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Full-Text Articles in Chemistry

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 …


Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher Jan 2024

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is exclusively produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically. Here, we show quantitative evidence that this occurs during the oxidation of biomass with environmentally ubiquitous hydroxyl radicals. Pine wood boards exposed to iron nails and natural weather conditions for 12 years yielded a …


Abiotic Stress Mitigation: A Case Study From 21 Trials Using A Natural Organic Matter Based Biostimulant Across Multiple Geographies, Rachel L. Sleighter, Terry Hanson, David Holden, Kristen M. Richards Jan 2023

Abiotic Stress Mitigation: A Case Study From 21 Trials Using A Natural Organic Matter Based Biostimulant Across Multiple Geographies, Rachel L. Sleighter, Terry Hanson, David Holden, Kristen M. Richards

Chemistry & Biochemistry Faculty Publications

Crop productivity and yields can be greatly diminished by abiotic stress events including drought, extreme temperatures, excess moisture, and saline irrigation water. Multiple stressors occurring simultaneously can further exacerbate the strain on plants. Various types of biostimulants have been shown to mitigate abiotic stress and here, the results of 21 trials on corn, wheat, soybean, and various high-value crops are discussed in the context of the abiotic stress that either occurred naturally or was experimentally induced. Treatments in these trials included stressed and non-stressed plants, as well as either an untreated control or grower standard fertilizer applications alone and in …


Application Of Chemostratigraphic Methods To Floodplain Alluvial Deposits Within The Big Harris Creek Basin, North Carolina, Samantha N. Sullivan, Jerry R. Miller, Carmen L. Huffman Jan 2022

Application Of Chemostratigraphic Methods To Floodplain Alluvial Deposits Within The Big Harris Creek Basin, North Carolina, Samantha N. Sullivan, Jerry R. Miller, Carmen L. Huffman

Chemistry & Biochemistry Faculty Publications

Big Harris Creek, North Carolina, possesses a geomorphic history and alluvial stratigraphic record similar to many drainages in southern Appalachian Piedmont. An approximately 1 km reach of Upper Stick Elliott Creek, a tributary to Big Harris Creek, was used herein to (1) explore the use of chemostratigraphic methods to define and correlate late Holocene alluvial deposits along this relatively uncontaminated rural stream containing legacy sediments (historic, anthropogenically derived deposits), and (2) interpret depositional floodplain processes within small (<10 km2), headwater drainages. The lithofacies within four floodplain sections were described in channel banks and sampled at about 5 cm intervals. …


Stratospheric Aerosol Composition Observed By The Atmospheric Chemistry Experiment Following The 2019 Raikoke Eruption, Chris D. Boone, Peter F. Bernath, Keith Labelle, Jeff Crouse Jan 2022

Stratospheric Aerosol Composition Observed By The Atmospheric Chemistry Experiment Following The 2019 Raikoke Eruption, Chris D. Boone, Peter F. Bernath, Keith Labelle, Jeff Crouse

Chemistry & Biochemistry Faculty Publications

Infrared aerosol spectra derived from Atmospheric Chemistry Experiment measurements following the June 2019 Raikoke volcanic eruption are used to evaluate the composition of stratospheric aerosols in the Arctic. A blanket of aerosols, spanning an altitude range from the tropopause (8–11 km) to 20 km, persisted in the stratosphere over northern latitudes for many months. The aerosols within this blanket were almost exclusively sulfates. The percentage of sulfuric acid in the aerosols decreased over time, dropping below 50% H2SO4 concentration at some altitudes by March 2020. Contrary to previous reports, the aerosol blanket was not comprised of smoke …


Soil Labile Organic Carbon Fractions And Soil Enzyme Activities After 10 Years Of Continuous Fertilization And Wheat Residue Incorporation, Ligan Zhang, Xi Chen, Yujun Xu, Mengcan Jin, Xinxin Ye, Hongjian Gao, Wenying Chu, Jingdong Mao, Michael L. Thompson Jul 2020

Soil Labile Organic Carbon Fractions And Soil Enzyme Activities After 10 Years Of Continuous Fertilization And Wheat Residue Incorporation, Ligan Zhang, Xi Chen, Yujun Xu, Mengcan Jin, Xinxin Ye, Hongjian Gao, Wenying Chu, Jingdong Mao, Michael L. Thompson

Chemistry & Biochemistry Faculty Publications

Labile organic carbon (LOC) fractions and related enzyme activities in soils are considered to be early and sensitive indicators of soil quality changes. We investigated the influences of fertilization and residue incorporation on LOC fractions, enzyme activities, and the carbon pool management index (CPMI) in a 10-year field experiment. The experiment was composed of three treatments: (1) no fertilization (control), (2) chemical fertilizer application alone (F), and (3) chemical fertilizer application combined with incorporation of wheat straw residues (F + R). Generally, the F + R treatment led to the highest concentrations of the LOC fractions. Compared to the control …


Measured Optical Absorption Cross Sections Of Tio, Peter Bernath Jan 2020

Measured Optical Absorption Cross Sections Of Tio, Peter Bernath

Chemistry & Biochemistry Faculty Publications

A laboratory emission spectrum of TiO in the visible and near-infrared regions (476–1176 nm) has been calibrated and corrected. High-resolution experimental absorption cross sections for TiO with natural isotopic abundance are provided at a temperature of about 2300 K. These cross sections have been compared with those derived from the ExoMol line list. The experimental cross sections can be used directly as a template for cross correlation TiO detection in hot Jupiter exoplanets.


Phosgene In The Upper Troposphere And Lower Stratosphere: A Marker For Product Gas Injection Due To Chlorine-Containing Very Short Lived Substances, Jeremy J. Harrison, Martyn P. Chipperfield, Ryan Hossaini, Christopher D. Boone, Sandip Dhomse, Wuhu Feng, Peter F. Bernath Jan 2019

Phosgene In The Upper Troposphere And Lower Stratosphere: A Marker For Product Gas Injection Due To Chlorine-Containing Very Short Lived Substances, Jeremy J. Harrison, Martyn P. Chipperfield, Ryan Hossaini, Christopher D. Boone, Sandip Dhomse, Wuhu Feng, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Abstract: Phosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results …


Formation Of Water-Soluble Organic Matter Through Fungal Degradation Of Lignin, Seyyedhadi Khatami, Ying Deng, Ming Tien, Patrick G. Hatcher Jan 2019

Formation Of Water-Soluble Organic Matter Through Fungal Degradation Of Lignin, Seyyedhadi Khatami, Ying Deng, Ming Tien, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Lignin is a major component of decaying terrestrial vegetation in soils and has been reported to contribute substantially to the formation of soil carbon humus and associated water extracts of soil. To better understand this process of humification, lignin from brown-rot degraded wood is subjected to a white-rot fungus (Phanerochaete chrysosporium)whose enzymes are particularly effective in lignin degradation. This enzymatic attack was monitored by ultrahigh resolution mass spectrometry of water soluble extracts of the fungal cultures. The ensuing molecular level characterizations showed that the P. chrysosporium fungi induced aromatic ring oxidations followed by ring opening as expected. However, …


Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher Apr 2018

Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

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 about 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 …


Surface Oxygenation Of Biochar Through Ozonization For Dramatically Enhancing Cation Exchange Capacity, Matthew D. Huff, Sarah Marshall, Haitham A. Saeed, James Weifu Lee Jan 2018

Surface Oxygenation Of Biochar Through Ozonization For Dramatically Enhancing Cation Exchange Capacity, Matthew D. Huff, Sarah Marshall, Haitham A. Saeed, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Background

Biochar cation exchange capacity (CEC) is a key property that is central to biochar environmental applications including the retention of soil nutrients in soil amendment and removal of certain pollutants in water-filtration applications.

Results

This study reports an innovative biochar-ozonization process that dramatically increases the CEC value of biochars by a factor of 2. The ozonized biochars also show great improvement on adsorption of methylene blue by as much as a factor of about 5. In this study, biochar samples treated with and without ozone were analyzed by means of pH and CEC assays, water field capacity measurement, elemental …


A Near-Global Atmospheric Distribution Of N2o Isotopologues, Peter F. Bernath, Mahdi Yousefi, Eric Buzan, Chris D. Boone Oct 2017

A Near-Global Atmospheric Distribution Of N2o Isotopologues, Peter F. Bernath, Mahdi Yousefi, Eric Buzan, Chris D. Boone

Chemistry & Biochemistry Faculty Publications

The distributions of the four most abundant isotopologues and isotopomers (N2O, 15NNO, N15NO, and NN18O of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near-global picture of N2O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20-30% in the upper stratosphere and even more over the poles. These observations are …


New And Improved Infra-Red Absorption Cross Sections And Ace-Fts Retrievals Of Carbon Tetrachloride (Ccl4), Jeremy J. Harrison, Christopher D. Boone, Peter F. Bernath Jan 2017

New And Improved Infra-Red Absorption Cross Sections And Ace-Fts Retrievals Of Carbon Tetrachloride (Ccl4), Jeremy J. Harrison, Christopher D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Carbon tetrachloride (CCl4) is one of the species regulated by the Montreal Protocol on account of its ability to deplete stratospheric ozone. As such, the inconsistency between observations of its abundance and estimated sources and sinks is an important problem requiring urgent attention (Carpenter et al., 2014) [5]. Satellite remote-sensing has a role to play, particularly limb sounders which can provide vertical profiles into the stratosphere and therefore validate stratospheric loss rates in atmospheric models. This work is in two parts. The first describes new and improved high-resolution infra-red absorption cross sections of carbon tetrachloride/dry synthetic air over …


Introducing Global Peat-Specific Temperature And Ph Calibrations Based On Brgdgt Bacterial Lipids, B.D.A. Naafs, G. N. Imglis, Y. Zheng, M. J. Amesbury, H. Biester, R. Bindler, J. Blewett, M. A. Burrows, D. Del Castillo Torres, F. M. Chambers, P. G. Hatcher Jan 2017

Introducing Global Peat-Specific Temperature And Ph Calibrations Based On Brgdgt Bacterial Lipids, B.D.A. Naafs, G. N. Imglis, Y. Zheng, M. J. Amesbury, H. Biester, R. Bindler, J. Blewett, M. A. Burrows, D. Del Castillo Torres, F. M. Chambers, P. G. Hatcher

Chemistry & Biochemistry Faculty Publications

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (−8 to 27 °C) and pH (3–8) range …


Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke Mar 2016

Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke

Chemistry & Biochemistry Faculty Publications

Nitrous oxide (N2O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth's limb since 2004 and derives profiles of N2O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N2O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N2O is present at all latitudes, during all seasons. The results are consistent with an N2O …


Water Vapour Variability In The High-Latitude Upper Troposphere- Part 2: Impact Of Volcanic Eruptions, Christopher E. Sioris, Jason Zou, C. Thomas Mcelroy, Chris D. Boone, Patrick E. Sheese, Peter F. Bernath Jan 2016

Water Vapour Variability In The High-Latitude Upper Troposphere- Part 2: Impact Of Volcanic Eruptions, Christopher E. Sioris, Jason Zou, C. Thomas Mcelroy, Chris D. Boone, Patrick E. Sheese, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellitebased remote sensing mission are chosen. The Puyehue-Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account …


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 …


Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath Dec 2015

Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath

Chemistry & Biochemistry Faculty Publications

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on board the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite has been measuring the limb radiance in 10 broadband infrared channels over the altitude range from ~ 400 km to the Earth's surface since 2002. The kinetic temperatures and CO2 volume mixing ratios (VMRs) in the mesosphere and lower thermosphere have been simultaneously retrieved using SABER limb radiances at 15 and 4.3 μm under nonlocal thermodynamic equilibrium (non-LTE) conditions. This paper presents results of a validation study of the SABER CO2 VMRs obtained with a two-channel, self-consistent …


Growth In Stratospheric Chlorine From Short-Lived Chemicals Not Controlled By The Montreal Protocol, R. Hossaoni, M. P. Chipperfield, A. Saiz-Lopez, J. J. Harrison, R. Von Glasow, R. Sommariva, E. Atlas, M. Navarro, S. A. Montzka, W. Feng, P. F. Bernath Jun 2015

Growth In Stratospheric Chlorine From Short-Lived Chemicals Not Controlled By The Montreal Protocol, R. Hossaoni, M. P. Chipperfield, A. Saiz-Lopez, J. J. Harrison, R. Von Glasow, R. Sommariva, E. Atlas, M. Navarro, S. A. Montzka, W. Feng, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection …


Simulation Of Energetic Particle Precipitation Effects During The 2003-2004 Arctic Winter, C. E. Randall, V. L. Harvey, L. A. Holt, D. R. Marsh, D. Kinnison, B. Funke, P. F. Bernath Jun 2015

Simulation Of Energetic Particle Precipitation Effects During The 2003-2004 Arctic Winter, C. E. Randall, V. L. Harvey, L. A. Holt, D. R. Marsh, D. Kinnison, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Energetic particle precipitation (EPP) during the 2003-2004 Arctic winter led to the production and subsequent transport of reactive odd nitrogen (NOx=NO+NO2) from the mesosphere and lower thermosphere (MLT) into the stratosphere. This caused NOx enhancements in the polar upper stratosphere in April 2004 that were unprecedented in the satellite record. Simulations of the 2003-2004 Arctic winter with the Whole Atmosphere Community Climate Model using Specified Dynamics (SD-WACCM) are compared to satellite measurements to assess our understanding of the observed NOx enhancements. The comparisons show that SD-WACCM clearly displays the descent of NOx produced …


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 …


Characterization Of Terrestrial Dissolved Organic Matter Fractionated By Ph And Polarity And Their Biological Effects On Plant Growth, Rachel L. Sleighter, Paolo Caricasole, Kristen M. Richards, Terry Hanson, Patrick G. Hatcher Jan 2015

Characterization Of Terrestrial Dissolved Organic Matter Fractionated By Ph And Polarity And Their Biological Effects On Plant Growth, Rachel L. Sleighter, Paolo Caricasole, Kristen M. Richards, Terry Hanson, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Background: Humic substances are ubiquitous in the environment, complex mixtures, and known to be beneficial to plant growth. To better understand and identify components responsible for plant growth stimulation, a terrestrial aquatic DOM sample was fractionated according to pH and polarity, obtaining acid-soluble and acid-insoluble portions, as well as acid-soluble hydrophobic and hydrophilic fractions using C18. The various fractions were characterized then evaluated for their biological effects on plant growth using bioassays with corn at two carbon rates.

Results: Approximately 43% and 57% of the carbon, and 31% and 69% of the iron, was found in the acid-insoluble and acid-soluble …


Use Of Esi-Fticr-Ms To Characterize Dissolved Organic Matter In Headwater Streams Draining Forest-Dominated And Pasture-Dominated Watersheds, Yuehan Lu, Xiaping Li, Rajaa Mesfioui, James E. Bauer, R. M. Chambers, Elizabeth A. Canuel, Patrick G. Hatcher Jan 2015

Use Of Esi-Fticr-Ms To Characterize Dissolved Organic Matter In Headwater Streams Draining Forest-Dominated And Pasture-Dominated Watersheds, Yuehan Lu, Xiaping Li, Rajaa Mesfioui, James E. Bauer, R. M. Chambers, Elizabeth A. Canuel, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest-or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8-87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C …


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 …


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 …


Atmospheric Effects Of Energetic Particle Precipitation In The Arctic Winter 1978-1979 Revisted, L. A. Holt, C. E. Randall, V. L. Harvey, E. E. Remsberg, G. P. Stiller, B. Funke, P. F. Bernath, K. A. Walker Jan 2012

Atmospheric Effects Of Energetic Particle Precipitation In The Arctic Winter 1978-1979 Revisted, L. A. Holt, C. E. Randall, V. L. Harvey, E. E. Remsberg, G. P. Stiller, B. Funke, P. F. Bernath, K. A. Walker

Chemistry & Biochemistry Faculty Publications

[1] The Limb Infrared Monitor of the Stratosphere (LIMS) measured polar stratospheric enhancements of NO2 mixing ratios due to energetic particle precipitation (EPP) in the Arctic winter of 1978–1979. Recently reprocessed LIMS data are compared to more recent measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) to place the LIMS measurements in the context of current observations. The amount of NOx (NO + NO2) entering the stratosphere that has been created by EPP in the mesosphere and lower thermosphere (EPP-NOx) has been quantified …


Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm Jan 2012

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

The goal of this study is to determine how H2O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H2O characteristics that are robust across data sets and that can be used to evaluate …