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Full-Text Articles in Physical Sciences and Mathematics

Unraveling Sources Of Cyanate In The Marine Environment: Insights From Cyanate Distributions And Production During The Photochemical Degradation Of Dissolved Organic Matter, Rui Wang, Jihua Liu, Yongle Xu, Li Liu, Kenneth Mopper Jan 2024

Unraveling Sources Of Cyanate In The Marine Environment: Insights From Cyanate Distributions And Production During The Photochemical Degradation Of Dissolved Organic Matter, Rui Wang, Jihua Liu, Yongle Xu, Li Liu, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton …


Spectroscopic Characterization Of Oceanic Dissolved Organic Matter Isolated By Reverse Osmosis Coupled With Electrodialysis, John R. Helms, Jingdong Mao, Hongmei Chen, E. Michael Perdue, Nelson W. Green, Patrick G. Hatcher, Kenneth Mopper, Aron Stubbins Jan 2015

Spectroscopic Characterization Of Oceanic Dissolved Organic Matter Isolated By Reverse Osmosis Coupled With Electrodialysis, John R. Helms, Jingdong Mao, Hongmei Chen, E. Michael Perdue, Nelson W. Green, Patrick G. Hatcher, Kenneth Mopper, Aron Stubbins

Chemistry & Biochemistry Faculty Publications

Oceanic dissolved organic matter (DOM) is one of the largest pools of reduced carbon on Earth, yet DOM remains poorly chemically characterized. Studies to determine the chemical nature of oceanic DOM have been impeded by the lack of efficient and non-fractioning methods to recover oceanic DOM. Here, a DOM fraction (~40 to 86% recovery) was isolated using reverse osmosis/electrodialysis (RO/ED) and analyzed by solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Samples were obtained from biogeochemically distinct environments: photobleached surface gyre, productive coastal upwelling zone, oxygen minimum, North Atlantic Deep Water, and North Pacific Deep Water. A ubiquitous ‘background’ refractory …


Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber Jan 2015

Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber

Chemistry & Biochemistry Faculty Publications

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter …


Wavelength And Temperature-Dependent Apparent Quantum Yields For Photochemical Formation Of Hydrogen Peroxide In Seawater, David J. Kieber, Gary W. Miller, Patrick J. Neale, Kenneth Mopper Jan 2014

Wavelength And Temperature-Dependent Apparent Quantum Yields For Photochemical Formation Of Hydrogen Peroxide In Seawater, David J. Kieber, Gary W. Miller, Patrick J. Neale, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Wavelength and temperature-dependent apparent quantum yields (AQYs) were determined for the photochemical production of hydrogen peroxide using seawater obtained from coastal and oligotrophic stations in Antarctica, the Pacific Ocean at Station ALOHA, the Gulf of Mexico, and at several sites along the East Coast of the United States. For all samples, AQYs decreased exponentially with increasing wavelength at 25 °C, ranging from 4.6 × 10−4 to 10.4 × 10−4 at 290 nm to 0.17 × 10−4 to 0.97 × 10−4 at 400 nm. AQYs for different seawater samples were remarkably similar irrespective of expected differences in the composition and concentrations …


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 …


A Coupled Geochemical And Biogeochemical Approach To Characterize The Bioreactivity Of Dissolved Organic Matter From A Headwater Stream, Rachel L. Sleighter, Rose M. Cory, Louis A. Kaplan, Hussain A.N. Abdulla, Patrick G. Hatcher Jan 2014

A Coupled Geochemical And Biogeochemical Approach To Characterize The Bioreactivity Of Dissolved Organic Matter From A Headwater Stream, Rachel L. Sleighter, Rose M. Cory, Louis A. Kaplan, Hussain A.N. Abdulla, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

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% …


Estimating Hydroxyl Radical Photochemical Formation Rates In Natural Waters During Long-Term Laboratory Irradiation Experiments, Luni Sun, Hongmei Chen, Hussain A. Abdulla, Kenneth Mopper Jan 2014

Estimating Hydroxyl Radical Photochemical Formation Rates In Natural Waters During Long-Term Laboratory Irradiation Experiments, Luni Sun, Hongmei Chen, Hussain A. Abdulla, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study it was observed that, during long-term irradiations (>1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (<1 day), but not long term irradiations. Only the ‘instantaneous’ formation rates, which were obtained by adding probes to aliquots at each time point and irradiating these sub-samples for a short time (≤2 h), were found appropriate for accurately estimating ˙OH photochemical formation rates during long-term laboratory irradiation experiments. Our results also showed that in iron- and dissolved organic matter (DOM)-rich water samples, ˙OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources possibly from DOM photoreactions. Pathways of ˙OH formation in long-term irradiations in relation to H2O2 and iron concentrations are discussed.


Improved Method For Quantifying The Air-Sea Flux Of Volatile And Semi-Volatile Organic Carbon, Emily Hauser, Rebecca M. Dickhut, Renee Falconer, Andrew S. Wozniak Jan 2013

Improved Method For Quantifying The Air-Sea Flux Of Volatile And Semi-Volatile Organic Carbon, Emily Hauser, Rebecca M. Dickhut, Renee Falconer, Andrew S. Wozniak

Chemistry & Biochemistry Faculty Publications

A method for quantifying the diffusive air-sea exchange of gaseous organic carbon (OC) was developed. OC compounds were separated into two operational pools-those that were kinetically air limited in diffusion across the air-sea interface and those that were water limited-during simultaneous air/water sampling. The method separates OC compounds into low Henry's law constant (low-H) semivolatile OC (SOC) and high Henry's law constant (high-H) volatile OC (VOC) pools that can be categorized by relating diffusion kinetic parameters to Henry's Law constant. Air limited (low-H; H << similar to 0.1 L atm mol(-1)) compounds were collected in pure water traps and were quantified as dissolved OC, whereas …


Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut Jan 2011

Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut

Chemistry & Biochemistry Faculty Publications

Atmospheric particulate matter samples were collected from mid-Atlantic and northeastern U. S. (Virginia and New York, respectively) sites to assess the fossil versus contemporary sources contributing to aerosol organic carbon (OC) and the implications for its deposition to watersheds. Mean particulate matter total OC (TOC) deposition rates (wet + dry deposition) were calculated to be 1.6 and 2.4 mg C m-2 d-1 for the Virginia and New York sites, respectively. Wet deposition of particulate TOC was determined to be the dominant depositional mode, accounting for >65% (Virginia) and >80% (New York) of total aerosol TOC deposition. Isotopic mass …


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 …


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 …