Source: CONNECTICUT AGRICULTURAL EXPERIMENT STATION submitted to NRP
CHLORDANE PROFILES IN CONNECTICUT AIR
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
0187947
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Feb 2, 2001
Project End Date
Feb 2, 2004
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
CONNECTICUT AGRICULTURAL EXPERIMENT STATION
PO BOX 1106
NEW HAVEN,CT 06504
Performing Department
ANALYTICAL CHEMISTRY
Non Technical Summary
Chlordane is a persistent pollutant which has been found in Connecticut soils and air samples. This project compares concentrations of chlordane in soils with the concentrations in the air directly above those soils to determine if volatilization of chlordane from soils is the source of chlordane to the air.
Animal Health Component
100%
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1330110200025%
1330410200050%
1335220200025%
Knowledge Area
133 - Pollution Prevention and Mitigation;

Subject Of Investigation
0110 - Soil; 0410 - Air; 5220 - Pesticides;

Field Of Science
2000 - Chemistry;
Goals / Objectives
1. Determine the "normal" background concentration, compositional and chiral profiles for chlordane residues in ambient Connecticut air. This will include air samples taken above sites with high concentrations of chlordane in the soil as a result of past usage of chlordane and sites with low or no observable concentrations of chlordane. 2. Relate observed concentrations and compositional profiles of chlordane in air to the sources of the chlordane compounds. Potential sources include volatilization from chlordane contaminated sites in Connecticut or transport into Connecticut through the atmosphere 3. High concentrations of chlordane residues have been observed in soils near some Connecticut home foundations. Determine concentrations of chlordane in the indoor air of these homes and compare those concentrations to the external ambient air.
Project Methods
Soil and air samples will be taken from multiple sites around the State of Connecticut to determine typical composition and chiral profiles. These sites will include our experimental plot, the Lockwood Farm, the CAES Valley Laboratory, as well as other sites identified in our earlier soil surveys as having either high concentrations of chlordane in the soil (potential sources), or low or non-detectable concentrations (background sites). At each site soil samples will be taken from the top 6" of a soil. The soil will be sieved to remove stones, and the soil will be analyzed for chlordane compounds using our current procedures. In brief, a microwave assisted extraction using 2:3 acetone:hexane, this is followed by sample clean-up and chiral gas chromatography ion trap detection mass spectrometry (GC/ITD-MS). High volume air samples will be obtained at each site by drawing air through a glass fiber filter (GFF) to collect particulate matter in the air and then a precleaned polyurethane foam (PUF) plug to collect vapor phase organic compounds. The GFF will be extracted by the microwave procedure while the PUF will be soxhlet extracted with petroleum ether. Following extraction the samples will undergo clean-up and GC/ITD-MS analysis. Technical chlordane is composed of mixture of over 140 different compounds. The three most abundant of which are cis-chlordane (CC), trans-chlordane (TC) and trans-nonachlor (TN). TC and CC are chiral compounds, racemic in the technical mixture but potentially non-racemic in weatthered chlordane residues. Racemic standards of TC, CC and the achiral TN will be used to prepare a series of calibration standards in isooctane with individual enantiomer concentrations of 12.5, 25, 50, 125, 250, and 500 ng/mL. Each calibration standard will also contain oxychlordane, a chlordane metabolite, at twice the concentration of the other compounds. Two ions from the most intense chlorine cluster, the (M-Cl)+ ion, of each compound are selected for quantification. The observed isotope ratio from the selected pair of ions for each analyte is determined for standards and for samples. Internal standard calibration curves for each analyte will be generated from the sum of the two extracted ions as compared to the sum of ions from one of the internal standards. Enantiomer ratios for chiral compounds (ER, +/-) will be calculated from each ion in the pair. All sample data will be compiled and tabulated. Data for the various samples will be compared. We will attempt to draw correlations between soil concentrations and the air concentrations above those soil samples. We will also examine the relationships between air concentration, air temperature, and sampler height. Monthly monitoring of air from the CAES plot will be conducted allowing us to examine seasonal effects. These data will be used to determine typical background concentrations of chlordane in air in Connecticut and the sources of chlordane to that air.

Progress 02/02/01 to 02/02/04

Outputs
Chlordane has been banned since 1988, but soil-bound residues continue to be observed. Chlordane has been found in both indoor and outdoor ambient air. We are conducting studies to help explain the continued presence of chlordane in ambient air. Chlordane was originally applied as a mixture of over 140 different related compounds. The primary active ingredients of this mixture were cis-chlordane, trans-chlordane, and trans-nonachlor and together they comprised about 25% of the total. Two of the three primary active ingredients are chiral, present as racemates in the technical mixture. Therefore, analysis of the relative concentrations of both chiral and achiral components of the technical mixture in environmental samples can differentiate enantioselective processes (such as microbial degradation) from physical-chemical processes (such as volatilization). We have examined the compositional and chiral profiles of chlordane in Connecticut ambient air at four locations (2 urban, 1 suburban, 1 rural) within Connecticut and compared these data to those reported for ambient air in other parts of the country. We are also conducting studies at a weathered contaminated site from a chlordane application over 40 years ago. Air samples were collected using high volume samplers to draw air through glass fiber filters (to remove particulate matter) and polyurethane foam plugs to collect the vapor phase chlordane compounds. The samples were collected at three different heights above the contaminated plot, and at the four other locations. Samples for each height and location were collected every two weeks. Vapor phase samples were extracted using Soxhlet extraction cleaned up with florisil column chromatography and analyzed using chiral gas chromatography /electron impact ion trap mass spectrometry. The results of these analyses show that the ambient air concentrations and profiles in Connecticut are similar to ambient concentrations and profiles in other parts of the country. These air concentrations are consistent with a source related to the volatilization of chlordane from locations where it was used as a termiticide around homes. Air collected above the contaminated plot shows that the concentration decreases with height and that the concentrations from above the plot are higher than concentrations observed at the other locations. Furthermore, the results also show that the enantiomeric fractions (EFs) of chiral chlordane components changed with height. Samples taken at lower heights had EFs more similar to soil EFs than samples taken at the same location but a greater height. Together these results indicate that chlordane from this 40-year-old application continues to volatilize from this site. The data were used to develop a model of the volatilization from the experimental plot. This model led to the conclusion that volatilization occurs from the top-most cm of soil. The chlordane in this surface layer is lost at a rate exceeding the rate at which the surface layer is replenished from the soil reservoir, though cultivation processes can quickly replenish the surface layer by mixing the surface with the reservoir.

Impacts
This research has shown that chlordane present in Connecticut air is likely the result of volatilization of chlordane from locations where it was used as a termiticide. Once volatilized the chlordane can be transported, thus the chlordane in Connecticut air is a sum of both chlordane volatilized within the state as well as chlordane transported into the state with air from other regions. This volatilization tends to occur from the topmost centimeter of contaminated soil, and can be affected by cultivation practices. This knowledge can lead to improved management of the residues of this pollutant. The long-term impact of identifying chlordane-contaminated sites is to avoid planting edible plants in these areas and to avoid human exposure to contaminated soil. Overall, there will be less human exposure to pesticides, thereby reducing health risks.

Publications

  • Eitzer, B.D., Iannucci-Berger, W., Mattina, M.J.I. 2003. Volatilization of Weathered Chiral and Achiral Residues from Soil. Environ. Sci. Technol. 37:4887-4893.


Progress 01/01/02 to 12/31/02

Outputs
The pesticide chlordane was widely used in the United States for both agricultural and residential applications from the time of its introduction in the 1940s through its banning by the Environmental Protection Agency in 1988. It has been shown to be both toxic and persistent in the environment. It has been suggested that persistent pesticide residues become tightly bound to soil over time and become hard to extract from soil. Despite these suggestions banned persistent pesticides, including chlordane, are still being found in ambient air samples. We are conducting studies to help elucidate the environmental fate of these compounds, which will in turn help to explain their continued presence in ambient air. Our studies have focused on chlordane, originally applied as a mixture of over 140 different related compounds known as technical chlordane. We have examined the compositional and chiral profiles of chlordane in Connecticut ambient air at several locations and compared these data to those reported for ambient air in other parts of the country. We are also conducting studies at a weathered contaminated site from a single chlordane application over 40 years ago. Samples of ambient air are collected using high volume samplers to draw air through glass fiber filters and polyurethane foam plugs. The samples were collected at three different heights above the contaminated plot, and at four other locations (2 urban, 1 suburban, 1 rural). Samples for each height and location were collected every two weeks. Vapor phase samples were extracted using Soxhlet extraction cleaned up with florisil column chromatography and analyzed using chiral gas chromatography /electron impact ion trap mass spectrometry. The results of these analyses to date show that the ambient air concentrations in Connecticut are similar to ambient concentrations in other parts of the country. Air collected above the contaminated plot shows that the concentration decreases with height and that the concentrations from above the plot are higher than concentrations observed at the other locations. Furthermore, the results also show that the enantiomeric fractions (EFs) of chiral chlordane components changed with height. Samples taken at lower heights had EFs more similar to soil EFs than samples taken at the same location but a greater height. Together these results indicate that chlordane from this 40-year-old application continues to volatilize from this site. Use of wind speed data, time profiles for ambient air concentrations and comparison with ambient background samples allow us to conclude that volatilization from weathered residues is occurring, is a phenomenon which is dependant on both temperature and soil cultivation, and occurs from the topmost centimeter of soil.

Impacts
Knowledge of the volatilization rate of chlordane from soils and concentrations in ambient air allows us to better understand the environmental fate of chlordane. This in turn can lead to improved management of chlordane residues and allow us to lower the risk to the public from this toxic and persistent pollutant.

Publications

  • Mattina, M.J.I., White, J., Eitzer, B., and Iannucci-Berger, W. 2002. Cycling of weathered chlordane residues in the environment: Compositional and chiral profiles in contiguous soil, vegetation, and air compartments. Environ. Toxicol. Chem. 21:281-288.


Progress 01/01/01 to 12/31/01

Outputs
The pesticide chlordane was widely used in the United States for both agricultural and residential applications from the time of its introduction in the 1940s through its banning by the Environmental Protection Agency in 1988. It has been shown to be both toxic and persistent in the environment. As applied, chlordane was not a single compound, but a mixture of over 140 different related compounds known as technical chlordane. It has been suggested that these persistent residues become tightly bound to soil over time and become hard to extract from soil. We have inititiated studies which show that although weathered residues may be tightly bound at least a portion of those residues can still volatilize from the soil. We have been studying the compositional and chiral profiles of chlordane in Connecticut soils and the ambient air overlaying those soils. Our studies are currently focused on a site contaminated by a single chlordane application over 40 years ago. Samples of ambient air are collected using high volume samplers and polyurethane foam plugs at three different heights above the contaminated plot; along with background ambient air samples from alternate sites, and, soil samples from the plot and background sites. Air samples for each height and location are collected every two weeks. Samples are extracted using Soxhlet extraction, cleaned up with florisil column chromatography, and analyzed using chiral gas chromatography /electron impact ion trap mass spectrometry. To date, the results of these analyses show that the ambient air concentration above the plot decreases with height and that air samples taken from above the plot have higher concentrations than background sites. The results also show that the enantiomeric fractions (EFs ) of the chiral chlordane components changed with height. The closer the sample was to the soil the greater the agreement in EFs between the soil and the air. Together these results indicate that chlordane is volatilizing from this site. Use of wind speed data and comparison with ambient background samples produce an estimated volatilization rate of 1.4% of the chlordane present in the top 10 cm of soil and a 49 year half-life based on volatilization.

Impacts
Knowledge of the volatilization rate of chlordane from soils and concentrations in ambient air allows us to better understand the environmental fate of chlordane. This in turn can lead to improved management of chlordane residues and allow us to lower the risk to the public from this toxic and persistent pollutant.

Publications

  • "Compositional and Chiral Profiles of Weathered Chlordane Residues in Soil", Brian D. Eitzer, Mary Jane Incorvia Mattina, William Ianucci-Berger. Environmnental Toxicology and Chemistry, 2001, 20, 2198-2204.