2000 Progress Report: Fluorescent Whitening Agents As Facile Pollution Markers In Shellfishing Waters

EPA Grant Number: R827072C001
Subproject: this is subproject number 001 , established and managed by the Center Director under grant R827072
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: Alabama Center For Estuarine Studies (ACES)
Center Director: Shipp, Robert L.
Title: Fluorescent Whitening Agents As Facile Pollution Markers In Shellfishing Waters
Investigators: Cioffi, Eugene A.
Institution: University of South Alabama
EPA Project Officer: Packard, Benjamin H
Project Period: October 1, 1999 through September 30, 2001
Project Period Covered by this Report: October 1, 1999 through September 30, 2000
RFA: Alabama Center For Estuarine Studies (ACES) (1999) RFA Text |  Recipients Lists
Research Category: Estuarine Studies , Targeted Research


Within the past several years, the Alabama Department of Public Health (ADPH) has closed numerous shellfish resources to the taking of shellfish due to elevated bacteriological levels coliform bacteria. Often, closure is a result of either overloaded point sources during a storm event, or non-point source pollution due to septic failure, illicit storm drain connections, etc. Besides the obvious health-related impact due to potential disease vectors, concomitant increased nutrient loading promotes eutrophication and diminished water quality. One of the main problems associated in determining the cause (human/nonhuman) and prevention of fecal coliform bacteria contamination is the inability to precisely determine the source of contamination.

Progress Summary:

Two newer techniques have been utilized to help identify the source of pollution attributed to human activity. The applications of high-resolution fluorescence spectroscopy and nuclear magnetic resonance spectroscopy have shown promise in the quantitation and unequivocal identification of anthropogenic pollutants. Detergents are used in very large quantities, contributing a significant portion of the load of anthropogenic chemicals to the aquatic environment. Fluorescent whitening agents (FWAs) contribute only 0.15% of the total mass of most laundry detergents, and may be discharged to a municipal treatment plant, a septic system, or to a stormwater drainage system (through an illegal connection). These moderately water soluble, fluorescent organic compounds have a high affinity for cellulosic material. In addition, specialty FWAs are used extensively by the paper industry, to whiten pulp and finished paper goods. Since all FWAs absorb UV light at ~ 350nm and emit visible blue light at a maximum of ~ 430nm, they may readily be detected with a high-resolution spectrofluorometer at a high sensitivity (< 50 parts per trillion). The recovery of FWAs in nearby waters (surface, ground, or estuarine waters), in conjunction with elevated bacteriological results, is indicative of ineffective natural cleansing of wastewaters. The recovery of FWA's in stormdrain systems in conjunction with elevated bacteriological (and/or nutrient) results indicates human-related contamination such as an illegal wastewater discharge to the storm drain system. The recovery of specialty FWAs in fresh or estuarine waters are indicative of industrial discharges.

This study is investigating the utilization of fluorescent whitening agents (FWAs) as anthropogenic markers of pollution in the Mobile Bay estuarine system. Individual authentic FWAs have been fully characterized using high-resolution fluorescence spectroscopy and nuclear magnetic spectroscopy (1H and 13C). Several solid-phase supports were investigated for the selective preconcentration of individual FWA classes; C-18 solid supports are the most efficacious for general FWA isolation. The concerted use of C-18 solid-phase extraction and ion-pairing chromatography (tert-butyl ammonium hydroxide/methanol) afforded a reasonably low limit of detection (< 10 ppt), high reproducibility (0.5 to 4.8% RSD), and a wide linear range (0.01-10,000 µg/L; r2 = 0.991). The high overall recoveries of FWAs appear to be independent of sample matrices. Both laboratory and field protocols have been established for sampling and isolation of FWAs. A systematic field survey has been initiated with known point sources, and is currently being expanded to include areas likely to contain both domestic and industrial discharges. Field sampling is logged using a differential global positioning system (DGPS), and laboratory data validated as outlined in the QA/QC plan. Individual FWA isolates have been examined using NMR spectroscopy, and preliminary analyses indicate that larger sample volumes or indirect 1H detection may be necessary for unequivocal individual FWA identification (via spin-coupling analysis). The thermodynamic properties of the individual FWAs are being investigated using both semi-empirical molecular dynamics and ab initio computational techniques, in order to understand the long FWA residence lifetimes the environment, their slow molecular isomerization, and to perhaps predict the ultimate fate of these anthropogenic materials.

Journal Articles:

No journal articles submitted with this report: View all 1 publications for this subproject

Supplemental Keywords:

estuarine research, coastal ecosystem, human modifications, land and water use, watersheds, aquatic ecosystems, pollution markers, coliform bacteria, nutrient loading, wet weather flows, spectropscopic studies., RFA, Scientific Discipline, Water, ECOSYSTEMS, Ecosystem Protection/Environmental Exposure & Risk, estuarine research, Aquatic Ecosystems & Estuarine Research, Environmental Chemistry, Restoration, Aquatic Ecosystem, Aquatic Ecosystems, Environmental Monitoring, Ecology and Ecosystems, Aquatic Ecosystem Restoration, Environmental Engineering, nuclear magnetic resonance, coastal ecosystem, nutrient dynamics, estuaries, shellfish, nutrient loading, spectroscopic studies, pollution markers, coastal environments, whitening agents, water quality

Progress and Final Reports:

Original Abstract
  • Final

  • Main Center Abstract and Reports:

    R827072    Alabama Center For Estuarine Studies (ACES)

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R827072C001 Fluorescent Whitening Agents As Facile Pollution Markers In Shellfishing Waters
    R827072C002 Red Snapper Demographics on Artificial Reefs: The Effect of Nearest-Neighbor Dynamics
    R827072C003 Stabilization of Eroding Shorelines in Estuarine Wave Eliminates with Constructed Fringe Wetlands Incorporating Offshore Breakwaters
    R827072C004 Interaction Between Water Column Structure and Reproduction in Jellyfish Populations Of Mobile Bay (SGER)
    R827072C005 Effects of Variation in River Discharge and Wind-Driven Resuspension on Higher Trophic Levels in the Mobile Bay Ecosystem
    R827072C006 Results of Zooplankton Component
    R827072C007 Benthic Study Component
    R827072C008 A Preliminary Survey of Macroalgal and Aquatic Plant Distribution in the Mobile Tensaw Delta
    R827072C009 Fisheries-induced changes in the structure and function of shallow water "nursery habitats": an experimental assessment
    R827072C010 Effects Of Variation in River Discharge and Wind-Driven Resuspension on Lower Trophic Levels of the Mobile Bay Ecosystem
    R827072C011 Evaluation of Alabama Estuaries as Developmental Habitat for Juvenile Sea Turtles
    R827072C012 Effects of Salinity Stress on Natural and Anthropogenically-Derived Bacteria in Estuarine Environments
    R827072C013 The Role of Land-Use/Land-Cover and Sub-estuarine Ecosystem Nitrogen Cycling in the Regulation of Nitrogen Delivery to a River Dominated Estuary; Mobile Bay, Alabama
    R827072C014 Environmental Attitudes of Alabama Coastal Residents: Public Opinion Polls and Environmental Policy
    R827072C015 Synthesis and Characterization of an Electrochemical Peptide Nucleic Acid Probe
    R827072C016 Determinants of Small-Scale Variation in the Abundance of the Blue Crab Callinectes Sapidus
    R827072C017 Effects of Estrogen Pollution on the Reproductive Fitness of the Gulf Pipefish, Syngnathus scovelli
    R827072C019 A Model for Genetic Diversity Aquatic Insects of the Mobile/Tensaw River Delta
    R827072C020 Evaluating Trophic Processes as Indicators of Anthropogenic Eutrophication in Coastal Ecosystems: An Exploratory Analysis
    R827072C021 Effects of Anthropogenic Eutrophication on the Magnitude and Trophic Fate of Microphytobenthic Production in Estuaries
    R827072C022 Characteristics of Ship Waves and Wind Waves in Mobile Bay
    R827072C023 Methods Comparison Between Stripping Voltammetry and Plasma Emission Spectroscopy for Metals in Mobile Bay
    R827072C024 Changes in Water Conditions and Sedimentation Rates Associated With Construction of the Mobile Bay Causeway
    R827072C025 Cold-Induced Hibernation of Marine Vibrios in the Gulf of Mexico: A Study of Cell-Cell Communication and Dormancy in Vibrio vulnificus
    R827072C026 Holocene Sedimentary History of Weeks Bay, AL: Human and Natural Impacts on Deposition in a Gulf Coast Estuary
    R827072C027 Shelter Bottlenecks and Self-Regulation in Blue Crab Populations: Assessing the Roles of Nursery Habitats and Juvenile Interactions for Shelter Dependent Organisms
    R827072C028 Predicting Seagrass Survival in Nutrient Enriched Waters: Toward a New View of an Existing Paradigm
    R827072C029 DMSP and its Role as an Antioxidant in the Salt Marsh Macrophyte Spartina alterniflora
    R827072C030 A Preliminary Survey of Aerial and Ground-Dwelling Insects of the Mobile/Tensaw Delta
    R827072C031 Natural Biogeochemical Tags of Striped Mullet, Mugil cephalus, Estuarine Nursery Areas in the North Central Gulf of Mexico
    R827072C032 Resolution of Sedimentation Rates in Impacted Coastal Environments Using 137Cs and 210Pb Markers: Dog River and Fowl River Embayments
    R827072C033 Investigation of the Use of Pulse Amplitude Modulated (PAM) Fluorometry as an Indicator of Submerged Aquatic Vegetation Health in Mobile Bay
    R827072C034 Influence of Invasive Plant Species in Determining Diversity of Aquatic Vegetation in the Mobile-Tensaw Delta
    R827072C035 The Influence of Shallow Water Hydrodynamics on the Importance of Seagrass Detritus in Estuarine Food Webs
    R827072C036 Food Web Interactions, Spatial Subsidies and the Flow of Energy Between the Mobile Bay Delta and Offshore Waters: A SGER Proposal to the Alabama Center for Estuarine Studies
    R830651C001 Meteorological Modeling of Hurricanes and Coastal Interactions: A Stability Study For Vertical Pressure Levels
    R830651C002 Characterization of Glycoprotein Cues Used by the Parasitic Rhizocephalan Barnacle Loxothylacus texanus To Identify Its Blue Crab Host, Callinectes sapidus
    R830651C003 Survey of Diamondback Terrapin Populations in Alabama Estuaries
    R830651C004 An Assessment of Environmental Contaminant Levels in Water and Dragonfly Larvae Tissues from the Mobile/Tensaw Delta