Anal. Chem. 1091, 63, 270R-292R (T3) Lab. Med. 1989, 20, 153-154. e w W P S to computerized devices and (T4) Applkatbn of the medical d manutactdng processes: medkal d e w W gutdance for FDA investlgetom, flrst draft of Compknce and SvveWlance, DMsbn of Com plienCe Prowam, Food and Drug Admlnlstratbn, Publk Health Service, Department of Health and Human Services: Rockvllle MD, Nov 1990. (T5) Butch, s. H. Lab. w .1991, 22, 18-22. (T6) College of Amerkan Pathdoglsts: Commission on Laboratory AccredC tatbn. Inspection Checkllst, Sectlon I. Laboratory GeneraCComputer services, 1990. (T7) 1990 M k r w R Annual Report, p 8. (T8) Schlender, 6. R. FWUM 1991, 123 (4), 12-13. (T9) Shekr, R. PC Wedc 1991. 8 (I), 1-10. (T10) Infocorp. Into Wwld 1991, 13 (4), 45. ( T l l ) €bCt?Vn&S 1991, 64 (l), 52-54. (T12) M&w, M. K. CompUtcK System News 1991. Feb 4, 10, 35. (T13) Marshall, M. Into War# 1991, 73 (2), 21. (T14) A b , R.; Weikrt, M.; Pasla, 0. (3. CAP Tod8y 1890, 4 (ll), 42-43. i990,4, w - 2 9 . ( ~ 1 5 )sk~ei,E. CAP (T16) Schbnder, 6. R. Fortwn, 1989. 120 (7). 100-1 12. (T17) Brooks, F. P. I€€€ m U t W 1987, 20 (4), 10-19. (T18) kooks, F. P. The M y U h l Man Month: € w y s on Soffwafe €nginwnhg; AddlsorrWesby: Reading, MA, 1975. (Tl9) Kahn, R. E. Sci. Am. 1987, 257(4), 138-143. (T20) Andrews, A. D. Roceedlhgs of the 13th Annual Syrnpxlum on ComputrW -fkm h Msdkal Cam; IEEE Computer Society Press: Wash ."1 DC, 1989 pp 638-843. (T21) Van Lente, F.; Castelkni, W.; Chou, D.; Matzen, R. N.; Galen, R. S. Clln. Chem. 1986, 32, 1719-1725.
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(T22) Cechner, R. L.; Sutheimer, C. A. J. Anal. Toxicol. 1990, 14 (5), 280-284. (T23) Conneily, D. P. Am. J . Clln. P a m . 1990, 94 (4, Suppi. l), S7-Sl4. (T24) Champlne, G. A. I€€€ Computer 1980, 13 (1l), 84-98. (T25) Standard specification for transferring clinical laboratory data messages between independent computer systems, deslgnatlon E1236-88. 1988 Annual Book of ASTM Sta&r&; American Society for TesWng Materlals: Philadelphla, 1988; pp 362-377. (T26) McDonald, C. J. proceedlnBs of the 141h Annual S y " on Computer Appllcetbns In M d c a I Cafe; IEEE Computer Soclety Press: Los Alamltos, CA, 1990; pp 9-14. (T27) Chou, D.; Van Lente, F.; Casteilani, W. Clln. Chem. 1990, 36, 1586-1587. (T28) Health level seven stend$rds: an application protocd for electronic data interchange in health care environment, versbn 2; K7: Philadelphia, 1988. (T29) McDoneld, C. J.; Hammond, W. E. Ann. Intem. Med. 1989, 110, 333-335. (T30) Rlshel. W. R o c d n g s of the 72U1 Annual S y " on ConpUrer AppwCetioM h hkx#cal Cam; IEEE Computer soclety Press: Washington, DC, 1988; Pp 687-890. (T31) Ostler, D. V.; Harrington, J. J.; Hannemyr, G. Rocer?dln@sof the 14th Annual Symposium on Computer Applicetbns In h k l b l Cere; IEEE Computer Soclety Press: Los Alamltos, CA, 1990 pp 235-238. (T32) Nolan, L. S.; Shabot, M. M. Fhx&ngs of the 14th Annual Symposium on Computer Appllcctbns In kledlcel Cafe; IEEE Computer Socbty Press: Los Alamltos, CA. 1990; pp 216-219. (T33) Eveiuatlon of the TrCSecvke laboratory system: costlbeneflt analysis of Trllab System, NRMC Oakland; Arthur D. Lmle: Cambridge. MA, 1983.
Environmental Analysis Ray E. Clement*
Ontario Ministry of the Environment, Laboratory Services Branch, 125 Resources Road, P.O.Box 213, Rexdale, Ontario, Canada M9W 5Ll
Marsha L. Langhorst The Dow Chemical Company, Analytical Sciences Laboratory, 1602 Building, Midland, Michigan 48640
Gary A. Eiceman Department of Chemistry, New Mexico State University, Las Cruces, New Mexico 88003
INTRODUCTION This review covers developments in analytical chemistry as applied to environmental analysis for 1989-1990. A few articles appearing in 1988 are also included. Environmental analysis in its broadest context could include almost everything, but since reviews on water, air, and pesticide analysis 270 R
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have also been prepared, we have omitted most references to r n e r a l air- and water-quality parameters, workplace/inustrial h giene issues, indoor air, and most herbicide/pesticide residle studies. Guidelines, regulations, risk assessment, and modeling are not covered; nor are human levels and commercial food. We emphasize the detection and quantitation of trace metals and trace organics in real environmental @ 1991 American Chemical Soclety
ENVIRONMENTAL ANALYSIS
matrices, including industrial emissions, landfill sites, spills and emergency response, ambient air, drinkin /surface/ groundwaters, marine samples, incinerators, mobi e sources, soils, sediments, and some biota. Studies on back round levels, development of environmental databases, QA/%C, the use of chemometrics to analyze data, sampling, sample preparation, analyte separation, detection, and related topics are emphasized. Most literature review was done b using the Chemical Abstracts Service CA Selects for Gas Ciromatography, Inorganic Analytical Chemistry, and Pollution Monitoring. Individual computer searches of the Chemical Abstracts and Analytical Abstracts databases were also performed. The princi al factors that make environmental analysis difficult are t t e range and complexity of sample types. Accordingly, this review is organized by matrix rather than analyte or method used. Since this review appears for the first time, we would appreciate comments on how to improve the organization of the review or concerning the scope of our coverage.
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GENERAL REVIEWS procedures were reviewed by Keith Environmentalsamp ( A I ) and Bryden (A2).T e problems of analytical reliability and comparability of results were discussed in another review (A3). Several reviews of atomic spectroscopy techniques as a plied to environmental analysis have appeared (A4-AIO). &ese include a book that describes chromatography interfaced to various atomic spectroscopy techni ues (A4),ICPMS (A5, A6), ICP and DCP (A7, A8), and aqarge review that covered many atomic spectrometry techniques (A9). Other reviews concerned the use of activation analysis ( A I I ) and char ed-particle accelerators (AI2) for environmental trace m e d analysis. General reviews of inorganic mass spectrometry (AI3) and nuclear and atomic spectroscopy techniques (AI4) include environmental applications. The use of membrane systems for piezoelectric and electrochemical sensing in environmental chemistry has also been reviewed (AI5). Analytical methods for specific analytes have been reviewed; this includes ICPOES for silicate analysis (AIO),ICPMS for lo -lived radionuclides (A@,interlaboratory testa for low-level raxoactivity (A16), thallium (AI7), technetium-99 (AI@, mercury (AI9),arsenic speciation (A20),and the use of the Kjeldahl method for nitrogen determination (A21). A book on trace-element speciation (A22) and a review on the use of ion chromatographyfor the certification of standard reference materials (A23) have also appeared. The use of microwave ovens for sample preparation has grown considerably in recent years, as reflected in a recent book (A24) and a number of reviews (A25-A28). Various radiochemical and radiometric methods for the determination of radionuclides in various environmental matrices have been reviewed (A45). Many reviews of the anal sis of trace organics in the environment have also been pubshed. Topics covered include the use of ion chromato ra hy in the steel industry (A29), GC/MS (A30, A31), G8/#T-IR (A32), supercritical fluid extraction (A33) and chromatography (A34), and coupled LC/GC (A35). A general review of the determination of organic com ounds in water, sediment, standards, and soil was prepareaby Nubbe (A36). More specific reviews on the analysis of samples for organic halogens in marine pollution (A37),planar olychloroaromatic compounds (A38),chemical monitorin oPoffshore oil and gas o erations (A39),the use of li uid cLomatography in pesticig analysis (A40),the use of G%/MS to determine chlorinated dioxins[ dibenzofurans (A41),PCBs (A42),and the polycyclic aromatic hydrocarbons (A43). Weeks reviewed the application of multidimensional resonance two-photon ionization MS-based analysis for the determination of polycyclic aromatic compounds in complex environmental samples (A44).
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AIR ANALYSIS APPLICATIONS This portion of the review deals with environmental air monitoring and emphasizes the application of analytical methodology to the determination of evbome pollutanta. The applications areas covered include monitoring of fixed industrial sources (process vents and fugitive emissions from equipment leaks), fixed combustion sources (primarily in-
cinerators), mobile sources, ambient air, and wastesite emissions (landfii and wastewater), including databases. In addition, some papers on accidental releases and emergencies and atmospheric transport and deposition have been included. Further, some papers on the subjects of detection limits, standards, and quality assurance have been reviewed. F i n d , the subject of remote sensing has been highlighted. WhiG the review is organized by applications areas, it is intended to highlight improved methodologies for sampling and analysis, detection limits, and what pollutants have been monitored. Air Analy8l8: Book8 and Reviews
Recently published books are excellent comprehensive reviews of methods and instrumentation for environmental air monitoring (BI-B5). One book contains sections that broadly review general techniques, that provide an extensive collection of air anal is methods, and that describes methods for specific c o m y n Zin workplace air (BI). Approximately 150 methods are escribed. Another book extensively covers air sam ling techniques and instrumentation (B2). Recent proceexings contain summaries of the technical programs from the annual EPA/A&WMA conference held in North Carolina (B3-B5). This review is intended to complement other general reviews on the subject of environmental monitoring (B6),including the Analytical Chemistry review on Air Pollution (B7). More specific reviews were published that centered on the use of various analytical techniques in air monitoring, inatomic spectromcluding surface acoustic wave sensors (B8), etry (B9),laser photoacoustic spectroscop (BIO), annular piezoelectric c stals (B27),l!M3 (BB), lidar denuders (BII), systems (B29),and long ath %-IR (B30). Other revlews of a specific nature i n c l u d J a review on products of incomplete combustion (BI2),a review of processing schemes for detection and control of odors in wastewater treatment plants (BI3), and a review of samplers for airborne agricultural dust (including microorganisms) (€24). Three publications reviewed sampling techniques (B3I-B33), and one discussed the quality assurance of air methods (B34). The literature of the past two years contains reviews that deal with specific chemical species, including aerosols and acid aerosols (B15-B18), nitrous oxide (BI9),sulfur oxides (B20), trace atmospheric elements (B21),lead (B22),organometallic compounds (B23),radon (B24,B25), light hydrocarbons (B26), polycyclic aromatic compounds (B35), and atmospheric trace elements (B36). Flxed Sources
Industrial Sources and General Methodology. Butadiene emissions were collected and analyzed from the process vent stream of a production plant manufacturing synthetic rubber from styrene and butadiene (CI).A test method, validated for the determination of acrylonitrile emissions, train consisting of a methanol fded midget utilized a samp impinger followe by a charcoal tube. The collected samples were analyzed by as chromatography (GC) with N-selective detection (C2). &as chromatography with flame ionization detection (GC-FID) methods were developed for monitoring ethylene oxide emissions from production plants and commercial sterilizers ((23). The li opolysaccharide (endotoxin) content in airborne dust sampis from three poultry slaughterhouses was determined by the chromogenic Limulus amebocyte lysate assay and by gas chromatography-mass spectrometry (GC/MS) analysis of lipopolysaccharide-derived 3-hydroxy fatty acids. The results were compared (C4). A shrouded aerosol sampling probe was developed for sampling aerosol particles that is reported to have only 13% loss of particles compared with 39% loss for an isokinetic probe (C5a). The design and testing of a sampling line for monitorin instrumentation a t a nuclear power plant were reported. %he line materials and operating conditions were optimized for transport of noble gases, aerosols, iodine, and tritium (C56). Combustion Sources/Incineration. The emissions from a large incinerator and soil samples from the vicinity were analyzed to assess the pollutant load of the plant and to determine the fate of olycyclic aromatic hydrocarbons (PAHs), polychlorinatef dibenzo-p-dioxins (PCDDs) and
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Ray E. C l o " i is a research scientist with the Ontario Ministry of the Environment, Laboratory Services Branch. He graduated . with his Ph.D. from the University of Waterloo in 1981, under the supervision of Professor Emeritus F. W. Karasek. His principal research areas involve the use of GC-MS and GC-MS-MS for the determination of trace concentrations of Chlorinated dibenze pdioxins and dibenzofurans in complex environmental matrices. He has authored over 90 publications in this and related areas and has coauthored or edited 4 books. Dr. clement has taught undergraduate and graduate courses on analytical instrumentation and environmental analysis and is currently nonorary notessor at the University of Western Ontario and Adjunct Research Professor at Carleton University. Dr. Clement also serves on the editorial board of Chemosphere.
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Manha L. Laghont is a Research Leader at the Dow Chemical Co. in the Analytical Sciences Laboratory of Michigan Research and Development. She joined Dow in 1975 upon graduation from the University of IiiC nois. She has primarily been involved in the development of chromatographic methods and instrumentation for the trace analysis of compounds in environmental matrices (air, water, biologicals) and Dow products to support Dow research and production projects. Her recent work deals primarily with environmental air monitoring .efforts,-including process emission monitoring, fugitive emlssion monitoring, and ambient air monitoring. One current activity involves the use of high-speed microchip gas chromatography for in situ monitoring of process vapors to support process waste and emission reduction projects. I n the past, she has also been involved in the analytical aspects of air monitoring from an industrial hygiene perspective. Marsha Langhorst has authored or coauthored 25 papers in the area of analytical chemistry and is a member of the Air & Waste Management Association, the American Chemical Society, Analytical Chemistry Division and Chromatography Section. aary A. E k m a n is Professor of Chemistry at New Mexico State University inb Las Cruces, NM. He received his Ph.D. degree in 1978 at the University of Colorado and was a postdoctoral fellow at the University of Waterloo, Ontario, from 1978 to 1980. I n 1987-1988 he was a Senior Research Fellow at the US Army Chemical Research, Development and Engineering Center at Aberdeen Proving Gd., MD. He has been on the faculty at New Mexico State University since 1980. His research interests include the development of selective chromatographic phases, use of GCIMS for environmental research, and the development of ion mobility spectrometry as a chemical sensor, process monitor, and chromatographic detector. He also has Interests in atmospheric presure ion-molecule chemistry exemplified by the electron capture detector. He regularly teaches separations chemistry and electronics at the graduate level and quantitative analysis at the undergraduate level. Eiceman currently serves on the advisory board for Critical Reviews In Analytical Chemistry.
01 chlorinated dibenzofurans (PCDFs), polychlorinated Kiptenyls (PCBs),and inorganic species (Pb, Zn, Cd, Mn, Cr) (C6u). A procedure was described that could differentiate incinerator fly ash from other sources of particles in urban air (C6b, C7). One paper described the requirements and challenges of trial burn testing a large incinerator as mandated by the US EPA under RCRA (CS). Audit results from the determinations of Principle Organic Hazardous Constituents (POHC) using the Volatile Organics Sampling Train (VOST) and bag methods during RCRA trial burns were summarized (C9). A fluidized-bed incinerator with CaO injection into the bed was shown to have considerably lower levels of PCDDs/PCDFs in the post-combustion zone than observed in various other incinerators around the world. Levels of PCCDs/PCDFs were 10 times lower than an incinerator in Ontario, Canada (CIO). Several apers dealt with the methodology for sampling and analysis. gas sampler was described for in situ monitoring of combustible gases in the flue stack of fossil fuel-fired boilers
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(Cll).It consisted of a hollow fiber separator composed of PTFE or Kapton through which the gaseous species in the flue gas are transferred into a carrier gas stream to a solid-state sensor. The membrane allows the transfer of CO and H but limits the transfer of moisture, C02, and particulate matter. Another sampling train was used for monitoring PCDDs, PCDFs, and other chlorinated organics in incinerator flue gas (C12). The evaluation of passivated stainless steel canisters for sampling emissions of volatile organic compounds (VOCs) from hazardous waste incineration was reported (C13). Eighteen nonpolar volatile organic compounds in canisters were stable for 2 weeks in a matrix containing water and HC1 vapors. A field comparative evaluation of total hydrocarbon continuous emission monitors at hazardous waste incinerator facilities was published (CI4). One paper reviewed the development of laser-based resonance ionization spectroscopy for continuous monitoring of emissions from the incineration of chlorinated hydrocarbon-containin municipal and hazardous wastes. Details were pr esente on sensitivity, selectivity, and applications (C15). A storage study of fly ash found that samples are best preserved when packaged in Teflonwrapped glass dishes and stored at -79 "C in the dark (C16). A simple sampling and sample preparation procedure was described for collection of organics from incinerator streams (C17). A method was published where megabore capillary GC replaced packed-column GC for the analysis of samples collected using VOST. Response factors for target compounds showed coefficients of variation
