Final Report: Source Identification, Transformation, and Transport Processes of N-, O- and S- Containing Organic Chemicals in Wetland and Upland Sediments.

EPA Grant Number: R825513C004
Subproject: this is subproject number 004 , established and managed by the Center Director under grant R825513
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: HSRC (1989) - South and Southwest HSRC
Center Director: Reible, Danny D.
Title: Source Identification, Transformation, and Transport Processes of N-, O- and S- Containing Organic Chemicals in Wetland and Upland Sediments.
Investigators: Catallo, W. James
Institution: Louisiana State University - Baton Rouge
EPA Project Officer: Hahn, Intaek
Project Period: January 1, 1995 through January 1, 1997
Project Amount: Refer to main center abstract for funding details.
RFA: Hazardous Substance Research Centers - HSRC (1989) RFA Text |  Recipients Lists
Research Category: Hazardous Substance Research Centers , Land and Waste Management


The purpose of this study was to evaluate the transformation pathways and major transport processes of representative N-,O-, and S-containing pollutants in prominent wetland and upland sediments under oxidized (aerobic), reduced (methanogenic), and "redox pulsed" (alternately flooded and drained) conditions. Target chemical mixtures included materials of concern at hazardous waste sites, Defense and Energy Department facilities, and dredge disposal sites. The transformation sequences and apparent stable endpoints of target analytes were documented and related to the sediment type and sediment physicochemical variables (grain size distribution, organic matter content, Eh regime). The result was a time series profile of chemical and biological transformation under conditions found in different natural sediments, and an evaluation of different transport processes which might become important during these transformations. That is, the time course changes in chemical fine structure in the mixtures in response to sediment variables will be documented and the significance of these to environmental mobility and ultimate fates will be explored. These data are useful when evaluating the sources of unknown chemical mixtures which have been in sediments for varying periods of time (e.g. dredge materials, sediment cores), and for predicting mobility, lability, and risk/hazard associated with fresh mixtures. Changes in partitioning, metal complexation chemistry, and electrochemistry of the target compounds and mixtures were evaluated in time using microcosms, in vitro assays (leaching, phase transfer, partitioning), and electroanalyses, and these data will be related to estimates of quantum mechanical and thermodynamic properties determined using models (chemical estimation SARs, MOPAC and MMP2). Quantitative studies on selective transport processes mediated by redox reactions also will be performed. Briefly, indirect (redox-mediated dissolution of inorganic colloids and minerals, mineralization of organic matter, and/or solubilization of metals) and direct (oxidation/reduction of the analyte) phase transfer mechanisms were also examined.

Summary/Accomplishments (Outputs/Outcomes):

The mixtures evaluated in this study were: 1) a coal anthracene oil containing high levels of PAHs, N-O-and S-heterocycles, nitriles, phenols, and amines (e.g., quinoline, acridine, benzo(h)quinoline, 1-aminopyrene). The compound spectrum in this mixture is similar to those found in wood preservation wastes, petrochemical waste streams, incinerator exhausts, urban air particulates and other high temperature pyrolysates. These materials were added to a) controlled Eh and, b) simulated tidal marsh microcosms developed in this laboratory for organic chemical fate studies. Model sediments were a freshwater wetland sediment (Spring Bayou, LA), a Crowley, LA silt loam agricultural soil and an estuarine clay (Terrebonne, LA). Three treatments were established for each sediment: microcosms will be maintained under a) well oxidized (Eh>250 mV) conditions, b) highly reduced/methanogenic (Eh>-350 mV) conditions and c) variably oxidized and reduced ("pulsed") conditions. Redox potentials were monitored using a field deployable Eh data logger. At intervals, sample were extracted from the microcosms and analyzed quantitatively and qualitatively using GC, GC-MS and other techniques. All sediment fate data from the microcosms were referenced to identical sediments that have been sterilized using high intensity radiation (1-2 Mrad) from a cobalt-60 source.

Identification of transformation products were performed using interpretation of mass spectra and data from previous and on-going deuterated tracer studies of transformation sequences. Partitioning behavior of the mixtures were evaluated in biphasic liquid systems, and in the sediment water systems under oxidized and reduced conditions. The Eh of the redox-pulse systems were logged in a time series, and this allows for an evaluation of time-dependent sorption-desorption regimes and the importance of redox-active metal chemistry in the transformation and mobility of the chemicals.

  • Developed synthesis of protiated and stable-isotope (deuterium) labeled standards for a range of previously unavailable PAHs, azarenes, S- and O-heterocycles, and nitroaromatic compounds.
  • Deployed these standards in micro- and mesocosm experiments evaluating the effects of hydrology (flooded, drained, and tidally-pulsed) on biochemical processes.
  • Developed tide simulation micro- and mesocosms containing plants, sediments, and microbes in configurations found in field settings.

  • Journal Articles on this Report : 10 Displayed | Download in RIS Format

    Other subproject views: All 21 publications 12 publications in selected types All 10 journal articles
    Other center views: All 392 publications 154 publications in selected types All 106 journal articles
    Type Citation Sub Project Document Sources
    Journal Article Catallo WJ, Henk W, Younger L, Mills O, Thiele DJ, Meyers SP. Trace metal uptake by Pichia spartinae, an endosymbiotic yeast in the salt marsh cord grass Spartina alterniflora. Chemistry and Ecology 1996;13(2):113-131 R825513C004 (Final)
    not available
    Journal Article Catallo WJ, Junk T. Sonochemical dechlorination of hazardous wastes in aqueous systems. Waste Management 1995;15(4):303-309. R825513C004 (Final)
    not available
    Journal Article Catallo WJ, Schlenker M, Gambrell RP, Shane BS. Toxic chemicals and trace metals from urban and rural Louisiana lakes: Recent historical profiles and toxicological significance. Environmental Science & Technology 1995;29(6):1436-1445. R825513C004 (Final)
  • Other: ACS Publications PDF
  • Journal Article Catallo WJ. Transformation of N-, O-, and S-heterocycles (NOSHs) in estuarine sediments: Effects of redox potential and sediment particle size. Chemosphere 1996;33(12):2543-2563. R825513C004 (Final)
    not available
    Journal Article Catallo WJ. Historical profiles of toxic chemical in urban and rural Louisiana lake sediments: Epidmiological significance. Journal of the Louisiana State Medical Society 1995;147(4):159-167. R825513C004 (Final)
    not available
    Journal Article Junk T, Catallo WJ. Preparative supercritical deuterium exchange in arenes and heterocycles. Tetrahedron Letters 1996;37(20):3445-3348. R825513C004 (Final)
    not available
    Journal Article Junk T, Catallo WJ. Hydrogen isotope exchange reactions involving C-H (D, T) bonds. Chemical Society Reviews 1997;26:401-406. R825513C004 (Final)
    not available
    Journal Article Junk T, Catallo WJ, Civilis LD. Synthesis of polydeuterated benzothiazoles via supercritical deuteration of anilines. Journal Labelled Compounds & Radiopharmaceuticals 1997;39(8):625-630. R825513C004 (Final)
    not available
    Journal Article Junk T, Catallo WJ. Environmental transformation products of 2,4,6-trinitrotoluene. Chemical Speciation and Bioavailability 1998;10(2):47-52. R825513C004 (Final)
    not available
    Journal Article Junk T, Catallo WJ, Elguero J. Synthesis in superheated aqueous media: Preparation of fully deuterated pyrazoles and quinoxalines. Tetrahedron Letters 38(36):6309-6312. R825513C004 (Final)
    not available

    Supplemental Keywords:

    biogeochemical processes, contaminant mobility, and hydrology., RFA, Scientific Discipline, Waste, Water, Ecosystem Protection/Environmental Exposure & Risk, Chemical Engineering, Contaminated Sediments, Environmental Chemistry, Fate & Transport, Hazardous Waste, Ecology and Ecosystems, Hazardous, Environmental Engineering, environmental technology, sediment treatment, amines, hazardous waste management, hazardous waste treatment, risk assessment, fate and transport, contaminated marine sediment, soil and groundwater remediation, biodegradation, contaminated sediment, nitrites, kinetics, chemical contaminants, contaminated soil, PAH, bioremediation of soils, marine sediments, remediation, chemical kinetics, hydrology, oil spills, Phenol, biotransformation, currents, organic chemicals, anaerobic biotransformation, extraction of metals, technology transfer, heavy metals, CERCLA, aquifer fate and treatment, technical outreach

    Progress and Final Reports:

    Original Abstract
  • 1995

  • Main Center Abstract and Reports:

    R825513    HSRC (1989) - South and Southwest HSRC

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R825513C001 Sediment Resuspension and Contaminant Transport in an Estuary.
    R825513C002 Contaminant Transport Across Cohesive Sediment Interfaces.
    R825513C003 Mobilization and Fate of Inorganic Contaminant due to Resuspension of Cohesive Sediment.
    R825513C004 Source Identification, Transformation, and Transport Processes of N-, O- and S- Containing Organic Chemicals in Wetland and Upland Sediments.
    R825513C005 Mobility and Transport of Radium from Sediment and Waste Pits.
    R825513C006 Anaerobic Biodegradation of 2,4,6-Trinitrotoluene and Other Nitroaromatic Compounds by Clostridium Acetobutylicum.
    R825513C007 Investigation on the Fate and Biotransformation of Hexachlorobutadiene and Chlorobenzenes in a Sediment-Water Estuarine System
    R825513C008 An Investigation of Chemical Transport from Contaminated Sediments through Porous Containment Structures
    R825513C009 Evaluation of Placement and Effectiveness of Sediment Caps
    R825513C010 Coupled Biological and Physicochemical Bed-Sediment Processes
    R825513C011 Pollutant Fluxes to Aquatic Systems via Coupled Biological and Physicochemical Bed-Sediment Processes
    R825513C012 Controls on Metals Partitioning in Contaminated Sediments
    R825513C013 Phytoremediation of TNT Contaminated Soil and Groundwaters
    R825513C014 Sediment-Based Remediation of Hazardous Substances at a Contaminated Military Base
    R825513C015 Effect of Natural Dynamic Changes on Pollutant-Sediment Interaction
    R825513C016 Desorption of Nonpolar Organic Pollutants from Historically Contaminated Sediments and Dredged Materials
    R825513C017 Modeling Air Emissions of Organic Compounds from Contaminated Sediments and Dredged Materials title change in last year to "Long-term Release of Pollutants from Contaminated Sediment Dredged Material"
    R825513C018 Development of an Integrated Optic Interferometer for In-Situ Monitoring of Volatile Hydrocarbons
    R825513C019 Bioremediation of Contaminated Sediments and Dredged Material
    R825513C020 Bioremediation of Sediments Contaminated with Polyaromatic Hydrocarbons
    R825513C021 Role of Particles in Mobilizing Hazardous Chemicals in Urban Runoff
    R825513C022 Particle Transport and Deposit Morphology at the Sediment/Water Interface
    R825513C023 Uptake of Metal Ions from Aqueous Solutions by Sediments
    R825513C024 Bioavailability of Desorption Resistant Hydrocarbons in Sediment-Water Systems.
    R825513C025 Interactive Roles of Microbial and Spartina Populations in Mercury Methylation Processes in Bioremediation of Contaminated Sediments in Salt-Marsh Systems
    R825513C026 Evaluation of Physical-Chemical Methods for Rapid Assessment of the Bioavailability of Moderately Polar Compounds in Sediments
    R825513C027 Freshwater Bioturbators in Riverine Sediments as Enhancers of Contaminant Release
    R825513C028 Characterization of Laguna Madre Contaminated Sediments.
    R825513C029 The Role of Competitive Adsorption of Suspended Sediments in Determining Partitioning and Colloidal Stability.
    R825513C030 Remediation of TNT-Contaminated Soil by Cyanobacterial Mat.
    R825513C031 Experimental and Detailed Mathematical Modeling of Diffusion of Contaminants in Fluids
    R825513C033 Application of Biotechnology in Bioremediation of Contaminated Sediments
    R825513C034 Characterization of PAH's Degrading Bacteria in Coastal Sediments
    R825513C035 Dynamic Aspects of Metal Speciation in the Miami River Sediments in Relation to Particle Size Distribution of Chemical Heterogeneity