; Feng, Chenghong; Chen, Jing

2013-01-01

Dissolved organic matter (DOM) in sediment pore waters from Yangtze estuary of China based on abundance, UV absorbance, molecular weight distribution and fluorescence were investigated using a combination of various parameters of DOM as well as 3D fluorescence excitation emission matrix spectra (F-EEMS) with the parallel factor and principal component analysis (PARAFAC-PCA). The results indicated that DOM in pore water of Yangtze estuary was very variable which mainly composed of low aromaticity and molecular weight materials. Three humic-like substances (C1, C2, C4) and one protein-like substance (C3) were identified by PARAFAC model. C1, C2 and C4 exhibited same trends and were very similar. The separation of samples on both axes of the PCA showed the difference in DOM properties. C1, C2 and C4 concurrently showed higher positive factor 1 loadings, while C3 showed highly positive factor 2 loadings. The PCA analysis showed a combination contribution of microbial DOM signal and terrestrial DOM signal in the Yangtze estuary. Higher and more variable DOM abundance, aromaticity and molecular weight of surface sediment pore water DOM can be found in the southern nearshore than the other regions primarily due to the influence of frequent and intensive human activities and tributaries inflow in this area. The DOM abundance, aromaticity, molecular weight and fluorescence intensity in core of different depth were relative constant and increased gradually with depth. DOM in core was mainly composed of humic-like material, which was due to higher release of the sedimentary organic material into the porewater during early diagenesis. PMID:24155904

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy.

PubMed

Hur, Jin; Lee, Bo-Mi

2011-06-01

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions. Copyright © 2011 Elsevier Ltd. All rights reserved.

Understanding microbial/DOM interactions using fluorescence and flow cytometry

NASA Astrophysics Data System (ADS)

Fox, Bethany; Rushworth, Cathy; Attridge, John; Anesio, Alexandre; Cox, Tim; Reynolds, Darren

2015-04-01

The transformation and movement of dissolved organic carbon (DOC) within freshwater aquatic systems is an important factor in the global cycling of carbon. DOC within aquatic systems is known to underpin the microbial food web and therefore plays an essential role in supporting and maintaining the aquatic ecosystem. Despite this the interactions between bacteria and dissolved organic matter (DOM) are not well understood, although the literature indicates that the microbial processing of bioavailable DOM is essential during the production of autochthonous, labile, DOM. DOM can be broadly characterised by its fluorescing properties and Coble et al. (2014) define terrestrially derived DOM as exhibiting "peak C" fluorescence, whilst labile microbially derived DOM is defined as showing "peak T" fluorescence. Our work explores the microbial/DOM interactions by analysing aquatic samples using fluorescence excitation and emission matrices (EEMs) in conjunction with microbial consumption of dissolved oxygen. Environmental and synthetic water samples were subjected to fluorescence characterisation using both fluorescence spectroscopy and in situ fluorescence sensors (Chelsea Technologies Group Ltd.). PARAFAC analysis and peak picking were performed on EEMs and compared with flow cytometry data, used to quantify bacterial numbers present within samples. Synthetic samples were created using glucose, glutamic acid, nutrient-rich water and a standard bacterial seed. Synthetic samples were provided with terrestrially derived DOM via the addition of an aliquot of environmental water. Using a closed system approach, samples were incubated over time (up to a maximum of 20 days) and analysed at pre-defined intervals. The main focus of our work is to improve our understanding of microbial/DOM interactions and how these interactions affect both the DOM characteristics and microbial food web in freshwater aquatic systems. The information gained, in relation to the origin, microbial processing and subsequent production of DOM, will inform the development of a new generation of in situ fluorescence sensors. Ultimately, our aim is develop a novel technology that enables the monitoring of ecosystem health in freshwater aquatic systems.

Photochemical reactivities of dissolved organic matter (DOM) in a sub-alpine lake revealed by EEM-PARAFAC: An insight into the fate of allochthonous DOM in alpine lakes affected by climate change.

PubMed

Du, Yingxun; Zhang, Yuanyuan; Chen, Feizhou; Chang, Yuguang; Liu, Zhengwen

2016-10-15

Due to climate change, tree line advance is occurring in many alpine regions. Within the next 50 to 100years, alpine lake catchments are expected to develop increased vegetation cover similar to that of sub-alpine lake catchments which currently exist below the tree line. Such changes in vegetation could trigger increased allochthonous DOM inputs to alpine lakes. To understand the fate of allochthonous DOM in alpine lakes impacted by climate change, the photochemical reactivity of DOM in sub-alpine Lake Tiancai (located 200m below the tree line) was investigated by excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) and UV-Vis spectra analysis. With photo-exposure, a decrease in apparent DOM molecular weight was observed and 32% DOM was photomineralized to CO2. Interestingly, the aromaticity of DOM increased after photodegradation, as evidenced by increases in both the specific UV absorbance at 254nm (SUVA254) and the humification index (HIX). Five EEM-PARAFAC components were identified, including four terrestrially-derived substances (C1, C2, C3 and C4; allochthonous) and one tryptophan-like substance (C5; autochthonous). Generally, allochthonous DOM represented by C2 and C3 exhibited greater photoreactivity than autochthonous DOM represented by C5. C4 was identified as a possible photoproduct with relatively high aromaticity and photorefractive tendencies and contributed to the observed increase in SUVA254 and HIX. UV light facilitated the photodegradation of DOM and had the greatest effect on the removal of C3. This study provides information on the transformation of EEM-PARAFAC components in a sub-alpine lake, which is important in understanding the fate of increased allochthonous DOM inputs to alpine lakes impacted by climate change. Copyright © 2016 Elsevier B.V. All rights reserved.

Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine.

PubMed

Platikanov, Stefan; Tauler, Roma; Rodrigues, Pedro M S M; Antunes, Maria Cristina G; Pereira, Dilson; Esteves da Silva, Joaquim C G

2010-09-01

This study focuses on the factors that affect trihalomethane (THMs) formation when dissolved organic matter (DOM) fractions (colloidal, hydrophobic, and transphilic fractions) in aqueous solutions were disinfected with chlorine. DOM fractions were isolated and fractionated from filtered lake water and were characterized by elemental analysis. The investigation involved a screening Placket-Burman factorial analysis design of five factors (DOM concentration, chlorine dose, temperature, pH, and bromide concentration) and a Box-Behnken design for a detailed assessment of the three most important factor effects (DOM concentration, chlorine dose, and temperature). The results showed that colloidal fraction has a relatively low contribution to THM formation; transphilic fraction was responsible for about 50% of the chloroform generation, and the hydrophobic fraction was the most important to the brominated THM formation. When colloidal and hydrophobic fraction solutions were disinfected, the most significant factors were the following: higher DOM fraction concentration led to higher THM concentration, an increase of pH corresponded to higher concentration levels of chloroform and reduced bromoform, higher levels of chlorine dose and temperature produced a rise in the total THM formation, especially of the chlorinated THMs; higher bromide concentration generates higher concentrations of brominated THMs. Moreover, linear models were implemented and response surface plots were obtained for the four THM concentrations and their total sum in the disinfection solution as a function of the DOM concentration, chlorine dose, and temperature. Overall, results indicated that THM formation models were very complex due to individual factor effects and significant interactions among the factors. In order to reduce the concentration of THMs in drinking water, DOM concentrations must be reduced in the water prior to the disinfection. Fractionation of DOM, together with an elemental analysis of the fractions, is important issue in the revealing of the quality and quantity characteristics of DOM. Systematic study composed from DOM fraction investigation and factorial analysis of the responsible parameters in the THM formation reaction can, after an evaluation of the adjustment of the models with the reality, serves well for the evaluation of the spatial and temporal variability in the THM formation in dependence of DOM. However, taking into consideration the natural complexity of DOM, different operations and a strict control of them (like coagulation/flocculation and filtration) has to be used to quantitatively remove DOM from the raw water. Assuming that this study represents a local case study, similar experiments can be easily applied and will supply with relevant information every local water treatment plant meeting problems with THM formation. The coagulation/flocculation and the filtration stages are the main mechanisms to remove DOM, particularly the colloidal DOM fraction. With the objective to minimize THMs generation, different unit operation designed to quantitatively remove DOM from water must be optimized.

The flux of organic matter through a peatland ecosystem: The role of cellulose, lignin, and their control of the ecosystem oxidation state

NASA Astrophysics Data System (ADS)

Worrall, Fred; Moody, Catherine S.; Clay, Gareth D.; Burt, Tim P.; Rose, Rob

2017-07-01

This study used thermogravimetric analysis (TGA) to study the transit of organic C through a peatland ecosystem. The biomass, litter, peat soil profile, particulate organic matter (POM), and dissolved organic matter (DOM) fluxes were sampled from the Moor House National Nature Reserve, a peat-covered catchment in northern England where both the dry matter and carbon budget for the catchment were known. The study showed that although TGA traces showed distinct differences between organic matter reservoirs and fluxes, the traces could not readily be associated with particular functionalities or elemental properties. The TGA trace shows that polysaccharides are preferentially removed by humification and degradation with residual peat being dominated by lignin compositions. The DOM is derived from the degradation of lignin while the POM is derived from erosion of the peat profile. The carbon lost as gases (CO2 and CH4) was estimated to be composed of 92 to 95% polysaccharide carbon. The composition of the organic matter lost from the peat ecosystem means that the oxidative ratio (OR) of the ecosystem experienced by the atmosphere was between 0.96 and 0.99: currently, the Intergovernmental Panel on Climate Change uses an OR value of 1.1 for all ecosystems.

Limnology of the Green Lakes Valley: Phytoplankton ecology and dissolved organic matter biogeochemistry at a long-term ecological research site

USGS Publications Warehouse

Miller, Matthew P.; McKnight, Diane M.

2015-01-01

Background: Surface waters are the lowest points in the landscape, and therefore serve as excellent integrators and indicators of changes taking place in the surrounding terrestrial and atmospheric environment.Aims: Here we synthesise the findings of limnological studies conducted during the past 15 years in streams and lakes in the Green Lakes Valley, which is part of the Niwot Ridge Long-term Ecological Research (LTER) Site.Methods: The importance of these studies is discussed in the context of aquatic ecosystems as indicators, integrators, and regulators of environmental change. Specifically, investigations into climatic, hydrologic, and nutrient controls on present-day phytoplankton, and historical diatom, community composition in the alpine lake, Green Lake 4, are reviewed. In addition, studies of spatial and temporal patterns in dissolved organic matter (DOM) biogeochemistry and reactive transport modelling that have taken place in the Green Lakes Valley are highlighted.Results and conclusions: The findings of these studies identify specific shifts in algal community composition and DOM biogeochemistry that are indicative of changing environmental conditions and provide a framework for detecting future environmental change in the Green Lakes Valley and in other alpine watersheds. Moreover, the studies summarised here demonstrate the importance of long-term monitoring programmes such as the LTER programme.

Oligotrophic wetland sediments susceptible to shifts in microbiomes and mercury cycling with dissolved organic matter addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Emily B.; Gabor, Rachel S.; Schooler, Shon

Recent advances have allowed for greater investigation into microbial regulation of mercury toxicity in the environment. In wetlands in particular, dissolved organic matter (DOM) may influence methylmercury (MeHg) production both through chemical interactions and through substrate effects on microbiomes. We conducted microcosm experiments in two disparate wetland environments (oligotrophic unvegetated and high-C vegetated sediments) to examine the impacts of plant leachate and inorganic mercury loadings (20 mg/L HgCl 2) on microbiomes and MeHg production in the St. Louis River Estuary. Our research reveals the greater relative capacity for mercury methylation in vegetated over unvegetated sediments. Further, our work shows howmore » mercury cycling in oligotrophic unvegetated sediments may be susceptible to DOM inputs in the St. Louis River Estuary: unvegetated microcosms receiving leachate produced substantially more MeHg than unamended microcosms. We also demonstrate (1) changes in microbiome structure towards Clostridia, (2) metagenomic shifts toward fermentation, and (3) degradation of complex DOM; all of which coincide with elevated net MeHg production in unvegetated microcosms receiving leachate. Altogether, our work shows the influence of wetland vegetation in controlling MeHg production in the Great Lakes region and provides evidence that this may be due to both enhanced microbial activity as well as differences in microbiome composition.« less

Oligotrophic wetland sediments susceptible to shifts in microbiomes and mercury cycling with dissolved organic matter addition

DOE PAGES

Graham, Emily B.; Gabor, Rachel S.; Schooler, Shon; ...

2018-04-03

Recent advances have allowed for greater investigation into microbial regulation of mercury toxicity in the environment. In wetlands in particular, dissolved organic matter (DOM) may influence methylmercury (MeHg) production both through chemical interactions and through substrate effects on microbiomes. We conducted microcosm experiments in two disparate wetland environments (oligotrophic unvegetated and high-C vegetated sediments) to examine the impacts of plant leachate and inorganic mercury loadings (20 mg/L HgCl 2) on microbiomes and MeHg production in the St. Louis River Estuary. Our research reveals the greater relative capacity for mercury methylation in vegetated over unvegetated sediments. Further, our work shows howmore » mercury cycling in oligotrophic unvegetated sediments may be susceptible to DOM inputs in the St. Louis River Estuary: unvegetated microcosms receiving leachate produced substantially more MeHg than unamended microcosms. We also demonstrate (1) changes in microbiome structure towards Clostridia, (2) metagenomic shifts toward fermentation, and (3) degradation of complex DOM; all of which coincide with elevated net MeHg production in unvegetated microcosms receiving leachate. Altogether, our work shows the influence of wetland vegetation in controlling MeHg production in the Great Lakes region and provides evidence that this may be due to both enhanced microbial activity as well as differences in microbiome composition.« less

Principal component analysis to assess the composition and fate of impurities in a large river-embedded reservoir: Qingcaosha Reservoir.

PubMed

Ou, Hua-Se; Wei, Chao-Hai; Deng, Yang; Gao, Nai-Yun

2013-08-01

Qingcaosha Reservoir (QR) is the largest river-embedded reservoir in east China, which receives its source water from the Yangtze River (YR). The temporal and spatial variations in dissolved organic matter (DOM), chromophoric DOM (CDOM), nitrogen, phosphorus and phytoplankton biomass were investigated from June to September in 2012 and were integrated by principal component analysis (PCA). Three PCA factors were identified: (1) phytoplankton related factor 1, (2) total DOM related factor 2, and (3) eutrophication related factor 3. Factor 1 was a lake-type parameter which correlated with chlorophyll-a and protein-like CDOM (r = 0.793 and r = 0.831, respectively). Factor 2 was a river-type parameter which correlated with total DOC and humic-like CDOM (r = 0.668 and r = 0.726, respectively). Factor 3 correlated with total nitrogen and phosphorus (r = 0.864 and r = 0.621, respectively). The low flow speed, self-sedimentation and nutrient accumulation in QR resulted in increases in PCA factor 1 scores (phytoplankton biomass and derived CDOM) in the spatial scale, indicating a change of river-type water (YR) to lake-type water (QR). In summer, the water temperature variation induced a growth-bloom-decay process of phytoplankton combined with the increase of PCA factor 2 (humic-like CDOM) in the QR, which was absent in the YR.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially mediated DOM turnover in the upwelling region off the coast of Peru

NASA Astrophysics Data System (ADS)

Galgani, Luisa; Engel, Anja

2016-04-01

The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4° S, and 82.0 to 77.5° W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation-emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 nm-1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15° S. By EEMs, we identified five fluorescent components (F1-5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m-1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air-sea gas exchange in this area.

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.

Light limitation plays a central role in regulating DOM reactions in temperate watersheds

NASA Astrophysics Data System (ADS)

Yoon, B.; Hosen, J. D.; Kyzivat, E.; Fair, J. H.; Weber, L.; Aho, K. S.; Stubbins, A.; Lowenthal, R. S.; Raymond, P. A.

2017-12-01

Biological uptake and photochemical oxidation determine how much dissolved organic matter (DOM) can be removed and exported from inland waters. It is thus critical to understand the control on the biological and photochemical oxidation of DOM, and identify potential synergy between these two DOM removal processes. Yet, the variability of biological and photochemical lability, and the prevalence of priming effects between the two removal mechanisms are poorly understood at larger spatiotemporal scale. To address this knowledge gap, we analyzed the lability of 900 samples collected throughout the Connecticut River across two years (n = 510 for biolability, n=394 for photolability). Furthermore, we measured the effect of photochemical priming for biological removal and of biological priming for photochemical removal (n= 151, n=146, respectively). Our results show that photolability is on average 5 times greater than biolability, and that the mass of photolabile DOM can be predicted from UV absorbance at 254 nm. Photochemical DOM removal also led to additional "unlocking" of previously bio-recalcitrant DOM in 80% of the samples, and increased the biological lability by threefold on average. Scaling further, we extrapolate our model to estimate that the DOM fluxes leaving the Connecticut River and the Mississippi River are 49% and 45% photolabile, respectively. The significant photoreactivity observed across the samples and the subsequent increase in biolability demonstrate that sunlight is a more potent agent of DOM removal than the biological reactions. Yet, the photolability of DOM fluxes leaving the Connecticut River and Mississippi River indicates that the full photo-oxidation potential is not achieved due to light limitation.

Comparison of the discriminative stimulus effects of dimethyltryptamine with different classes of psychoactive compounds in rats.

PubMed

Gatch, Michael B; Rutledge, Margaret A; Carbonaro, Theresa; Forster, Michael J

2009-07-01

There has been increased recreational use of dimethyltryptamine (DMT), but little is known of its discriminative stimulus effects. The present study assessed the similarity of the discriminative stimulus effects of DMT to other types of hallucinogens and to psychostimulants. Rats were trained to discriminate DMT from saline. To test the similarity of DMT to known hallucinogens, the ability of (+)-lysergic acid diethylamide (LSD), (-)-2,5-dimethoxy-4-methylamphetamine (DOM), (+)-methamphetamine, or (+/-)3,4-methylenedioxymethyl amphetamine (MDMA) to substitute in DMT-trained rats was tested. The ability of DMT to substitute in rats trained to discriminate each of these compounds was also tested. To assess the degree of similarity in discriminative stimulus effects, each of the compounds was tested for substitution in all of the other training groups. LSD, DOM, and MDMA all fully substituted in DMT-trained rats, whereas DMT fully substituted only in DOM-trained rats. Full cross-substitution occurred between DMT and DOM, LSD and DOM, and (+)-methamphetamine and MDMA. MDMA fully substituted for (+)-methamphetamine, DOM, and DMT, but only partially for LSD. In MDMA-trained rats, LSD and (+)-methamphetamine fully substituted, whereas DMT and DOM did not fully substitute. No cross-substitution was evident between (+)-methamphetamine and DMT, LSD, or DOM. DMT produces discriminative stimulus effects most similar to those of DOM, with some similarity to the discriminative stimulus effects of LSD and MDMA. Like DOM and LSD, DMT seems to produce predominately hallucinogenic-like discriminative stimulus effects and minimal psychostimulant effects, in contrast to MDMA which produced hallucinogen- and psychostimulant-like effects.

Actinide Sorption in Rainier Mesa Tunnel Waters from the Nevada Test Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, P; Zavarin, M; Leif, R

2007-12-17

The sorption behavior of americium (Am), plutonium (Pu), neptunium (Np), and uranium (U) in perched Rainier Mesa tunnel water was investigated. Both volcanic zeolitized tuff samples and groundwater samples were collected from Rainier Mesa, Nevada Test Site, NV for a series of batch sorption experiments. Sorption in groundwater with and without the presence of dissolved organic matter (DOM) was investigated. Am(III) and Pu(IV) are more soluble in groundwater that has high concentrations of DOM. The sorption K{sub d} for Am(III) and Pu(IV) on volcanic zeolitized tuff was up to two orders of magnitude lower in samples with high DOM (15more » to 19 mg C/L) compared to samples with DOM removed (< 0.4 mg C/L) or samples with naturally low DOM (0.2 mg C/L). In contrast, Np(V) and U(VI) sorption to zeolitized tuff was much less affected by the presence of DOM. The Np(V) and U(VI) sorption Kds were low under all conditions. Importantly, the DOM was not found to significantly sorb to the zeolitized tuff during these experiment. The concentration of DOM in groundwater affects the transport behavior of actinides in the subsurface. The mobility of Am(III) and Pu(IV) is significantly higher in groundwater with elevated levels of DOM resulting in potentially enhanced transport. To accurately model the transport behavior of actinides in groundwater at Rainier Mesa, the low actinide Kd values measured in groundwater with high DOM concentrations must be incorporated in predictive transport models.« less

Temporal Dynamics in the Concentration, Flux, and Optical Properties of Tree-Derived Dissolved Organic Matter in an Epiphyte-Laden Oak-Cedar Forest

NASA Astrophysics Data System (ADS)

Van Stan, John T.; Wagner, Sasha; Guillemette, François; Whitetree, Ansley; Lewis, Julius; Silva, Leticia; Stubbins, Aron

2017-11-01

Studies on the fate and transport of dissolved organic matter (DOM) along the rainfall-to-discharge flow pathway typically begin in streams or soils, neglecting the initial enrichment of rainfall with DOM during contact with plant canopies. However, rain water can gather significant amounts of tree-derived DOM (tree-DOM) when it drains from the canopy, as throughfall, and down the stem, as stemflow. We examined the temporal variability of event-scale tree-DOM concentrations, yield, and optical (light absorbance and fluorescence) characteristics from an epiphyte-laden Quercus virginiana-Juniperus virginiana forest on Skidaway Island, Savannah, Georgia (USA). All tree-DOM fluxes were highly enriched in dissolved organic carbon (DOC) compared to rainfall, and epiphytes further increased concentrations. Stemflow DOC concentrations were greater than throughfall across study species, yet larger throughfall water yields produced greater DOC yields versus stemflow. Tree-DOM optical characteristics indicate it is aromatic-rich with fluorescent DOM dominated by humic-like fluorescence, containing 10-20% protein-like (tryptophan-like) fluorescence. Storm size was the only storm condition that strongly correlated with tree-DOM concentration and flux; however, throughfall and stemflow optical characteristics varied little across a wide range of storm conditions (from low magnitude events to intense tropical storms). Annual tree-DOM yields from the study forest (0.8-46 g C m-2 yr-1) were similar to other yields from discrete down-gradient fluxes (litter leachates, soil leachates, and stream discharge) along the rainfall-to-discharge flow path.

Characterization and Fate of Dissolved Organic Matter in the Lena Delta Region, Siberia

NASA Astrophysics Data System (ADS)

Goncalves-Araujo, R.; Stedmon, C. A.; Heim, B.; Dubinenkov, I.; Kraberg, A.; Moiseev, D.; Bracher, A.

2016-02-01

Connectivity between the terrestrial and marine environment in the Artic is changing as a result of climate change, influencing both freshwater budgets and the supply of carbon to the sea. This study characterizes the optical properties of dissolved organic matter (DOM) within the Lena Delta region and evaluates the behavior of DOM across the fresh water-marine gradient. Six fluorescent components (four humic-like; one marine humic-like; one protein-like) were identified by Parallel Factor Analysis (PARAFAC) with a clear dominance of allochthonous humic-like signals. Colored DOM (CDOM) and dissolved organic carbon (DOC) were highly correlated and had their distribution coupled with hydrographical conditions. Higher DOM concentration and degree of humification were associated with the low salinity waters of the Lena River. Values decreased towards the higher salinity Laptev Sea shelf waters. Results demonstrate different responses of DOM mixing in relation to the vertical structure of the water column, as reflecting the hydrographical dynamics in the region. Two mixing curves for DOM were apparent. In surface waters above the pycnocline there was a sharper decrease in DOM concentration in relation to salinity indicating removal. In the bottom water layer the DOM decrease within salinity was less. We propose there is a removal of DOM occurring primarily at the surface layer, which is likely driven by photodegradation and flocculation.

Spatial and seasonal variations in stream water delta34S-dissolved organic matter in northern Sweden.

PubMed

Giesler, Reiner; Björkvald, Louise; Laudon, Hoalmar; Mörth, Carl-Magnus

2009-01-15

The discharge of terrestrial dissolved organic matter (DOM) by streams is an important cross-system linkage that strongly influences downstream aquatic ecosystems. Isotopic tracers are important tools that can help to unravel the source of DOM from different terrestrial compartments in the landscape. Here we demonstrate the spatial and seasonal variation of delta34S of DOM in 10 boreal streams to test if the tracer could provide new insights into the origin of DOM. We found large spatial and seasonal variations in stream water delta34S-DOM values ranging from -5.2 per thousand to +9.6 per thousand with an average of +4.0 +/- 0.6 (N = 62; average and 95% confidence interval). Large seasonal variations were found in stream water delta34S-DOM values: for example, a shift of more than 10 per thousand during the spring snowmelt in a wetland-dominated stream. Spatial differences were also observed during the winter base flow with higher delta34S-DOM values in the fourth-order Krycklan stream at the outlet of the 68 km2 catchment compared to the small (< 1 km2) headwater streams. Our data clearly show that the delta34S-DOM values have the potential to be used as a tracer to identify and generate new insights about terrestrial DOM sources in the boreal landscape.

Effects of molecular weight on the diffusion coefficient of aquatic dissolved organic matter and humic substances.

PubMed

Balch, J; Guéguen, C

2015-01-01

In situ measurements of labile metal species using diffusive gradients in thin films (DGT) passive samplers are based on the diffusion rates of individual species. Although most studies have dealt with chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefficient (D) and molecular weight (MW) of 11 aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48×10(-6) to 5.31×10(-6) cm(2) s(-1). Humic substances had diffusion coefficient values ranging from 3.48×10(-6) to 6.05×10(-6) cm(2) s(-1), congruent with previous studies. Molecular weight of aquatic DOM and HS samples (∼500-1750 Da) measured using asymmetrical flow field-flow fractionation (AF4) strongly influenced D, with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. The influence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated with DOM in aquatic environments. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

USGS Publications Warehouse

Poulin, Brett A.; Ryan, Joseph N.; Nagy, Kathryn L.; Stubbins, Aron; Dittmar, Thorsten; Orem, William H.; Krabbenhoft, David P.; Aiken, George R.

2017-01-01

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Metabolomics Reveal Optimal Grain Preprocessing (Milling) toward Rice Koji Fermentation.

PubMed

Lee, Sunmin; Lee, Da Eun; Singh, Digar; Lee, Choong Hwan

2018-03-21

A time-correlated mass spectrometry (MS)-based metabolic profiling was performed for rice koji made using the substrates with varying degrees of milling (DOM). Overall, 67 primary and secondary metabolites were observed as significantly discriminant among different samples. Notably, a higher abundance of carbohydrate (sugars, sugar alcohols, organic acids, and phenolic acids) and lipid (fatty acids and lysophospholipids) derived metabolites with enhanced hydrolytic enzyme activities were observed for koji made with DOM of 5-7 substrates at 36 h. The antioxidant secondary metabolites (flavonoids and phenolic acid) were relatively higher in koji with DOM of 0 substrates, followed by DOM of 5 > DOM of 7 > DOM of 9 and 11 at 96 h. Hence, we conjecture that the rice substrate preprocessing between DOM of 5 and 7 was potentially optimal toward koji fermentation, with the end product being rich in distinctive organoleptic, nutritional, and functional metabolites. The study rationalizes the substrate preprocessing steps vital for commercial koji making.

Fractions and biodegradability of dissolved organic matter derived from different composts.

PubMed

Wei, Zimin; Zhang, Xu; Wei, Yuquan; Wen, Xin; Shi, Jianhong; Wu, Junqiu; Zhao, Yue; Xi, Beidou

2014-06-01

An experiment was conducted to determine the fractions of molecular weights (MW) and the biodegradability of dissolved organic matter (DOM) in mature composts derived from dairy cattle manure (DCM), kitchen waste (KW), cabbage waste (CW), tomato stem waste (TSW), municipal solid waste (MSW), green waste (GW), chicken manure (CM), sludge (S), and mushroom culture waste (MCW). There were distinct differences in the concentration and MW fractions of DOM, and the two measures were correlated. Fraction MW>5kDa was the major component of DOM in all mature composts. Determined 5day biochemical oxygen demand (BOD5) of DOM was correlated to the concentration of DOM and all MW fractions except MW>5kDa, indicating that the biodegradability of DOM was a function of the content and proportion of fraction MW<5kDa. This study suggests that the amount and distribution of low MW fractions affect DOM biodegradability. Copyright © 2014 Elsevier Ltd. All rights reserved.

When soils become sediments: Large-scale storage of soils in sandpits and lakes and the impact of reduction kinetics on heavy metals and arsenic release to groundwater.

PubMed

Vink, Jos P M; van Zomeren, Andre; Dijkstra, Joris J; Comans, Rob N J

2017-08-01

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl 2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Core-size regulated aggregation/disaggregation of citrate-coated gold nanoparticles (5-50 nm) and dissolved organic matter: Extinction, emission, and scattering evidence

NASA Astrophysics Data System (ADS)

Esfahani, Milad Rabbani; Pallem, Vasanta L.; Stretz, Holly A.; Wells, Martha J. M.

2018-01-01

Knowledge of the interactions between gold nanoparticles (GNPs) and dissolved organic matter (DOM) is significant in the development of detection devices for environmental sensing, studies of environmental fate and transport, and advances in antifouling water treatment membranes. The specific objective of this research was to spectroscopically investigate the fundamental interactions between citrate-stabilized gold nanoparticles (CT-GNPs) and DOM. Studies indicated that 30 and 50 nm diameter GNPs promoted disaggregation of the DOM. This result-disaggregation of an environmentally important polyelectrolyte-will be quite useful regarding antifouling properties in water treatment and water-based sensing applications. Furthermore, resonance Rayleigh scattering results showed significant enhancement in the UV range which can be useful to characterize DOM and can be exploited as an analytical tool to better sense and improve our comprehension of nanomaterial interactions with environmental systems. CT-GNPs having core size diameters of 5, 10, 30, and 50 nm were studied in the absence and presence of added DOM at 2 and 8 ppm at low ionic strength and near neutral pH (6.0-6.5) approximating surface water conditions. Interactions were monitored by cross-interpretation among ultraviolet (UV)-visible extinction spectroscopy, excitation-emission matrix (EEM) spectroscopy (emission and Rayleigh scattering), and dynamic light scattering (DLS). This comprehensive combination of spectroscopic analyses lends new insights into the antifouling behavior of GNPs. The CT-GNP-5 and -10 controls emitted light and aggregated. In contrast, the CT-GNP-30 and CT-GNP-50 controls scattered light intensely, but did not aggregate and did not emit light. The presence of any CT-GNP did not affect the extinction spectra of DOM, and the presence of DOM did not affect the extinction spectra of the CT-GNPs. The emission spectra (visible range) differed only slightly between calculated and actual mixtures of CT-GNP-5 or -10 with DOM, whereas emissions for mixtures of CT-GNP-30 or -50 with DOM were enhanced at the surface plasmon resonance (SPR) wavelength. The emission spectra (ultraviolet range) for protein-like constituents of DOM were quenched. Resonance Rayleigh scattering (RRS) was more intense for the CT-GNP-30 and -50 than for the CT-GNP-5 and -10 controls. Intensity-based DLS particle size distributions (PSDs) of DOM controls, CT-GNP-5 and -10 nm controls, and 5- and 10 nm GNP-DOM mixtures exhibited multimodal aggregation. Analyses of CT-GNP-5 and CT-GNP-10 nm mixtures with DOM indicated overcoating of DOM molecules occurred in close proximity (< 10 nm) to GNPs, whereas similar overcoating was not supported for the CT-GNP-30 or -50 mixtures with DOM. These fundamental observations can be exploited to improve our comprehension of nanomaterial interactions with environmental systems.

Inhibition of precipitation and aggregation of metacinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

USGS Publications Warehouse

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

1999-01-01

Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (???3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (??? x 10-8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5 x 10-5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 ??m filter but was removed by centrifugation). At Hg concentrations greater than 5 x 10-4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 ??m filter. Organic matter rich in aromatic moleties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (???3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (???5??10-8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5??10-5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 ??m filter but was removed by centrifugation). At Hg concentrations greater than 5??10-4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 ??m filter. Organic matter rich in aromatic moieties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.

Molecular and optical properties of tree-derived dissolved organic matter in throughfall and stemflow from live oaks and eastern red cedar

NASA Astrophysics Data System (ADS)

Stubbins, Aron; Silva, Leticia M.; Dittmar, Thorsten; Van Stan, John T.

2017-03-01

Studies of dissolved organic matter (DOM) transport through terrestrial aquatic systems usually start at the stream. However, the interception of rainwater by vegetation marks the beginning of the terrestrial hydrological cycle making trees the headwaters of aquatic carbon cycling. Rainwater interacts with trees picking up tree-DOM, which is then exported from the tree in stemflow and throughfall. Stemflow denotes water flowing down the tree trunk, while throughfall is the water that drips through the leaves of the canopy. We report the concentrations, optical properties (light absorbance) and molecular signatures (ultrahigh resolution mass spectrometry) of tree-DOM in throughfall and stemflow from two tree species (live oak and eastern red cedar) with varying epiphyte cover on Skidaway Island, Savannah, Georgia, USA. Both stemflow and throughfall were enriched in DOM compared to rainwater, indicating trees were a significant source of DOM. The optical and molecular properties of tree-DOM were broadly consistent with those of DOM in other aquatic ecosystems. Stemflow was enriched in highly colored DOM compared to throughfall. Elemental formulas identified clustered the samples into three groups: oak stemflow, oak throughfall and cedar. The molecular properties of each cluster are consistent with an autochthonous aromatic-rich source associated with the trees, their epiphytes and the microhabitats they support. Elemental formulas enriched in oak stemflow were more diverse, enriched in aromatic formulas, and of higher molecular mass than for other tree-DOM classes, suggesting greater contributions from fresh and partially modified plant-derived organics. Oak throughfall was enriched in lower molecular weight, aliphatic and sugar formulas, suggesting greater contributions from foliar surfaces. While the optical properties and the majority of the elemental formulas within tree-DOM were consistent with vascular plant-derived organics, condensed aromatic formulas were also identified. As condensed aromatics are generally interpreted as deriving from partially combusted organics, some of the tree-DOM may have derived from the atmospheric deposition of thermogenic and other windblown organics. These initial findings should prove useful as future studies seek to track tree-DOM across the aquatic gradient from canopy roof, through soils and into fluvial networks.

Dissolved organic matter and aluminum oxide nanoparticles synergistically cause cellular responses in freshwater microalgae.

PubMed

Ye, Nan; Wang, Zhuang; Wang, Se; Fang, Hao; Wang, Degao

2018-06-07

This study investigated the impact of dissolved organic matters (DOM) on the ecological toxicity of aluminum oxide nanoparticles (Al 2 O 3 NPs) at a relatively low exposure concentration (1 mg L -1 ). The unicellular green alga Scenedesmus obliquus was exposed to Al 2 O 3 NP suspensions in the presence of DOM (fulvic acid) at various concentrations (1, 10, and 40 mg L -1 ). The results show that the presence of DOM elevated the growth inhibition toxicity of Al 2 O 3 NPs towards S. obliquus in a dose-dependent manner. Moreover, the combination of DOM at 40 mg L -1 and Al 2 O 3 NPs resulted in a synergistic effect. The relative contribution of Al-ions released from Al 2 O 3 NPs to toxicity was lower than 5%, indicating that the presence of the particles instead of the dissolved ions in the suspensions was the major toxicity sources, regardless of the presence of DOM. Furthermore, DOM at 10 and 40 mg L -1 and Al 2 O 3 NPs synergistically induced the upregulation of intercellular reactive oxygen species levels and superoxide dismutase activities. Analysis of the plasma malondialdehyde concentrations and the observation of superficial structures of S. obliquus indicated that the mixtures of DOM and Al 2 O 3 NPs showed no significant effect on membrane lipid peroxidation damage. In addition, the presence of both DOM and Al 2 O 3 NPs contributed to an enhancement in both the mitochondrial membrane potential and the cell membrane permeability (CMP) in S. obliquus. In particular, Al 2 O 3 NPs in the presence of 10 and 40 mg L -1 DOM caused a greater increase in CMP compared to Al 2 O 3 NPs and DOM alone treatments. In conclusion, these findings suggest that DOM at high concentrations and Al 2 O 3 NPs synergistically interrupted cell membrane functions and triggered subsequent growth inhibition toxicity.