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  • 1
    Online Resource
    Online Resource
    New York :Cambridge University Press,
    Keywords: Water chemistry. ; Electronic books.
    Description / Table of Contents: This is the first comprehensive text on the theory and practice of aquatic organic matter fluorescence analysis, written by the experts who pioneered the research area. The book will be of interest to those establishing field, laboratory, or industrial applications of fluorescence, including advanced students and researchers.
    Type of Medium: Online Resource
    Pages: 1 online resource (408 pages)
    Edition: 1st ed.
    ISBN: 9781139905831
    Series Statement: Cambridge Environmental Chemistry Series
    DDC: 572/.435809162
    Language: English
    Note: Cover -- Half-title -- Series information -- Title page -- Copyright information -- Table of contents -- List of contributors -- About the Editors -- Preface -- Part I Introduction -- 1 The Principles of Fluorescence -- 1.1 Luminescence -- 1.2 The Relevance of Quantum Mechanics and Electronic Theory -- 1.2.1 Wave-Particle Duality and Quantization of Energy and Matter -- 1.2.1.1 Subatomic Particles -- 1.2.1.2 Quantized Matter and Energy -- 1.2.1.3 Copenhagen Interpretation -- 1.2.2 Chemical Bonding and Molecular Orbitals -- 1.2.2.1 Sigma Bonds (s Bonds) -- 1.2.2.2 Pi Bonds (p Bonds) -- 1.2.2.3 Antibonding Orbitals -- 1.2.2.4 Nonbonded Electrons -- 1.3 Understanding the Fluorescence Process -- 1.3.1 Electronic Transitions -- 1.3.1.1 Spin Multiplicity -- 1.3.1.2 Absorption -- 1.3.1.3 Franck-Condon Principle -- 1.3.2 Nonradiative Decay -- 1.3.2.1 Vibrational Relaxation -- 1.3.2.2 Internal Conversion and Intersystem Crossing -- 1.3.3 Radiative Decay -- 1.3.4 Fluorescence -- 1.3.4.1 Stokes Shift -- 1.3.4.2 Fluorescence Decay Kinetics -- 1.3.4.3 Fluorescence Efficiency (Quantum Yield) -- 1.3.4.4 Fluorescence Quenching -- 1.3.4.5 Influence of Molecular Structure on Fluorescence -- 1.3.4.6 The Effect of pH -- 1.3.4.7 Effects of Solvents on Fluorescence Emission -- 1.3.4.8 The Heavy Atom Effect -- 1.3.4.9 Fluorescence Spectra -- 1.3.4.10 Scattering of Radiation -- 1.3.4.11 Normalization of Fluorescence Intensities -- References -- 2 Fluorescence and Dissolved Organic Matter: A Chemist's Perspective -- 2.1 Introduction -- 2.2 Theory -- 2.2.1 Absorption -- 2.2.2 Fluorescence -- 2.3 DOM Fluorescence -- 2.4 Fluorophores of Interest -- 2.4.1 Amino Acids and Proteins -- 2.4.2 Simple Phenols -- 2.4.3 Indoles -- 2.4.4 Phenylpropanes -- 2.4.5 Oxygen Ring Compounds -- 2.4.6 Lignin -- 2.4.7 Quinones -- 2.4.8 Alkaloids -- 2.5 Factors Influencing DOM Fluorescence. , 2.5.1 Quenching -- 2.5.2 pH Effects -- 2.5.3 Interactions with Metals -- 2.5.4 Charge Transfer Interactions -- 2.6 Conclusions -- Acknowledgments -- References -- 3 Aquatic Organic Matter Fluorescence -- 3.1 Introduction -- 3.1.1 Peak Nomenclature -- 3.1.2 Humic-like EEM Components -- 3.1.3 Other EEM Components -- 3.1.4 Reconciling PARAFAC Model EEM Components -- 3.2 Fluorescence in Seawater -- 3.2.1 Introduction -- 3.2.2 CDOM in Coastal Ocean and Estuaries -- 3.2.3 CDOM in Open Ocean Waters -- 3.3 Fluorescence in Freshwater -- 3.3.1 Temporal Variation in DOM Source and Dynamics -- 3.3.2 Anthropogenic and Land Use Impacts on DOM -- 3.3.3 Transformations and Reactivity -- 3.3.4 Rainwater DOM Fluorescence -- 3.3.5 Dissolved Organic Carbon vs. Fluorescence Relationships -- 3.4 Fluorescence in Groundwater -- 3.4.1 Introduction -- 3.4.2 Groundwater NOM Fluorescence Characteristics -- 3.4.3 Groundwater Anthropogenic Organic Matter Characteristics -- 3.5 Fluorescence of Wastewater and Drinking Water -- 3.5.1 Wastewater Fluorescence -- 3.5.2 Drinking Water Fluorescence -- References -- Part II Instrumentation and Sampling -- 4 Sampling Design for Organic Matter Fluorescence Analysis -- 4.1 Introduction -- 4.2 Sample Collection -- 4.2.1 Contamination Sources -- 4.2.2 Blanks and Replicate Samples -- 4.2.3 Equipment Cleaning -- 4.2.4 Water Samplers -- 4.3 Sample Preservation -- 4.3.1 Filtration Techniques -- 4.3.2 Effects of Filtration on Fluorescence -- 4.4 Storage -- 4.4.1 General Comments -- 4.4.2 Refrigeration and Freezing -- 4.4.3 Poisoning - Acidification -- 4.5 Summary and Future Needs -- Acknowledgments -- References -- 5 Optical Spectroscopy Instrumentation Design, Quality Assurance, and Control: Bench-Top Fluorimetry -- 5.1 Introduction -- 5.2 Methods of Optical Spectroscopy -- 5.2.1 Absorption Spectroscopy -- 5.2.2 Optical Emission Spectroscopy. , 5.2.3 Scattering -- 5.2.4 Photoluminescence (Fluorescence and Phosphorescence) -- 5.3 The Fluorescence Spectrometer -- 5.3.1 The Ideal Fluorescence Spectrometer System -- 5.3.2 Basic Spectrofluorimeter Design -- 5.4 Measuring Fluorescence -- 5.4.1 Defining the Sensing Volume and Inner Filter Effects -- 5.4.2 Continuum Light Sources -- 5.4.3 Monochromators and Filters -- 5.4.4 Polarization Effects -- 5.4.5 Detectors -- 5.4.6 Measurement Systems: Data Acquisition Electronics and Software -- 5.4.7 Data Collection, Display, and Analysis Software -- 5.4.8 Instrument Performance Validation -- 5.4.9 Linearity, Signal to Noise, and Dynamic Range -- 5.4.10 Speed and Sensitivity -- 5.4.11 Wavelength Accuracy -- 5.4.12 Bandpass Selection -- 5.4.13 Stray Light -- 5.4.14 Cuvettes, Cleaning and Handling -- 5.4.15 Solvents and Contaminants -- 5.4.16 Background Signals: Rayleigh and Raman Scattering -- 5.4.17 Spectral Irradiance of the Excitation Channel -- 5.4.18 Correcting Excitation Signal Channels -- 5.4.19 Correcting Emission Signal Channels -- 5.4.20 Quantum Yield -- 5.4.21 Measuring Quantum Yields: The Three-Measurement Technique -- 5.4.22 Fluorescence Units - What Are They? -- References -- 6 Experimental Design and Quality Assurance: In Situ Fluorescence Instrumentation -- 6.1 Introduction -- 6.2 Historical Perspective of In Situ Sensors -- 6.2.1 Chlorophyll Field Sensors: Precursors to In Situ DOM Fluorometers -- 6.2.2 Evolution of DOM Field Sensors -- 6.3 Instrument Design Types -- 6.3.1 Sensor Configurations -- 6.3.2 Light Sources and Detectors -- 6.3.3 Optical Filters -- 6.3.4 Optical Configurations -- 6.3.5 Data Output -- 6.4 Calibration and Correction Procedures -- 6.4.1 Temperature Correction -- 6.4.2 Blank Subtraction -- 6.4.3 Standards and Intensity Calibration -- 6.4.4 Correction for Inner Filter Effects -- 6.4.5 Dynamic Range. , 6.5 Environmental Considerations -- 6.5.1 Factors of Concern -- 6.5.1.1 Particles -- 6.5.1.2 Bubbles -- 6.5.1.3 Dynamic Range -- 6.5.1.4 Temperature Effects -- 6.5.1.5 Biofouling -- 6.5.1.6 Understanding NOM Sources Within Environments -- 6.5.2 Sensor Choices for Specific Environments -- 6.5.2.1 Optically Dilute Systems -- 6.5.2.2 Optically Thick Systems -- 6.5.2.3 Turbid Systems -- 6.5.2.4 Energetically Flashy Environments -- 6.6 Revolutionizing NOM Studies via High-Resolution Fluorescence Measurements -- 6.6.1 Deployment Platforms -- 6.6.1.1 Spatial Resolution -- 6.6.1.2 Temporal Resolution -- 6.6.2 Importance of Scale -- 6.6.2.1 Neponset River Estuary in Boston Harbor- Small Temporal and Spatial Scales -- 6.6.2.2 Hudson River Estuary - Large Spatial and Small Temporal Scales -- 6.6.2.3 Mississippi Bight Region - Large Spatial and Temporal Scales -- 6.7 Remotely Sensed NOM Measurements -- 6.7.1 Fluorescent CDOM and Validation of Remote Sensing Products -- 6.7.2 Active Remote Sensors -- 6.7.3 Fluorescence of CDOM and Passive Sensors -- 6.7.4 Remote Sensing Summary -- 6.8 Summary -- Acknowledgments -- References -- Part III Environmental Effects -- 7 Physicochemical Effects on Dissolved Organic Matter Fluorescence in Natural Waters -- 7.1 Introduction -- 7.2 The Quenching of DOM Fluorescence -- 7.3 Effects of Molecular Weight and Fluorophore Size -- 7.4 Effect of Temperature -- 7.5 Effect of pH -- 7.6 Effect of Metals -- 7.7 Effect of Salinity (Ionic Strength) -- 7.8 Effect of Particles -- 7.9 Effect of Sunlight -- 7.10 Summary and Future Directions -- Acknowledgments -- References -- 8 Biological Origins and Fate of Fluorescent Dissolved Organic Matter in Aquatic Environments -- 8.1 Introduction -- 8.2. Sources -- 8.2.1 Allochthonous versus autochthonous -- 8.2.2 Terrestrial Organic Matter -- 8.2.3 Aquatic Organic Matter. , 8.3 Microbial Degradation of Fluorescent Dissolved Organic Matter -- 8.3.1 Bioavailability of FDOM -- 8.3.1.1 Amino Acid-like Fluorescence -- 8.3.1.2 Humic-like Fluorescence -- 8.3.2 Interactions between Photochemical and Microbial Degradation -- 8.4 Future Research -- Acknowledgments -- References -- Part IV Interpretation and Classification -- 9 Fluorescence Indices and Their Interpretation -- 9.1 Introduction -- 9.2 Overview of Common Fluorescence Indices -- 9.2.1 A "Humification Index" to Track Chemical Properties Developed by Kalbitz and Colleagues (HIX< -- sub> -- SYN< -- /sub> -- ) -- 9.2.2 Zsolnay's Humification Index to Identify Soil Organic Matter Properties (HIX< -- sub> -- EM< -- /sub> -- ) -- 9.2.3 Freshness Index to Identify Microbial Material in Marine DOM (the "ß/a" and "BIX" Index) -- 9.2.4 Fluorescence Index to identify Precursor Material in Freshwater DOM (FI) -- 9.2.5 The "Peak T/Peak C Ratio" to Identify Sewage Impact on Rivers -- 9.2.6 Redox Index as an Indicator of the Oxidation State of Quinone-Like Moieties -- 9.3 Applications of Fluorescence Indices -- 9.3.1 Using Fluorescence Indices to Identify Environmental Controls on Soil Organic Matter -- 9.3.2 The Development of a Fluorescence Index to Measure Organic Matter Humification Preserved in Cave Stalagmites -- 9.3.3 Understanding Controls on DOM Source and Quality in Surface Waters -- 9.3.4 Understanding DOM Changes in Estuaries -- 9.4 Spectroscopic Challenges toward Using the Indices -- 9.4.1 Instrument-Specific Effects and Proper EEM Correction -- 9.4.2 Concentration Issues and the Inner-Filter Effect -- 9.4.3 pH Effect on Fluorescence -- 9.5 Conclusions -- Acknowledgments -- References -- 10 Chemometric Analysis of Organic Matter Fluorescence -- 10.1 Introduction -- 10.2 Multivariate and Multiway Data Sets -- 10.3 Preprocessing of Data Matrices and Arrays. , 10.4 Exploratory Data Analysis.
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  • 2
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 40 (2013): 511–516, doi:10.1002/grl.50160.
    Description: Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11–61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m−2 yr−1. The basin-wide DIC yield was ~8.84 × 104 mol km−2 yr−1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr−1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers.
    Description: This project was supported by a grant from the National Science Foundation for the Global Rivers Project (NSF 0851101).
    Description: 2013-08-14
    Keywords: Inorganic carbon ; Carbon dioxide ; Carbon fluxes ; pH ; Alkalinity ; Congo River
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 3
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 119 (2014): 687–702, doi:10.1002/2013JG002442.
    Description: Dissolved organic carbon (DOC) and inorganic carbon (DIC, pCO2), lignin biomarkers, and theoptical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin, with the aim of examining how vegetation cover and hydrology influences the composition and concentration of fluvial carbon (C). Three sampling campaigns (February 2010, November 2010, and August 2011) spanning 56 sites are compared by subbasin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated shifting rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp subbasins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2,600 and 11,922 µatm, with swamp regions exhibiting extremely high pCO2 (10,598–15,802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers are largely driven by terrestrial ecosystem structure and that anthropogenic land use or climate change may impact fluvial C composition and reactivity, with ramifications for regional C budgets and future climate scenarios.
    Description: This work was supported by the National Science Foundation as part of the ETBC Collaborative Research: Controls on the Flux, Age, and Composition of Terrestrial Organic Carbon Exported by Rivers to the Ocean (0851101 and 0851015).
    Description: 2014-10-30
    Keywords: Dissolved organic matter ; Lignin ; CDOM ; pCO2 ; Aquatic ; Hydrology
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: text/richtext
    Format: application/vnd.ms-excel
    Format: application/pdf
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