Device for sequestration and concentration of polar organic...

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Reexamination Certificate

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C210S500230, C210S321800, C210S263000

Reexamination Certificate

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06478961

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to devices for sampling and sequestration of polar organic chemicals from water so as to permit analysis thereof.
BACKGROUND OF THE INVENTION
Global emissions of persistent bioconcentratable organic chemicals have resulted in a broad variety of adverse ecological effects and human suffering. Consequently, industry has developed less persistent, more water soluble chemicals. However, evidence is growing that the great quantities of these seemingly more environmentally friendly compounds (e.g., herbicides, new generation pesticides, and pharmaceutically related chemicals which have been historically viewed as totally benign) entering aquatic systems on a world-wide basis may be responsible for not only acutely toxic effects, but also are instrumental in causing sub-lethal chronic abnormalities. Adverse effects include altered behavior, neurotoxicity, and severely impaired reproduction. More insidious are the endocrine disrupting effects of exposure to the complex mixture of chemicals present in the environment. Numerous examples, such as increased vitellogenin levels (an estrogen controlled egg protein normally only found in females) in male fish from Las Vegas Wash near Lake Mead, Nev., nonfunctional testes in male alligators in Lake Apopka, Fla., reduced penis size in juvenile male otters in the Columbia River, feminized behavior in male western gulls in southern California, non-descended testicles in male Florida panthers, and masculinized female mosquito fish, unequivocally link such abnormalities to chemical exposures.
Although there are numerous reports on the negative effects of more polar endocrine disrupting chemicals on many forms of wildlife, a heated debate continues regarding the detrimental effects of these chemicals on human health. However, given the danger inherent in wildlife exposure to more water-soluble endocrine disrupting chemicals, and the potential deleterious effects resulting from prolonged human exposure, it is imperative that aquatic systems be monitored for the presence of a wide variety of polar organic chemicals currently entering the environment. While many techniques and methods are available to detect and quantify the non-polar organic contaminants, e.g., the DDT complex, polychlorinated biphenyls (PCBs), etc., of historic concern, similar approaches for waterborne polar organic contaminants are unavailable to environmental scientists. Monitoring of polar organic chemical species, potentially impacting wildlife and humans, and remediation of such contamination will be critical activities for the foreseeable future.
Although there has been considerable effort directed towards development of methods for actively sampling polar organic chemicals from water, this research has centered on the use of solid phase extraction employing specially modified polymeric resins in either a cartridge or imbedded in an inert membrane disk. See Hennion, M. C.; Pichon, V. 1994. Solid-Phase Extraction of Polar Organic Pollutants from Water.
Environ. Sci. Technol.,
28, 567A-583A; Barcelo/, D.; Hennion, M. C. 1997. Sampling of Polar Pesticides from Water Matrices.
Anal. Chim. Acta,
338, 3-18; International Sorbent Technology. ISOLUTE Env+®
The new generation of polystyrene polymer SPE columns
. International Sorbent Technology, United Kingdom. Pihlström, T. Hellström, A.; Axelsson, V. 1997. Gas Chromatographic Analysis of Pesticides in Water with Off-line Solid Phase Extraction.
Anal. Chim. Acta,
356,155-163. Hagen, D. F.; Markell, C. F.; Schmitt, G. A.; Blevins, D. D. 1990. Membrane Approach to Solid Phase Extractions.
Anal. Chim. Acta,
236, 157-164. Hagen, D. F.; St. Mayr, S. J.; Errede, L. A.; Carr, P. W. 1989. Composite Chromatographic Article, U.S. Pat. No. 4,810,381, Mar. 7, 1989. Dumont, P. J.; Fritz, J. S. 1995. Effects of Resin Sulfonation on the Retention of Polar Organic Compounds in Solid Phase Extraction.
J. Chromatogr. A,
691, 123-131; and Slobodnik, J.; Oztezkizam, Ö.; Lingeman, H.; Brinkman, U. A. th. 1996. The Solid Phase Extraction of Polar Pesticides from Environmental Water Samples on Graphitized Carbon and Empore-Activated Carbon Disk and On-line Coupling to Octadecyl-bonded Silica Analytical Columns.
J. Chromatogr. A,
750, 227-238.
Laboratories conducting analytical and toxicological research concerning the presence and toxicity of polar organic chemical species critically need sampling and analytical methods capable of defining the presence and amounts of bioavailable polar organic chemical residues.
Unfortunately, current sampling methods are not integrative over sufficient time intervals to sequester adequate amounts of polar organic chemical residues (many of which may have toxicological significance even at ultra-trace levels) to detect trace to ultra-trace levels and to cost effectively detect episodic releases. Also, current sequestration methods are not adequate for integratively isolating sufficient amounts of the mixtures of potentially toxic polar organic chemicals present in aquatic systems for use with bioassay procedures for toxicity testing. It is apparent that no current sampling approach provides a truly integrative method for determining bioavailable polar organic chemical residues. Because no practical sampling method exists that enabled the determination of polar organic chemical species in a passive, integrative manner (existing methods are designed only for point in time monitoring and lack the sensitivity required) at trace to ultra-trace levels, there is a need for a passive, efficient, integrative, and high capacity sampler for polar organic chemical residues.
SUMMARY OF THE INVENTION
The present invention represents a new approach for dealing with major problems associated with toxic polar organic chemicals in the environment, which are of concern to the world at large as well to U.S. governmental agencies such as USGS, FWS, EPA, DOE, NIOSH, OSHA, DOD, etc. This invention can be calibrated for use as a monitoring tool for polar organic chemical residues dissolved in a wide variety of aquatic ecosystems. In addition, other embodiments of this invention can be provided which would apply to large-scale projects such as monitoring industrial emissions, and remediation of point source contamination and the associated release of toxic chemical residues into aquatic ecosystems.
Because the device of the invention can be configured for in situ passive integrative concentration of readily biologically available dissolved phase polar organic chemicals, the invention offers a widely applicable abiotic assessment of organism exposure, thereby overcoming a major shortcoming of current techniques used by government agencies.
Although the invention has other applications, the principal utility of the invention is in monitoring of the time-weighted average potential for exposure of humans and other living organisms to water borne polar organic chemical species. The invention is a very valuable tool for defining the source, transport, and fate/degradation of toxic polar organic chemical residues. Further, because of the integrative sampling construction of the device of the invention, the device is applicable to the reduction of polar organic chemical species in aquatic systems of limited areal extent. This invention is useful to resource managers, regulators, and scientists responsible for determining the impact of chemicals on fish and wildlife resources and human health. The device of the invention enables the measurement of the amounts of polar organic chemical residues present in a broad array of aquatic systems, prediction of their potential adverse effects, and in some cases potential remediation of unacceptably high levels of these chemicals. In brief, government agencies, private sector personnel and members of the scientific community involved in monitoring/regulating environmental contaminants, specifically polar organic chemical species, will have extensive application for this invention.
Before considering the device of the invention in more detail, ref

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