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Articles 61 - 90 of 107

Full-Text Articles in Oceanography

The Marine Cyanate Cycle, Brittany Widner Apr 2016

The Marine Cyanate Cycle, Brittany Widner

OES Theses and Dissertations

Cyanate (OCN-) is a reduced nitrogen compound with the potential to serve as a nitrogen and carbon source for marine microbes. Evidence from genomes and culture studies indicated that several marine cyanobacterial groups, including representatives of the globally important genera Synechococcus and Prochlorococcus, might be capable of cyanate assimilation. However, prior to this study, the distribution, bioavailability, and production pathways of cyanate were unknown in natural systems due to the absence of a sensitive cyanate assay; and the ability of organisms to assimilate cyanate on relevant timescales was unknown because we lacked a suitable tracer for measuring uptake. I developed …


Temporal Variation In Optical Properties Of Chromophoric Dissolved Organic Matter (Cdom) In Southern California Coastal Waters With Nearshore Kelp And Seagrass, Catherine D. Clark, Warren J. De Bruyn, Paige Aiona Oct 2015

Temporal Variation In Optical Properties Of Chromophoric Dissolved Organic Matter (Cdom) In Southern California Coastal Waters With Nearshore Kelp And Seagrass, Catherine D. Clark, Warren J. De Bruyn, Paige Aiona

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Optical properties of chromophoric dissolved organic matter (CDOM) were measured in surf zone waters in diurnal field studies at a Southern California beach with nearshore kelp and seagrass beds and intertidal plant wrack. Absorption coefficients (aCDOM(300 nm)) ranged from 0.35 m21 to 3.7 m21 with short-term variability<1 h, increases at ebb and flood tides and higher values (6 m21) during an offshore storm event. Spectral slopes (S) ranged from 0.0028 nm21 to 0.017 nm21, with higher values after the storm; S was generally inversely correlated with aCDOM(300 nm). 3-D excitation–emission matrix spectra (EEMs) for samples with lower S values had humic-type peaks associated with terrestrial material (A, C), marine microbial material (M) and protein peaks, characteristic of freshly produced organic material. Samples with high S values had no or reduced protein peaks, consistent with aged material. Fluorescent indexes (f450/f500 >2.5, BIX>1.1) were consistent with microbial aquatic sources. Leachates of senescent kelp and seagrass had protein and humic-type EEM peaks. After solar simulator irradiation (4 h), protein peaks rapidly photochemically degraded, humic-type peak C increased in intensity and peak M disappeared. Optical characteristics of kelp leachates were most similar to field samples, …


Interpretation Of Complexometric Titration Data: An Intercomparison Of Methods For Estimating Models Of Trace Metal Complexation By Natural Organic Ligands, I. Pižeta, S. G. Sander, R. J. M. Hudson, D. Omanović, O. Baars, K. A. Barbeau, K. N. Buck, R. M. Bundy, G. Carrasco, P. L. Croot Jan 2015

Interpretation Of Complexometric Titration Data: An Intercomparison Of Methods For Estimating Models Of Trace Metal Complexation By Natural Organic Ligands, I. Pižeta, S. G. Sander, R. J. M. Hudson, D. Omanović, O. Baars, K. A. Barbeau, K. N. Buck, R. M. Bundy, G. Carrasco, P. L. Croot

OES Faculty Publications

With the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model their most common type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they were familiar with to model synthetic titration data that are typical of those obtained by applying state-of-the-art electrochemical methods – anodic stripping voltammetry (ASV) and competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE-ACSV) – to the analysis of natural …


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 …


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 …


Iron Sources And Dissolved-Particulate Interactions In The Seawater Of The Western Equatorial Pacific, Iron Isotope Perspectives, M. Labatut, F. Lacan, C. Pradoux, J. Chmeleff, A. Radic, J. W. Murray, F. Poitrasson, Anne M. Johansen, F. Thil Oct 2014

Iron Sources And Dissolved-Particulate Interactions In The Seawater Of The Western Equatorial Pacific, Iron Isotope Perspectives, M. Labatut, F. Lacan, C. Pradoux, J. Chmeleff, A. Radic, J. W. Murray, F. Poitrasson, Anne M. Johansen, F. Thil

All Faculty Scholarship for the College of the Sciences

This work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ56Fe) of 0.33 ± 0.11‰ (2SD) and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ56Fe between −0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. …


Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen Jan 2014

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …


Air-Sea Dimethylsulfide (Dms) Gas Transfer In The North Atlantic: Evidence For Limited Interfacial Gas Exchange At High Wind Speed, T. G. Bell, Warren J. De Bruyn, S. D. Miller, B. Ward, K. Christensen, E. S. Saltzman Jan 2013

Air-Sea Dimethylsulfide (Dms) Gas Transfer In The North Atlantic: Evidence For Limited Interfacial Gas Exchange At High Wind Speed, T. G. Bell, Warren J. De Bruyn, S. D. Miller, B. Ward, K. Christensen, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Shipboard measurements of eddy covariance dimethylsulfide (DMS) air-sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k(660)) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s(-1). At higher wind speeds the relationship between k(660) and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent …


Production Mechanisms, Number Concentration, Size Distribution, Chemical Composition, And Optical Properties Of Sea Spray Aerosols, Nicholas Meskhidze, Markus D. Petters, Kostas Tsigaridis, Tim Bates, Colin O'Dowd, Jeff Reid, Ernie R. Lewis, Brett Gantt, Magdalena D. Anguelova, Prakash V. Bhave, Andrew Wozniak Jan 2013

Production Mechanisms, Number Concentration, Size Distribution, Chemical Composition, And Optical Properties Of Sea Spray Aerosols, Nicholas Meskhidze, Markus D. Petters, Kostas Tsigaridis, Tim Bates, Colin O'Dowd, Jeff Reid, Ernie R. Lewis, Brett Gantt, Magdalena D. Anguelova, Prakash V. Bhave, Andrew Wozniak

Chemistry & Biochemistry Faculty Publications

(First paragraph)

The impact of sea spray aerosols on global climate remains one of the most uncertain components of the aerosol–radiation–climate problem, but has received less attention than the impacts of terrestrial and anthropogenic aerosols. The last decade has produced a large body of information regarding the sources and composition of marine aerosols, resulting in a reassessment of the complex role that sea spray particles play in climate and various geophysical phenomena. As sea spray aerosol contributes substantially to the preindustrial, natural background which provides the baseline on top of which anthropogenic forcing should be quantified, and because the ocean …


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 …


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 …


Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into Composition, Photochemical Transformation And Carbon Cycling, John Robert Helms Jul 2012

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into Composition, Photochemical Transformation And Carbon Cycling, John Robert Helms

Chemistry & Biochemistry Theses & Dissertations

This dissertation explores processes affecting the composition of dissolved organic matter (DOM) and how DOM composition changes in sunlit surface waters and in the dark interior ocean. Simulated solar irradiations were used to investigate the impact of photochemistry on terrestrial waters and deep ocean DOM. The photochemically mediated processes observed in Dismal Swamp samples included (i) light induced flocculation of up to 12% of the organic matter and 84% of the dissolved iron originally present; (ii) 74-88% mineralization of dissolved organic carbon (DOC) and 95-99% bleaching of chromophoric DOM (CDOM) during 110 days of irradiation; and (iii) nearly complete loss …


Global Estimates Of Mineral Dust Aerosol Iron And Aluminum Solubility That Account For Particle Size Using Diffusion-Controlled And Surface-Area-Controlled Approximations, Qin Han, Charles S. Zender, J. Keith Moore, Clifton S. Buck, Ying Chen, Anne Johansen, Christopher I. Measures Jun 2012

Global Estimates Of Mineral Dust Aerosol Iron And Aluminum Solubility That Account For Particle Size Using Diffusion-Controlled And Surface-Area-Controlled Approximations, Qin Han, Charles S. Zender, J. Keith Moore, Clifton S. Buck, Ying Chen, Anne Johansen, Christopher I. Measures

All Faculty Scholarship for the College of the Sciences

Mineral aerosol deposition is recognized as the dominant source of iron to the open ocean and the solubility of iron in the dust aerosol is highly variable, with measurements ranging from 0.01–80%. Global models have difficulty capturing the observed variations in solubility, and have ignored the solubility dependence on aerosol size. We introduce two idealized physical models to estimate the size dependence of mineral aerosol solubility: a diffusion‐controlled model and a surface‐area‐controlled model. These models produce differing time‐ and space‐varying solubility maps for aerosol Fe and Al given the dust age at deposition, size‐resolved dust entrainment fields, and the aerosol …


Isotopic Characterization Of Aerosol Organic Carbon Components Over The Eastern United States, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut, Xu Li, Ann P. Mcnichol Jan 2012

Isotopic Characterization Of Aerosol Organic Carbon Components Over The Eastern United States, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut, Xu Li, Ann P. Mcnichol

Chemistry & Biochemistry Faculty Publications

Carbon isotopic signatures (δ13C, Δ14C) of aerosol particulate matter total organic carbon (TOC) and operationally defined organic carbon (OC) components were measured in samples from two background sites in the eastern U.S. TOC and water-soluble OC (WSOC)δ13C values (−27 to −24‰) indicated predominantly terrestrial C3 plant and fossil derived sources. Total solvent extracts (TSE) and their aliphatic, aromatic, and polar OC components were depleted in δ13C (−30 to −26‰) relative to TOC and WSOC. Δ14C signatures of aerosol TOC and TSE (−476 to +25‰) suggest variable fossil contributions (∼5–50%) …


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 …


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 …


Oxygen Isotopes As A Tracer Of Dom Processes In River-Estuary Systems, Joy Ashley Matthews Jul 2010

Oxygen Isotopes As A Tracer Of Dom Processes In River-Estuary Systems, Joy Ashley Matthews

OES Theses and Dissertations

In the biogeochemical study of dissolved organic matter (DOM) in natural waters, stable isotopes are used to provide insight into both the sources of DOM and the processes affecting its alteration. Through the research presented here, oxygen isotopes are incorporated into the study of DOM through the adaptation of a pyrolysis elemental analysis isotope ratio mass spectrometer method, and sample preparation using two-stage ultrafiltration.

The application of oxygen isotopes to the study of DOM is demonstrated in two studies. First, natural abundance of δ18O in DOM is explored in the Delaware estuary. Using a two end-member mixing model, …


Air-Sea Gas Exchange Of Co2 And Dms In The North Atlantic By Eddy Covariance, Scott Miller, Christa Marandino, Warren J. De Bruyn, Eric S. Saltzman Jan 2009

Air-Sea Gas Exchange Of Co2 And Dms In The North Atlantic By Eddy Covariance, Scott Miller, Christa Marandino, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report the first simultaneous eddy covariance flux measurements of CO2 and dimethylsulfide (DMS) over the open ocean for two North Atlantic cruises. After normalization for Schmidt number, the two gases give essentially identical gas transfer coefficients and wind speed dependences for the wind speed range 2-10 ms(-1). The data indicate a linear relationship between the gas transfer coefficient and mean wind speed, with measured gas transfer coefficients slightly above the Wanninkhof (1992) parameterization, particularly at low wind speeds. Citation: Miller, S., C. Marandino, W. de Bruyn, and E. S. Saltzman (2009), Air-sea gas exchange of CO2 and DMS in …


A Chemical Ionization Mass Spectrometer For Continuous Underway Shipboard Analysis Of Dimethylsulfide In Near-Surface Seawater, Eric S. Saltzman, Warren J. De Bruyn, M. J. Lawler, Christa Marandino, C. A. Mccormick Jan 2009

A Chemical Ionization Mass Spectrometer For Continuous Underway Shipboard Analysis Of Dimethylsulfide In Near-Surface Seawater, Eric S. Saltzman, Warren J. De Bruyn, M. J. Lawler, Christa Marandino, C. A. Mccormick

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ('mini-CIMS') has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified …


Open Ocean Dms Air/Sea Fluxes Over The Eastern South Pacific Ocean, C. A. Marandino, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman Jan 2009

Open Ocean Dms Air/Sea Fluxes Over The Eastern South Pacific Ocean, C. A. Marandino, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110 degrees W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (k(DMS)) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8 +/- 2.2 nM and atmospheric mixing ratios were 340 +/- 370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with …


Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter Jan 2009

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …


Anthropogenic Osmium In Rain And Snow Reveals Global-Scale Atmospheric Contamination, Cynthia Chen, Peter N. Sedwick, Mukul Sharma Jan 2009

Anthropogenic Osmium In Rain And Snow Reveals Global-Scale Atmospheric Contamination, Cynthia Chen, Peter N. Sedwick, Mukul Sharma

OES Faculty Publications

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 x 10-15 g g-1 ( 5.3 x 10-14 mol kg-1. The osmium isotope composition (187Os/188Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈ 1.3) and mantle/cosmic dust (≈ 0.13). Here, we show that the 187Os/188Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximate to 0.2) …


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). …


Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman Jan 2008

Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Dimethylsulfide (DMS) atmospheric and oceanic concentrations and eddy covariance air/sea fluxes were measured over the N. Atlantic Ocean during July 2007 from Iceland to Woods Hole, MA, USA. Seawater DMS levels north of 55 degrees N ranged from 3 to 17 nM, with variability related to the satellite-derived distributions of coccoliths and to a lesser extent, chlorophyll. For the most intense bloom region southwest of Iceland, DMS air/sea fluxes were as high as 300 mu mol m(-2) d(-1), larger than current model estimates. The observations imply that gas exchange coefficients in this region are significantly greater than those estimated using …


A Tribute To Peter George Brewer In Celebration Of His 65th Birthday, George T. F. Wong, Robert F. Anderson, Michael P. Bacon, Hein J. W. De Baar, James W. Murray, Mary I. Scranton Jan 2008

A Tribute To Peter George Brewer In Celebration Of His 65th Birthday, George T. F. Wong, Robert F. Anderson, Michael P. Bacon, Hein J. W. De Baar, James W. Murray, Mary I. Scranton

OES Faculty Publications

Peter George Brewer is an ocean chemist of the rare breed that can cross back and forth over the divide between being a front-line research scientist and being a research executive. As if that is not remarkable enough, in the process, he has also demonstrated sustained growth in the depth, breadth, and diversity of his scientific endeavors. Some of his formidable contributions to ocean chemistry have already been highlighted in a profile of him as a major mover and shaker in the field (Irion, 2001). Here, we provide additional glimpses of him from the perspective of a group of individuals …


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 …


Determination Of Photochemically Produced Carbon Dioxide In Seawater, Emily M. White, David J. Kieber, Kenneth Mopper Jan 2008

Determination Of Photochemically Produced Carbon Dioxide In Seawater, Emily M. White, David J. Kieber, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

An analytical system was developed to determine photochemically produced carbon dioxide in marine waters. Our system was designed to measure low levels of carbon dioxide by maintaining a closed system to prevent atmospheric contamination during sample preparation, irradiation, and analysis. To detect low levels of photoproduced carbon dioxide in seawater, background dissolved inorganic carbon (DIC) was removed before irradiation. To strip out DIC, samples were acidified to pH 3.0 (converting DIC to carbon dioxide) and bubbled with low carbon dioxide air. The pH was then readjusted back to the original value, and the resulting low-DIC seawater samples were transferred pneumatically …


Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant Jan 2008

Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

To determine chromophoric dissolved organic matter (CDOM) sources in Southern California coastal waters, optical properties of a river outlet and adjacent tidally flushed salt marshes were monitored (dry season; June July 2001). Average absorption coefficients doubled at ebb vs. flood tides (4.8 +/- 1.5 vs. 2.1 +/- 0.9 m(-1); 300 nm), suggesting significant salt marsh CDOM inputs into coastal waters. Average spectral slopes were not statistically different for any sites or tides (0.010 +/- 0.002 nm(-1)), consistent with salt marsh CDOM dominating coastal waters. Three-dimensional fluorescence excitation-emission matrices (EEMs) at ebb tide showed contributions from terrestrial, protein, and marine humic-like …


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 …


Investigating The Spring Bloom In San Francisco Bay: Links Between Water Chemistry, Metal Cycling, Mercury Speciation, And Phytoplankton Community Composition, Allison C. Luengen Jan 2007

Investigating The Spring Bloom In San Francisco Bay: Links Between Water Chemistry, Metal Cycling, Mercury Speciation, And Phytoplankton Community Composition, Allison C. Luengen

Environmental Science

Investigating the spring bloom in San Francisco Bay: Links between water chemistry, metal cycling, mercury speciation, and phytoplankton community composition This dissertation addresses the relationship between two problems facing estuaries nationwide: nutrient enrichment and metal contamination. The focus is on the southern reach of San Francisco Bay, where high nutrient concentrations can control the magnitude of the predictably occurring spring phytoplankton bloom. The bloom in this study, in spring 2003, was one of the largest blooms on record, exceeding 150 μg L -1 of chlorophyll α. As the bloom grew, diatoms (e.g. Thalassiosira punctigera ) depleted dissolved nutrients from the …