W. T. Donaldson and A. W. Garrison
Regulations
U.S. Environmental Protection Agency Environmental Research Laboratory Athens. Ga. 30605
Reporting Impurities in Commercial Products A Master Analytical Scheme to identify and measure trace organics in commercial products could solve the regulatory reporting dilemma faced by industry An earlier article in this series (/) pointed to the necessity for an exhaustive analytical development program to meet proposed regulatory requirements by the U.S. Environmental Protection Agency for registration of pesticides. The Federal Register (2) calls for reporting all impurities in manufacturing use products and formulated use products at a concentration of 0.01% or higher. The applicant must also provide detailed analytical methods for all impurities reported. One manufacturer has estimated that the costs of complying with the analytical methods development requirements alone could be as high as $4.5 million for the registration of a single household disinfectant. The bulk of these costs is in the development of analytical methods for complex matrices. It is reasonable to expect that similar premanufacturing information will be recommended for chemicals regulated by the Toxic Substances Control Act. Because of these costs, industry and the ACS have both proposed that requirements for chemical analysis for trace impurities be limited to only those chemicals known to be toxic. Unfortunately, analytical experience to date has demonstrated that we cannot accurately predict what chemicals will be present at trace levels, and we cannot always predict toxic effects (PCB’s were manufactured for about 40 years before research revealed their harmful impact on fish and wildlife). The need to know what is in commercial products and the astronomical costs of meeting this need under current proposals create a dilemma and a tremendous challenge to the analytical chemist—not a challenge to amass armies of analytical chemists applying traditional approaches to the problem but a challenge to develop innovative concepts that will provide adequate, if not entirely complete, information at a justifiable cost. 458 A
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For example,
a compromise might industry standard analytical protocol could be developed that would identify and measure all impurities at a concentration above a level low enough to be considered insignificant for the vast majority of chemicals. Separate, more sensitive procedures could be applied for the determination of the very few chemicals known to be of concern at lower concentrations (e.g., 2,3,7,8tetrachlorodibenzo-p-dioxin). Application of such a protocol might appeal to both EPA and industry. The regulatory agency could be assured that a reliable and comprehensive analysis of the product had been made by a broadly tested protocol. The industry could be assured that it had fulfilled its regulatory obligations. The cost of applying such a protocol should be reasonable, particularly if commercial laboratories geared up to provide the analysis on a mass-production basis. Although a standard qualitativequantitative scheme may not provide the best possible analysis for every impurity in every product, the uniform application of the protocol would likely provide, by far, the largest amount of valuable information at the lowest
be reached between EPA and
if
a
Development of a comprehensive analytical protocol for analysis for trace impurities is not a pipe dream. It can be done today by combining appropriate state-of-the-art techniques, and cost-effective and successful application can be predicted with considerable confidence. Experience with the EPA analytical screening protocol for consent decree priority pollutants provides encouragement. This protocol was hastily developed within a three-month period to identify and measure, by gas chromatographymass spectrometry, 114 volatile organic compounds in industrial wastewaters at a detection level of about 10
ANALYTICAL CHEMISTRY. VOL. 51. NO. 4. APRIL 1979
ppb. Quantitation is precise only to an order of magnitude. Approximately 12 different commercial and government laboratories have applied the protocol to 5000 samples at an average cost of about $700 per sample (less than $7.00 per compound). The protocol is far from perfect, as pointed out in a previous article in this series (3), but its use is encouraging for several reasons: Even though the protocol is somewhat complex and requires sophisticated equipment, it has been broadly applied at reasonable cost; analysis of standard mixtures has demonstrated acceptably comparable results from different laboratories; and although only 114 compounds are identified and quantitated, GC retention times and detector responses and mass spectra are collected routinely on every sample for many additional compounds. A logical next step is to put together a comprehensive method that provides for extract ion of all compounds and identification and measurement of every compound for which a detector response and mass spectrum are obtained. Currently, EPA is developing just such a scheme through a contract to the Research Triangle Institute and Gulf South Research Institute (4). This scheme will he based on the use of a computerized GC-MS system. Sampling procedures, extractants, internal reference compounds, GC columns, and MS operating conditions will be specified so that all volatile organics (those that are amenable to gas chromatography) will be identified and measured from data collected on a single GC-MS run for each extract. Compounds are identified from automatic computer spectra matching. GC retention times and relative peak heights are computed by use of internal reference compounds; recovery factors and detector response factors for identified compounds are retrieved This article not subject to U.S. Copyright Published 1979 American Chemical Society
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from a computer library of data previously established for each chemical class. Taken together, this information allows computerized quantitation without reanalyzing the sample and avoids the necessity to maintain thousands of reference compounds, Generally, concentrations should be accurate to within a factor of two. The Master Analytical Scheme described above is designed for use with aqueous samples. Estimated detection limits will be 10 ppb for effluents, 1 ppb for ambient waters, and 0.1 ppb for finished drinking water. Cost of application is estimated at $3 000 per sample. This cost is quite a bargain when compared to a cost of $10 000 for providing quantitative information for just the 114 consent decree pollutants using the EPA protocol with sufficient spike and blank runs to compute recoveries and detector responses.
To analyze commercial products, the Master Analytical Scheme would have to be “front ended" to provide for dissolution of the product and its impurities. It would also have to he extended to nonvolatile compounds, probably by use of high-pressure liquid chromatography coupled with mass spectrometry. Insurmountable obstacles, then, no longer exist. Assuming that these obstacles will
be overcome
shortly, the analytical
chemists can offer regulatory agencies and industry the solution to the dilemma of chemical analysis for trace impurities in commercial products. Application of the entire protocol could be made for $20 000, satisfying the requirement to identify and report impurities. No additional methods development would be necessary; procedures for extracting only the compounds for which monitoring would be required would be already developed as a part of the protocol. The mass spectrometer could be replaced with less expensive detectors for monitoring previously identified compounds. (It is important to assert here that nonchemists should overcome their paranoia about GC-mass spectrometers. They are no longer “rare and exotic instruments.” They are used by more pollution control laboratories today than the number of pollution control laboratories using gas chromatographs 15 years ago. They are, for many purposes, more economical to use than gas chromatographs with other detectors.) We hereby challenge the analytical chemist to complete the development of the proposed system that will solve the problem of identifying and measuring trace organic impurities in commercial products. Its development
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ANALYTICAL CHEMISTRY. VOL. 51. NO. 4. APRl
1979
and adoption can reduce the analytical measurements cost of developing new products while providing the best attainable information. The successful application of the qualitative-quantitative approach requires that analytical chemists try the protocol that is to he standardized and collaborate in its improvement. If you want to join in this accomplishment, contact Dr. Wayne Garrison, who is in charge of EPA’s program to develop the Master Analytical Scheme. His address is U.S. Environmental Protection Agency Environmental Research laboratory College Station Road Athens, Ga. 30605
References (1) R. A. Libby, Anal Chem., 50, 1229A
fed. Regist., 43 (1321, 29707-10 (10 July 1978) (3) R. O. Kagel, R. H. Stehl, and W. B. Crujnmett. Anal. Chem.. 51, 223A (2)
(4) A. W. Garrison et a)., "An Automatic Sampler, A Master Scheme, and A Registry System for Organics in Water," Proc. 9th Annuel Materials Research Symp., NBS, in press.
