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1999 Progress Report: Organic Analysis
EPA Grant Number: R825433C040Subproject: 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: Levinson, Barbara
Project Period: October 1, 1996 through September 30, 2000
Project Period Covered by this Report: October 1, 1998 through September 30, 1999
RFA: Exploratory Environmental Research Centers (1992)
Research Category: Center for Ecological Health Research , Targeted Research
Description:
Objective:Develops techniques and methods for organic analysis in sediment cores, large masses of water, air and tissue, including multi-residue methods to detect not only a single contaminant but degradation products, metabolites and similar contaminants.
Progress Summary:The laboratory for Trace Organic Identification has been established in Meyer Hall. The instrumentation available includes gas chromatography (GC), infrared spectrometry (IR), ultraviolet/visible spectrophotometry (UV/VIS), Ion trap mass spectrometry (MS) and high pressure liquid chromatography (HPLC). The lab also has access to high field, high resolution and soft-ionization mass spectrometry. Many techniques and methods have been developed:
Measurement of Hydroxy Radical in Natural Waters. We hypothesize that hydroxy radical may be important in the degradation of a number of pesticides, particularly those which contain halogens. This technique will be useful to the Clear Lake, Tahoe, Sacramento Rivers projects.
Development of an Instrumental Data Library for Pesticides. Rapid identification of pesticides in a complex mixture by using spectral data including gas chromatographic retention index (I), infrared spectra (IR), and mass spectra (MS) was developed. It is generally recognized that identification of an unknown compound can be achieved by matching two different spectral data. Therefore, obtaining IR and MS in addition to GC retention index for pesticides was also the purpose of this study.
Development of an Analytical Method for Trace Organic Compounds in a Large Mass of Water. A liquid-liquid continuous extractor was modified to investigate trace organic chemicals present in ground and surface water such as the water from Lake Tahoe and Clear Lake and the Sacramento River.
Development of Gas chromatographic Method for the Determination of Carbofuran and Oxydemeton-methyl (ODM) as well as its Potential Transformation Product Deoxydemeton-methyl (DODM) in Ambient Air. The chemicals were trapped using XAD-4 resin and recovered with an organic solvent. The extraction efficiencies of carbofuran, ODM, and DODM from a XAD-4 resin with ethyl acetate were near 100%. A trapping efficiency study for ODM and DODM demonstrated that both compounds were relatively non-volatile at 35 ± 5 ¡C. Using the method developed, air sampling was conducted at agricultural sites in California where carbofuran, ODM, and DODM have been applied. The highest amount of carbofuran found in the ambient air samples was 2.1 mg. However, none of the samples collected from ambient air had a sufficient amount of ODM or DODM for the limit of quantitation (0.05 mg).
Development of a Fast and Sensitive (down to 1 ppb) Method of Esfenvalerate and cis/trans-Permethrin Analysis in Environmental Water Samples Using Solid-Phase Extraction (SPE) and Gas Chromatography with Electrolytic Conductivity Detection (GC-ELCD). Representative natural waters were collected from three locations in Northern California (Putah Creek, Sacramento River and Clear Lake) and in Nevada (Lake Tahoe). Samples were spiked with the three pesticides and concentrations were quantified.
Although environmental water samples varied in pH and appearance, recoveries were not significantly different from those of purified water. This was somewhat surprising since suspended solid loading varied from highest to lowest in the order Clear Lake < Putah Creek < Sacramento River < Lake Tahoe and since permethrin and esfenvalerate were highly lipophilic compounds which may partition from water to sediments in littoral enclosures.
Gas Chromatographic/Mass Spectrometric Method for Analysis of Chlorophenoxy Acid Herbicides: MCPB and MCPA in Peas. An analytical method for the determination of 2-methyl-4-chlorophenoxybutyric acid (MCPB) and its primary metabolite 2-methyl-4-chlorophenoxyacetic acid (MCPA) residues in peas was developed utilizing liquid-liquid partitioning, derivatization of acids with diazomethane, Florisil® column cleanup, and gas chromatography/mass spectrometry.
The limit of quantitation for MPCB and MPCA was 0.01 ppm. The minimum detectable value for MPCB and MPCA was 0.0045 ppm. Recoveries for MCPB in peas without pods, peas with pods, and dry peas ranged from 69-108%, 87-100%, and 81 -103%, respectively. Recoveries for MCPA in peas without pods, peas with pods, and dry peas ranged 63-94%, 72-86%, and 60-79%, respectively.
Recoveries for MCPB stored over 850 days ranged from 86-91%, 83-84%, and 77-85% for peas without pods, peas with pods, and dry peas, respectively. Recoveries for MCPA stored over 850 days ranged 74-78%, 71-72%, and 68-77% for peas without pods, peas with pods, and dry peas, respectively.
Pea samples treated with MCPB and control samples from the trial fields (Chualar, California; Kimberly, Idaho; Freeville, New York; Aurora, Oregon; Arlington, Wisconsin; Prosser, Washington) had residues levels less than 0.01 ppm except one (0.017 ppm). The method was validated down to the limit of quantitation at 0.01 ppm and the limit of detection at 0.0045 ppm.had no residues (MCPB or MCPA) above the limit of quantitation at 0.01 ppm except one dry peas sample obtained from Idaho which contained 0.017 ppm of MCPA.
Formation of genotoxic formaldehyde from methyl tert-butyl ether (MTBE) upon UV irradiation. Methyl tert-butyl ether (MTBE) has been used in reformulated gasoline in large quantities during the last decade. Consequently, concerns have been raised about its possible adverse effects to humans. Toxicity studies on MTBE have only begun recently. Direct inhalation is the major route of exposure to MTBE released into the air. However, vapor-phase MTBE produced toxic formaldehyde upon UV irradiation. In the present study, the formation of carbonyl compounds, in particular genotoxic formaldehyde, from MTBE by UV irradiation was investigated in order to assess possible adverse effect caused by MTBE in the environment. When 500 mL of MTBE was irradiated with a regular home fluorescent lamp for 16 h in an ethanol solution, 3.3 mmol formaldehyde was formed.
When vapor-phase MTBE was irradiated by a regular house fluorescent lamp, 0.306 mg of formaldehyde was formed from one g of MTBE. The amount of formaldehyde formed from MTBE may not be significant compared with the total amount of MTBE emitted from automobile exhaust. However, MTBE was found to be an additional source of toxic formaldehyde in the environment.
Other methods. Solid phase extraction and micro solid phase extraction which allow field sampling with rapid analysis will be developed for organic chemicals in ecosystems including pesticides, chlorinated hydrocarbons, and certain pigments. Sampling techniques are extremely important because often the methods used by laboratory researchers is not adaptable to field work. These methods are widely supplanting older column chromatography separations due to the easy of use, the reduced solvent use, and the large diversity of available phases. An important idea in the use of solid phase extraction cartridges is the quick application to field sampling in which 100 ml of water can be run through the cartridge with chemicals retained within the cartridge. These chemicals can then be eluted off the cartridges with minimal ease in a laboratory and analyzed quickly. This would reduce both preparation time of the field researcher and the laboratory researcher, while increasing efficiency and being cost effective. Applications such as the separation of pesticides from biological materials is one of the newer developmental uses of solid phase cartridges. Current projects such as the extraction of endosulfan and dicofol from egg matrices are being developed to rapidly analyze exposure of embryos and consequent developmental changes (A.1). Once a sample is prepared, modern advanced instrumentations such as High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), and Gas Chromatography/Mass Spectrometry (GC/MS) will allow positive identification of not only environmental contaminants but the metabolites as well.
Multi-residue methods will be developed that will not only detect a single contaminant but also the environmental degradation products, the metabolites, and similar types of contaminants. Multi-residue methods for chlorinated pesticides are often designed to detect one class such as dichlorodiphenylethanes (DDT, DDE, Dicofol, Methoxychlor). Metabolites such as Endosulfan Sulfate contain large polar groups which are not present in the parent compound (Endosulfan). These metabolites are not separated and analyzed in traditional separation schemes. This oversight would cause a large variance in the estimated determination of exposure against actual exposure, as a high percentage of many environmental contaminants are transformed and retained within the living system.
Analytical methods for biomarkers such as lipid peroxidation products will be developed. Continuing improvement within the field of biochemistry has lead to the identification of biomarkers within a living system. These biomarkers are usually only activated when exposure has occurred. These biomarkers can be quantified long before whole animal effects are seen. This is an excellent method for determination of exposure and potential ecological health problems. Lipid peroxidation is an early warning which can be measured from small biological samples such as blood or tissue.
Lipid peroxidation is the degradation of lipids often by small molecular weight aldehydes such as acrolein, malonaldehyde, fomaldehyde and acetaladehyde which are common lipid breakdown products. Acrolein which is marketed and used under the name Magnicide, is used as a herbicide and has also been shown to produce toxicity to the liver. Further research into the mechanism and ecological effects of acrolein will be carried out.
Future Activities:Dr. Shibamoto is currently on a three-year leave from his faculty responsibilities, having taken an EAP Directorship in Japan. He does not currently have a graduate student working on this project.
Supplemental Keywords:Ecosystem Protection/Environmental Exposure & Risk, Water, Scientific Discipline, RFA, Engineering, Chemistry, & Physics, Chemical Engineering, Analytical Chemistry, Environmental Chemistry, Monitoring/Modeling, Ecology and Ecosystems, Environmental Monitoring, aquatic ecosystem, mass spectrometry, gas chromatography, trace organic identification, ecological risk, MTBE, atmospheric deposition, hydroxyl radical, pesticides
Progress and Final Reports:
Original Abstract
Final 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