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Fresh Water Studies

Chemistry & Biochemistry Faculty Publications

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Full-Text Articles in Physical Sciences and Mathematics

An International Laboratory Comparison Of Dissolved Organic Matter Composition By High Resolution Mass Spectrometry: Are We Getting The Same Answer?, Jeffrey A. Hawkes, Juliana D'Andrilli, Jeffrey N. Agar, Mark P. Barrow, Stephanie M. Berg, Núria Catalán, Hongmei Chen, Rosalie K. Chu, Richard B. Cole, Thorsten Dittmar, Rémy Gavard, Gerd Gleixner, Patrick G. Hatcher, Chen He, Nancy J. Hess, Ryan H.S. Hutchins, Amna Ijaz, Hugh E. Jones, William Kew, Maryam Khaksari, Diana Catalina Palacio Lozano, Jitao Lv, Lynn R. Mazzoleni, Beatriz E. Noriega-Ortega, Helena Osterholz, Nikola Radoman, Christina K. Remucal, Nicholas D. Schmitt, Simeon K. Schum, Quan Shi, Carsten Simon, Gabriel Singer, Rachel L. Sleighter, Aron Stubbins, Mary J. Thomas, Nikola Tolic, Shuzhen Zhang, Phoebe Zito, David C. Podgorski Jan 2020

An International Laboratory Comparison Of Dissolved Organic Matter Composition By High Resolution Mass Spectrometry: Are We Getting The Same Answer?, Jeffrey A. Hawkes, Juliana D'Andrilli, Jeffrey N. Agar, Mark P. Barrow, Stephanie M. Berg, Núria Catalán, Hongmei Chen, Rosalie K. Chu, Richard B. Cole, Thorsten Dittmar, Rémy Gavard, Gerd Gleixner, Patrick G. Hatcher, Chen He, Nancy J. Hess, Ryan H.S. Hutchins, Amna Ijaz, Hugh E. Jones, William Kew, Maryam Khaksari, Diana Catalina Palacio Lozano, Jitao Lv, Lynn R. Mazzoleni, Beatriz E. Noriega-Ortega, Helena Osterholz, Nikola Radoman, Christina K. Remucal, Nicholas D. Schmitt, Simeon K. Schum, Quan Shi, Carsten Simon, Gabriel Singer, Rachel L. Sleighter, Aron Stubbins, Mary J. Thomas, Nikola Tolic, Shuzhen Zhang, Phoebe Zito, David C. Podgorski

Chemistry & Biochemistry Faculty Publications

High-resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive-ion and negative-ion mode electrospray ionization (ESI) HRMS analyses. The …

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Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper Jan 2016

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

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Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper Jan 2016

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

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Characterization And Photodegradation Of Dissolved Organic Matter (Dom) From A Tropical Lake And Its Dominant Primary Producer, The Cyanobacteria Microcystis Aeruginosa, Thais B. Bittar, Aron Stubbins, Armando A. H. Vieira, Kenneth Mopper Jan 2015

Characterization And Photodegradation Of Dissolved Organic Matter (Dom) From A Tropical Lake And Its Dominant Primary Producer, The Cyanobacteria Microcystis Aeruginosa, Thais B. Bittar, Aron Stubbins, Armando A. H. Vieira, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

This study investigates optical and high-resolution molecular signatures and photochemical degradation of DOM from the Barra Bonita Reservoir (BB-DOM), a tropical eutrophic lake, as well as from its dominant phytoplankton species, the cyanobacteria Microcystis aeruginosa (Microcystis-DOM). Consistent with a predominantly autotrophic source, BB-DOM and Microcystis-DOM exhibited high protein-like fluorescence and contained a large number of aliphatics. Microcystis-DOM was enriched in peptide-like formulae, while BB-DOM had higher chromophoric and fluorescent DOM(CDOM and FDOM) and was enriched in moderately unsaturated formulae, indicating additions of terrigenous DOM and/or in situ processing of autochthonous material in the lake. Consistent with …

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Compositions And Constituents Of Freshwater Dissolved Organic Matter Isolated By Reverse Osmosis, Yulong Zhang, Wen Huang, Jingdong Mao Jan 2014

Compositions And Constituents Of Freshwater Dissolved Organic Matter Isolated By Reverse Osmosis, Yulong Zhang, Wen Huang, Jingdong Mao

Chemistry & Biochemistry Faculty Publications

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state 13C nuclear magnetic resonance (13C 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 13C NMR and δ13C 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 …

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A Preliminary Examination Of An In Situ Dual Dye Approach To Measuring Light Fluxes In Lotic Systems, Elizabeth C. Minor, Elizabeth James, Jay A. Austin, Veronica Nelson, Ryan Lusk, Kenneth Mopper Jan 2013

A Preliminary Examination Of An In Situ Dual Dye Approach To Measuring Light Fluxes In Lotic Systems, Elizabeth C. Minor, Elizabeth James, Jay A. Austin, Veronica Nelson, Ryan Lusk, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Light is a critical parameter in aquatic ecosystems, affecting primary production and in situ photochemistry. However, measuring light exposure for suspended particles or dissolved components in a dynamic water column can be challenging with existing Eulerian approaches. Here, we assess the simultaneous deployment of two dyes differing in photolability (rhodamine WT and fluorescein) as a Lagrangian measure of sunlight exposure in a lotic system. Fluorescein is sensitive to light exposure; rhodamine WT is relatively photostable. We examined dye fluorescence at various pH, salinity, and temperature conditions. We also tested dye photolability as a function of pH and wavelength range. In …

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A Mini-Electrodialysis System For Desalting Small Volume Saline Samples For Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Hongmei Chen, Aron Stubbins, Patrick G. Hatcher Jan 2011

A Mini-Electrodialysis System For Desalting Small Volume Saline Samples For Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Hongmei Chen, Aron Stubbins, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated for the efficient desalting of small volume samples of seawater before analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Mini-ED FT-ICR mass spectra were compared with spectra for samples that were treated by C18 solid phase extraction, a commonly used method for rapid sample preparation for this type of analysis. In this comparison, it is clear that mini-ED provides more representative molecular information, compared with C18 isolation, and recovers the overwhelming majority of peaks from salt-free samples, indicating that it adequately represents the …

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Characterization Of Heterogeneities And Domains In Aquatic And Sedimentary Organic Matter By 1 H Spin Diffusion: Potential For Elucidating The Formation Mechanisms, Jingdong Mao, Xiaoyan Cao Jan 2011

Characterization Of Heterogeneities And Domains In Aquatic And Sedimentary Organic Matter By 1 H Spin Diffusion: Potential For Elucidating The Formation Mechanisms, Jingdong Mao, Xiaoyan Cao

Chemistry & Biochemistry Faculty Publications

Although the information on domains and heterogeneities of natural organic matter (NOM) can provide insights into its formation mechanisms, the appropriate solid-state NMR technique for measuring them is still lacking. The traditional technique requires mobility differences in NOM whereas NOM components are primarily rigid. We introduced a new 1H spin diffusion technique, 1H-13C two-dimensional heteronuclear correlation (2D HETCOR) NMR with 1H spin diffusion, for characterization of domains and heterogeneities in aquatic and sedimentary organic matter. It was achieved by collecting a series of 2D HETCOR spectra with a variable mixing time, tm', and …

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Effluent Organic Nitrogen (Eon): Bioavailability And Photochemical And Salinity-Mediated Release, Deborah A. Bronk, Quinn N. Roberts, Marta P. Sanderson, Elizabeth A. Canuel, Patrick G. Hatcher, Rajaa Mesfioui, Katherine C. Filippino, Margaret R. Mulholland, Nancy G. Love Jan 2010

Effluent Organic Nitrogen (Eon): Bioavailability And Photochemical And Salinity-Mediated Release, Deborah A. Bronk, Quinn N. Roberts, Marta P. Sanderson, Elizabeth A. Canuel, Patrick G. Hatcher, Rajaa Mesfioui, Katherine C. Filippino, Margaret R. Mulholland, Nancy G. Love

Chemistry & Biochemistry Faculty Publications

The goal of this study was to investigate three potential ways that the soluble organic nitrogen (N) fraction of wastewater treatment plant (WWTP) effluents, termed effluent organic N (EON), could contribute to coastal eutrophication - direct biological removal, photochemical release of labile compounds, and salinity-mediated release of ammonium (NH4+). Effluents from two WWTPs were used in the experiments. For the bioassays, EON was added to water from four salinities (∼0 to 30) collected from the James River (VA) in August 2008, and then concentrations of N and phosphorus compounds were measured periodically over 48 h. Bioassay results, based …

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Temporal Controls On Dissolved Organic Matter And Lignin Biogeochemistry In A Pristine Tropical River, Democratic Republic Of Congo, Robert G. M. Spencer, Peter J. Hernes, Rosmarie Ruf, Andy Baker, Rachael Y. Dyda, Aron Stubbins, Johan Six Jan 2010

Temporal Controls On Dissolved Organic Matter And Lignin Biogeochemistry In A Pristine Tropical River, Democratic Republic Of Congo, Robert G. M. Spencer, Peter J. Hernes, Rosmarie Ruf, Andy Baker, Rachael Y. Dyda, Aron Stubbins, Johan Six

Chemistry & Biochemistry Faculty Publications

Dissolved organic carbon (DOC), lignin biomarkers, and the optical properties of dissolved organic matter (DOM) were measured in the Epulu River (northeast Democratic Republic of Congo) with the aim of investigating temporal controls on the quantity and chemical composition of DOM in a tropical rainforest river. Three different periods defined by stages of the hydrologic regime of the region, (1) post dry flushing period, (2) intermediary period, and (3) start of the dry period/post flush, were sampled. Temporal variability in DOM quantity and quality was observed with highest DOC, lignin concentration (Σ8) and carbon‐normalized (Λ8) values …

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Electrospray And Photoionization Mass Spectrometry For The Characterization Of Organic Matter In Natural Waters: A Qualitative Assessment, William C. Hockaday, Jeremiah M. Pucell, Alan G. Marshall, Jeffery A. Baldock, Patrick G. Hatcher Jan 2009

Electrospray And Photoionization Mass Spectrometry For The Characterization Of Organic Matter In Natural Waters: A Qualitative Assessment, William C. Hockaday, Jeremiah M. Pucell, Alan G. Marshall, Jeffery A. Baldock, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Fourier-transform ion cyclotron resonance mass spectrometry (MS) has demonstrated potential to revolutionize the fields of limnology and chemical oceanography by identifying the individual molecular components of organic matter in natural waters. The use of MS for this purpose is made possible by the electrospray technique which successfully ionizes polar, nonvolatile organic molecules. Another recently developed ion source, atmospheric pressure photoionization (APPI), extends MS capabilities to less polar molecules. This article presents early results on the application of APPI MS to natural organic matter. We compare APPI MS and electrospray MS data for dissolved organic matter from Lake Drummond (Virginia, USA). …

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Photochemical Degradation Of Dissolved Organic Matter And Dissolved Lignin Phenols From The Congo River, Robert G. M. Spencer, Aron Stubbins, Peter J. Hernes, Kenneth Mopper, Anthony K. Aufdenkampe, Rachael Y. Dyda, Vincent L. Mwamba, Arthur M. Mangangu, Jose N. Wabakanghanzi, Johan Six Jan 2009

Photochemical Degradation Of Dissolved Organic Matter And Dissolved Lignin Phenols From The Congo River, Robert G. M. Spencer, Aron Stubbins, Peter J. Hernes, Kenneth Mopper, Anthony K. Aufdenkampe, Rachael Y. Dyda, Vincent L. Mwamba, Arthur M. Mangangu, Jose N. Wabakanghanzi, Johan Six

Chemistry & Biochemistry Faculty Publications

Photochemical degradation of Congo River dissolved organic matter (DOM) was investigated to examine the fate of terrigenous DOM derived from tropical ecosystems. Tropical riverine DOM receives greater exposure to solar radiation, particularly in large river plumes discharging directly into the open ocean. Initial Congo River DOM exhibited dissolved organic carbon (DOC) concentration and compositional characteristics typical of organic rich blackwater systems. During a 57 day irradiation experiment, Congo River DOM was shown to be highly photoreactive with a decrease in DOC, chromophoric DOM (CDOM), lignin phenol concentrations (Σ8) and carbon-normalized yields (Λ8), equivalent to losses of ~45, 85–95, >95 and …

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Absorption Spectral Slopes And Slope Ratios As Indicators Of Molecular Weight, Source, And Photobleaching Of Chromophoric Dissolved Organic Matter, John R. Helms, Aron Stubbins, Jason D. Ritchie, Elizabeth C. Minor, David J. Kieber, Kenneth Mopper Jan 2008

Absorption Spectral Slopes And Slope Ratios As Indicators Of Molecular Weight, Source, And Photobleaching Of Chromophoric Dissolved Organic Matter, John R. Helms, Aron Stubbins, Jason D. Ritchie, Elizabeth C. Minor, David J. Kieber, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

A new approach for parameterizing dissolved organic matter ( DOM) ultraviolet-visible absorption spectra is presented. Two distinct spectral slope regions ( 275-295 nm and 350-400 nm) within log-transformed absorption spectra were used to compare DOM from contrasting water types, ranging from wetlands (Great Dismal Swamp and Suwannee River) to photobleached oceanic water ( Atlantic Ocean). On the basis of DOM size-fractionation studies ( ultrafiltration and gel filtration chromatography), the slope of the 275-295- nm region and the ratio of these slopes (SR; 275-295- nm slope : 350-400- nm slope) were related to DOM molecular weight ( MW) and …

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Naturally Present Fatty Acids As Internal Calibrants For Fourier Transform Mass Spectra Of Dissolved Organic Matter, Rachel L. Sleighter, Georgina A. Mckee, Zhanfei Liu, Patrick G. Hatcher Jan 2008

Naturally Present Fatty Acids As Internal Calibrants For Fourier Transform Mass Spectra Of Dissolved Organic Matter, Rachel L. Sleighter, Georgina A. Mckee, Zhanfei Liu, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

The analysis of dissolved organic matter ( DOM) by Fourier transform ion cyclotron resonance mass spectrometry ( FTICR- MS) has gained wide interest recently, driven primarily by its ultrahigh resolving power and mass accuracy. Accurate calibration of mass spectra is a key step to successfully decipher the DOM components. We propose a simple and accurate method to internally calibrate the peaks in the complex spectra without the need to add a calibrant. Mass spectra of DOM samples from the Dismal Swamp, Virginia, and the lower Chesapeake Bay display the presence of naturally occurring fatty acids which can be readily recognized …

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Effects Of Salinity Changes On The Photodegradation And Ultraviolet-Visible Absorbance Of Terrestrial Dissolved Organic Matter, E. C. Minor, J. Pothen, B. J. Dalzell, H. Abdulla, K. Mopper Jan 2006

Effects Of Salinity Changes On The Photodegradation And Ultraviolet-Visible Absorbance Of Terrestrial Dissolved Organic Matter, E. C. Minor, J. Pothen, B. J. Dalzell, H. Abdulla, K. Mopper

Chemistry & Biochemistry Faculty Publications

We performed laboratory studies to determine the effects of salinity on the photodegradation of dissolved organic matter (DOM) from the Great Dismal Swamp, Virginia, an important source of terrestrial DOM to the lower Chesapeake Bay. Samples were created by mixing Great Dismal Swamp water (ionic strength approximate to 0 mol L-1) with modified artificial seawater solutions of differing salinities while keeping the final dissolved organic carbon (DOC) concentration constant. These samples were then irradiated for 24 h in a light box providing ultraviolet (UV) light similar to that of natural sunlight. Light absorbance and DOC concentrations decreased after …

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