Final Report: Organic Analysis

EPA Grant Number: R825433C040
Subproject: this is subproject number 040 , established and managed by the Center Director under grant R825433
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: EERC - Center for Ecological Health Research (Cal Davis)
Center Director: Rolston, Dennis E.
Title: Organic Analysis
Investigators: Shibamoto, Takayuki
Institution: University of California - Davis
EPA Project Officer: Hahn, Intaek
Project Period: October 1, 1996 through September 30, 2000
RFA: Exploratory Environmental Research Centers (1992) RFA Text |  Recipients Lists
Research Category: Center for Ecological Health Research , Targeted Research

Objective:

The objective of this research project was to develop new methods for analyzing organic chemicals, including pesticides and volatile organic compounds in various matrices (water, food, air, and ground), to assess their possible adverse effects on humans and ecosystems. In particular, we generated methods for analyzing: (1) trace organic compounds in a large mass of water; (2) the pesticides esfenvalerate and cis/trans-permethrin; (3) the herbicide 2-methyl-4-chlorophenoxybutyric acid (MCPB) and its derivative, 2-methyl-4-chlorophenoxyacetic acid (MCPA), in peas; (4) the naturally occurring pesticide rotenone; and (5) formaldehyde formed by ultraviolet (UV)-irradiated methyl tertiarybutyl ether (MTBE).

Summary/Accomplishments (Outputs/Outcomes):

The recovery of trace chemicals from a large mass of water is one of the most important sample-preparation steps for investigating the fate of chemicals in the environment. We modified a liquid-liquid continuous extractor to investigate trace organic chemicals present in groundwater and surface water, including water from Lake Tahoe, Clear Lake, and the Sacramento River.

We also developed a new method for analyzing pyrethroid pesticides in water samples. Many aquatic organisms are highly susceptible to pyrethroid intoxication, and applications typically made throughout the spring and summer months coincide with the spawning period of several fish species in California. We conducted esfenvalerate, cis-permethrin, and trans-permethrin analysis in surface waters using solid-phase extraction and gas chromatography (GC) with electrolytic conductivity detection.

MCPB has been used since 1954 for postemergence control of annual and perennial broad-leaved weeds in food crops, but analysis of MCPB and its primary metabolite, MCPA, by GC has proved difficult, especially when analyzing trace levels of MCPB and MCPA in food samples. Consequently, we developed a new method involving liquid-liquid partitioning, derivatization with diazomethane, Florisil® cleanup, and GC equipment outfitted with a fused silica capillary column and interfaced to a mass selective detector.

Rotenone is another pesticide regularly used on a wide variety of crops, although it occurs naturally in a variety of leguminous plants and is used in streams and lakes across the United States to restore populations of rare, threatened, or endangered native fish populations. Rotenone has been analyzed only by high performance liquid chromatography (HPLC), which is satisfactory for simple matrices such as water. The determination of rotenone, however, in more complex matrices, such as food and animal tissue, may require higher resolution and sensitivity than that provided by HPLC. We surmounted this limitation by designing a high-resolution capillary gas chromatographic method, which affords high sensitivity even in a complex matrix.

Analyzing toxic carbonyl compounds such as vapor-phase formaldehyde can be extremely difficult because of their high volatility and reactivity. This analysis, however, is an important undertaking because humans are primarily exposed to such compounds by breathing air. We developed a simple and specific derivatization method for analyzing formaldehyde produced by the widely used fuel additive MTBE upon UV-irradiation. This method allowed us to assess the potential risks of formaldehyde toxicity in relation to MTBE usage.

The following activities were accomplished:

• We developed a liquid-liquid continuous extractor that can recover trace amounts of pesticide-breakdown products, including benzene derivatives, fatty acid derivatives, and pthalate derivatives, from environmental water samples. Because some of these derivatives may be harmful to organisms (phthalate in particular is known to be an endocrine disruptor), the ability to detect and analyze these organic compounds is very important. Our new method will help other researchers assess the health risks of pesticide breakdown products in various bodies of water.

• We developed a fast, selective, and sensitive (300 pg) method of analyzing synthetic pyrethroids (esfenvalerate and cis- and trans-permethrin) in natural surface waters. Until now, no satisfactory method for this type of analysis existed. Detection and analysis of water samples thought to contain pyrethroid pesticides is important because many aquatic organisms are highly susceptible to pyrethroid intoxication, and these types of pesticides are widely used. Our new analytical method will allow researchers to assess the risks posed by these pesticides, and will ultimately help agricultural and environmental managers create new or adjust existing regulations concerning pyrethroid pesticide usage.

• We found that synthetic pyrethroid pesticides degrade quickly in natural waters. Therefore, we advise other researchers investigating pyrethroid pesticides to analyze water samples within 24 hours of collection to ensure accurate results.

• Using GC, we developed a trace analytical method for highly polar pesticides, MCPB and its primary metabolite MCPA. This kind of analysis previously was very difficult, and our new method makes it relatively easy for researchers to analyze trace amounts of MCPB and MCPA. Because these pesticides are widely used in crops, this analytical method is essential to ensure food safety.

• We validated our method down to the limit of quantitation at 0.01 ppm and to the limit of detection at 0.0045 ppm, satisfying U.S. Environmental Protection Agency (EPA) guidelines. Results from research performed with our method will be considered admissible by U.S. EPA standards.

• We developed a simple and specific method for analyzing formaldehyde released by UV irradiation of MTBE. Because formaldehyde poses serious health risks to humans, our research raises awareness of this additional hazard of MTBE, allows other researchers to investigate health hazards related to formaldehyde and MTBE, and may influence policy decisions concerning MTBE regulation.

• We created a simple and sensitive method for rotenone analysis that works for complex matrices such as food and animal tissue. Although rotenone is used frequently as an insecticide on crops, such a method previously was unavailable. Our innovation makes rotenone analysis more convenient for other researchers, thus expanding the available data about the effects and implications of rotenone usage.

Supplemental Keywords:

ecosystem, ecosystem protection, environmental exposure and risk, geographic area, international cooperation, water, terrestrial ecosystems, aquatic ecosystem, aquatic ecosystem restoration, aquatic ecosystems and estuarine research, biochemistry, ecological effects, ecological indicators, ecological monitoring, ecology and ecosystems, environmental chemistry, restoration, state, water and watershed, watershed, watershed development, watershed land use, watershed management, watershed modeling, watershed restoration, watershed sustainability, agricultural watershed, exploratory research environmental biology, California, CA, Clear Lake, Lake Tahoe, anthropogenic effects, aquatic habitat, biogeochemical cycling, ecological assessment, ecology assessment models, ecosystem monitoring, ecosystem response, ecosystem stress, environmental stress, environmental stress indicators, fish habitat, hydrologic modeling, hydrology, integrated watershed model, lake ecosystems, lakes, land use, nutrient dynamics, nutrient flux, water management options, water quality, wetlands., RFA, Scientific Discipline, Water, Ecosystem Protection/Environmental Exposure & Risk, Chemical Engineering, Environmental Chemistry, Monitoring/Modeling, Analytical Chemistry, Environmental Monitoring, Ecology and Ecosystems, Engineering, Chemistry, & Physics, hydroxyl radical, aquatic ecosystem, trace organic identification, mass spectrometry, MTBE, pesticides, gas chromatography, ecological risk, pesticide residue

Relevant Websites:

http://ice.ucdavis.edu/cehr/ Exit

Progress and Final Reports:

Original Abstract
  • 1997
  • 1998
  • 1999 Progress Report

  • Main Center Abstract and Reports:

    R825433    EERC - Center for Ecological Health Research (Cal Davis)

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R825433C001 Potential for Long-Term Degradation of Wetland Water Quality Due to Natural Discharge of Polluted Groundwater
    R825433C002 Sacramento River Watershed
    R825433C003 Endocrine Disruption in Fish and Birds
    R825433C004 Biomarkers of Exposure and Deleterious Effect: A Laboratory and Field Investigation
    R825433C005 Fish Developmental Toxicity/Recruitment
    R825433C006 Resolving Multiple Stressors by Biochemical Indicator Patterns and their Linkages to Adverse Effects on Benthic Invertebrate Patterns
    R825433C007 Environmental Chemistry of Bioavailability in Sediments and Water Column
    R825433C008 Reproduction of Birds and mammals in a terrestrial-aquatic interface
    R825433C009 Modeling Ecosystems Under Combined Stress
    R825433C010 Mercury Uptake by Fish
    R825433C011 Clear Lake Watershed
    R825433C012 The Role of Fishes as Transporters of Mercury
    R825433C013 Wetlands Restoration
    R825433C014 Wildlife Bioaccumulation and Effects
    R825433C015 Microbiology of Mercury Methylation in Sediments
    R825433C016 Hg and Fe Biogeochemistry
    R825433C017 Water Motions and Material Transport
    R825433C018 Economic Impacts of Multiple Stresses
    R825433C019 The History of Anthropogenic Effects
    R825433C020 Wetland Restoration
    R825433C021 Sierra Nevada Watershed Project
    R825433C022 Regional Transport of Air Pollutants and Exposure of Sierra Nevada Forests to Ozone
    R825433C023 Biomarkers of Ozone Damage to Sierra Nevada Vegetation
    R825433C024 Effects of Air Pollution on Water Quality: Emission of MTBE and Other Pollutants From Motorized Watercraft
    R825433C025 Regional Movement of Toxics
    R825433C026 Effect of Photochemical Reactions in Fog Drops and Aerosol Particles on the Fate of Atmospheric Chemicals in the Central Valley
    R825433C027 Source Load Modeling for Sediment in Mountainous Watersheds
    R825433C028 Stress of Increased Sediment Loading on Lake and Stream Function
    R825433C029 Watershed Response to Natural and Anthropogenic Stress: Lake Tahoe Nutrient Budget
    R825433C030 Mercury Distribution and Cycling in Sierra Nevada Waterbodies
    R825433C031 Pre-contact Forest Structure
    R825433C032 Identification and distribution of pest complexes in relation to late seral/old growth forest structure in the Lake Tahoe watershed
    R825433C033 Subalpine Marsh Plant Communities as Early Indicators of Ecosystem Stress
    R825433C034 Regional Hydrogeology and Contaminant Transport in a Sierra Nevada Ecosystem
    R825433C035 Border Rivers Watershed
    R825433C036 Toxicity Studies
    R825433C037 Watershed Assessment
    R825433C038 Microbiological Processes in Sediments
    R825433C039 Analytical and Biomarkers Core
    R825433C040 Organic Analysis
    R825433C041 Inorganic Analysis
    R825433C042 Immunoassay and Serum Markers
    R825433C043 Sensitive Biomarkers to Detect Biochemical Changes Indicating Multiple Stresses Including Chemically Induced Stresses
    R825433C044 Molecular, Cellular and Animal Biomarkers of Exposure and Effect
    R825433C045 Microbial Community Assays
    R825433C046 Cumulative and Integrative Biochemical Indicators
    R825433C047 Mercury and Iron Biogeochemistry
    R825433C048 Transport and Fate Core
    R825433C049 Role of Hydrogeologic Processes in Alpine Ecosystem Health
    R825433C050 Regional Hydrologic Modeling With Emphasis on Watershed-Scale Environmental Stresses
    R825433C051 Development of Pollutant Fate and Transport Models for Use in Terrestrial Ecosystem Exposure Assessment
    R825433C052 Pesticide Transport in Subsurface and Surface Water Systems
    R825433C053 Currents in Clear Lake
    R825433C054 Data Integration and Decision Support Core
    R825433C055 Spatial Patterns and Biodiversity
    R825433C056 Modeling Transport in Aquatic Systems
    R825433C057 Spatial and Temporal Trends in Water Quality
    R825433C058 Time Series Analysis and Modeling Ecological Risk
    R825433C059 WWW/Outreach
    R825433C060 Economic Effects of Multiple Stresses
    R825433C061 Effects of Nutrients on Algal Growth
    R825433C062 Nutrient Loading
    R825433C063 Subalpine Wetlands as Early Indicators of Ecosystem Stress
    R825433C064 Chlorinated Hydrocarbons
    R825433C065 Sierra Ozone Studies
    R825433C066 Assessment of Multiple Stresses on Soil Microbial Communities
    R825433C067 Terrestrial - Agriculture
    R825433C069 Molecular Epidemiology Core
    R825433C070 Serum Markers of Environmental Stress
    R825433C071 Development of Sensitive Biomarkers Based on Chemically Induced Changes in Expressions of Oncogenes
    R825433C072 Molecular Monitoring of Microbial Populations
    R825433C073 Aquatic - Rivers and Estuaries
    R825433C074 Border Rivers - Toxicity Studies