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Environmental Analysis Ray E. Clement’ and Carolyn J. Koester Ontario Ministry of the Environment and Energy, Laboratory Services Branch, 125 Resources Road, Etobicoke, Ontario, Canada M9P 3V6
Gary A. Eiceman Department of Chemistry, New Mexico State University, Las Cruces, New Mexico 88003 Review Contento Introduction and General Reviews Air Analysis Applications Air Analysis: Reviews Fixed Sources Mobile Sources Ambient Air Air Emissions from Waste and Waste Sites (Landfills, Wastewater) Accidenta and Emergencies Atmospheric Chemistry, Transport, and Deposition Biomonitoring/Bioassays Miscellaneous Air Topics Water Analysis Applications General Commenta Reviews and Discussions of Broad Importance Surface Water, Rivers, and Lakes Groundwater, Wells, Reservoirs, and Springs Drinking Water Seawaters and Coastal Waters Municipal Wastewater and Storm Water Industrial Wastewaters Landfill Leachate, Sludge, Waste Sites, and Runoff Bioindicators, Bioassays, and Biomonitors Methods for Aqueous Media Organic Compounds Metals and Inorganic Compounds Soil and Sediment Analysis Applications Inorganic Analytes Organic Analytes Biological Sample Analysis Applications Inorganic Analytes Organic and Organometallic Analytes MiscellaneousTopics Hazardous Wastes, Waste Sites, and Oils Data Analysis, Quality Control, and Standards Toxicity Testing and Biomonitoring
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INTRODUCTION This review covers developments in analytical chemistry ap lied to environmental analysis for 1991-1992. Some rezrences in late 1990 that were not covered in the previous review in this series ( A l ) are also included. As before we have excluded most referencesto general air and water quality parameters and pesticides, because other reviews in this volume cover these topics. Also excluded are most references to industrial hygiene issues, indoor air, guidelines and regulations, risk assessment, modeling, human levels, and commercial food. Em hasized are the detection and quantitation of trace me& and trace or anics in real environmental matrices. Related topics suc! as the use of chemo0003-2700/83/0365-0085R$12.00/0
metria for data analysis, uality assurance and quality control, sampling and Sam$ preparation, and others are also covered. Literature review was by manual examination of the CA Selects for Gas Chromato aphy, Inorganic Analytical Chemistry, and Pollution &nitoring, supplemented b computer searching of the Chemical Abstracts database &r special topics. Some 20 OOO individualabstracts were examined before choosing the ones that appear in this review. As before, the review is organized by matrix rather than analyte or method used.
GENERAL REVIEWS The tremendous growth in environmental analysis ap lications is reflected in the large number of review articles!a tt have appeared in the past two years. The role of the analytical chemist in thie owth was discussed by Grasselli (A2). Modernanalyticajfchemistry and environmental science (A3) and futuristic approaches to environmental analysis and monitoring (A4) were also discussed. EPA’s sampliy and analysis methods have been computerized and are avadable in database format (AS). Reviewson the instrumentalanal is of pollutants (A@,the fate of environmental pollutants and an inventory of regulations concerning the chlorinated dioxins and related compounds (A81 have also appeared. A number of reviews have dealt with the concerns of samplingand sample preparation. Sampling,sample stability and storage, and discussions of errors that can occur were reviewed in several papers (ASA12). Collection of soil moisture by using lyslmeters was reviewed by Scott (A13). Extraction and concentration of analytesby supercriticalfluid extraction (A14, A16), solid-phase extraction (A16),and by using su ported li uid membranes ( A 1 3 have also been reviewecf A recent%” provides extensive coverage of the preconcentration of trace elements by using a variety of techniques that include solvent extraction, formation of volatile compounds, use of polyurethane foam sorbents, isotachophoresis, membrane methods, coprecipitation, ion exchange,and electrochemicaland chromatographicmethods (A18). Barnes reviewed preconcentration and separation methods for inductively coupled plasma s ectrochemical analysis (A19). General analyticalaspectsofe!t prere & i t a for quantitative determination of metals and metalloi%swere extensively reviewed by Markus (A20). The importance of chromatography (A211and gas chromatography/mass spectrometry (A22-A26) techniques in environmental analysis has been reviewed. Reviews on the application of gas chromatography to marine organic pollutants (A27)and organometalliccompounds ( A B )have also appeared. Several reviews showed the importance of chromato aphic techniques for metal speciationin environmental samp% (A2SA32). A recent book was devoted to metal speciation in the environment (A33), and an overview of methods for elemental speciationwas presented by Van Loon (A34). Other reviewsdiscussedthe use of microwave-induced plasma as an element-specific detector in speciation studies ( A S ) , described the use of radiochemical methods in speciation studies (A36),and covered the role of speciation in aquatic toxicity (A37) and trace element speciation in the aquatic environment ( A B ) . Various as cta of the use of atomic spectrometry in environmen$analysis have been reviewed (A39, A40). Inductively cou led plasma mass spectrometry is increasing in importance or environmental application, as shown in
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Ray E. Clement is a researchscientistwith the Ontario Ministryof the Environmentand Energy, Laboratory Services Branch. He graduatedwith his Ph.D. from the University of Waterloo in 1981, under the supervision of Professor Emeritus F. W. Karasek. His principalresearchareas involve the use of GC-MS and GC-MS-MS for the determination of trace concentrations of chlorinateddibenzo-pdioxinsand 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 Honorary Professor at the University of Western Ontario and Adjunct Research Professor at Carleton University. Dr. Clement also serves on the editorial boards of Chemosphere and CRC Critical Reviews in Analytical Chemistry,
Carolyn J. Koester is a postdoctoralfellow with Trent University and with the Ontario Ministry of the Environment and Energy, LaboratoryServicesBranch. She received her Ph.D. from Indiana University in 1991, where she studied the atmospheric fate and deposition of chlorinated dioxins and furans under the directionof Distinguished Professor Ronald A. Hites. Dr. Koester’s current researchinvolvesthe development of particle beam LC/MS methods and electron capture, negativeionization, GC/ MS methods to investigate environmental problems. Gary A. Elceman is Professorof Chemistry at New Mexico State University in Las Cruces, NM. He receivedhis Ph.D. degree in 1978 at the University of Colorado and was a postdoctoralfellow at the University of Waterloo, Ontario, from 1978 to 1980. I n 1987-1988 he was a Senior Research Fellow at the US Army ChemicalResearch, 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 includethe developmentof selective chromatographic phases, use of GC/MS for environmental research, and the development of ion mobility spectrometry as a chemical sensor, process monitor, afid chromatographic detector. He also has interests in atmospheric pressure ion-molecule chemistry exemplified by the electroncapturedetector. He regularlyteaches separations chemistry and electronics at the graduate level and quantitative analysis at the undergraduatelevel. €iceman currently serves on the advisory board for Critical Reviews in Analytical Chemistry.
several reviews (A41-A43). Plasma sourcemass spectrometry is especially effective when used for chromatographic detection (A44). Jickells reviewed the application of inductively coupled plasma techniques and preconcentration to the analysis of atmospheric precipitation (A45). Other atomic spectrometry techniques reviewed include flame/furnace infrared emission spectrometry (A46),the use of GC/AAS for determination of organolead compounds (A47), and the application of AAS to marine analysis (A48). The characterization of interferences affecting selectivity in GC/AES has also been reviewed (A49). Many other techniques have been applied to environmental analysis. One of the newer ones involves the use of fiber optic chemical sensors and biosensors. A book (A50) and several reviews on various aspects of fiber optic chemical sensors (A51-A55) as applied to environmental analysis have appeared in the past two years. The application of various electroanalytical techniques to environmental analysis have been reviewed (A56-A58). The various techniques used include potentiometric stripping (A59),voltammetry (A60), and polarography (A61). Immunoassays show great promise for environmental monitoring (A62-A64). Reviews on the use of ion chromatography (A65-A67) and chemical sensors (A68-A 71) illustrate the growing use of these technologies 88R
ANALYTICAL CHEMISTRY, VOL. 65, NO. 12, JUNE 15, 1993
for environmental monitoring. Many other techniques applied to environmental analysis were also reviewed. These include the use of lasers (A72),liquid scintillation spectrometry (A73),vibrational spectroscopy(A74),hydride generation (A75),laser fluorescence(A76),isotopic tracers (A77),nuclear analytical techniques (A78),and accelerator-basedtechniques (A79). Microanalysistechniques including X-ray, secondary ion mass spectrometry, and related techniques have also been reviewed (A80-A82). Many reviews on the environmental occurrence,properties, and determination of specific analytes have also been published. Voluminous reviews on environmentally significant metals have appeared in three volumes (A83-A85). Other reviews have appeared on the determination of inorganic species (A86), chromatographic analysis of metals (A87), mercury and its compounds (A88), arsenic species (A89), organolead compounds (Ago),cadmium (A91),sulfur compounds (A92),actinides (A93),rare earth compounds (A94), semivolatileradionuclides (A95),and strontium and yttrium (A96). Reviews also appeared covering the determination of surfactants in environmental samples (A97), PCBs (A98), PCBs and dioxins/furans (A99),amines (AIOO),and hydrocarbons in seawater,biota, and sediments (A101). An indexed bibliography of toxic contaminants in water, sediments, and biota of the Great Lakes has also appeared (A102). In addition to all of the above, reviews of the analysis of specific environmental sample types have also appeared. The determination of analytes in air (A103,A104),aquatic sediments (A105,A106), soil (A107),and street and house dusts (A108) have all been reviewed. A critical review of site assessment methodologies (A109) has also been published.
AIR ANALYSIS APPLICATIONS This section covers the application and development of analytical techniques for the determination of airborne pollutants. The applications discussed are organized by emission type and include monitoring of fixed sources (industrial, combustion,fugitive,nuclear, and natural), mobile sources (vehicles), ambient air, and air emissions from waste sites. Other topics include remote sensing, statistical analysis of data, and novel techniques which show promise for becoming important in the future. The monitoring of wet and dry deposition is also included in this section because compoundsfound in wet and dry deposition are representative of atmospheric contamination. In addition, biomonitoring and bioassays, techniques which are newer to environmental applications, are reviewed. We consider only the determination of trace analytes and have chosen not to include a comprehensive review of the measurement of greenhouse gases, atmospheric radicals, or general sampling methods for gases and aerosols; these topics are covered in depth in the “Air Pollution” review in this issue. This section is also intended to provide insight as to which analytes provoke environmental concern. Air Analysis: Reviews Air monitoring is a global concern as shown by reviews of air pollution determination by gaseous and particulate sampling methods ( B I ) the , state of environmental analytical chemistry and pollution climates in Europe (BZ),and the monitoring of atmospheric pollutants from space (B3). Analyses of gas-phase organic compounds in the marine atmosphere (B4) and in the ambient air (B5)were reviewed. Methods for sampling large airborne particles associated with radioactivity were reviewed (B6). Considerations in selecting the sampling of particle, vapor, or both phases for certain compounds were discussed (B7). Many analytical techniques were reviewed. Selected applications of gas chromatography (GC) for environmental monitoring (B8) and gas extraction techniques for sample preparation in GC were summarized (B9). Reviews of photoacoustic spectroscopy (BIO),instrumental microanalytical techniques for the characterization of individual particles ( B I I ) ,nuclear activation techniques for the determination of trace elements (B12), particle-induced X-ray emission (PIXE) and complementary nuclear methods for trace element determination (B13),optical techniques (B14), ion chromatography (B15), and ion mobility spectrometry (B16) as applied to air monitoring were published.
ENVIRONMENTAL ANALYSIS
Because one of the goals of environmental monitoring is to provide information for risk assessment, the practice of health risk assessment and its impact on standards for toxic air contaminants has been examined in a review with 129 references (B17).
Fixed Sources Industrial Sources. Three methods for monitoring industrial emissions, including EPA protocols and other methods using flame ionization detection (FID) and on-line mass spectrometry (MS), were compared (C1). A few papers dealt with specific processes. A method for sampling olychlorinated dibenzo-p-dioxins and dibenzofurans (PzDD/ Fs) in corrosive off-gasesformed during the chlorination step in the magnesium production process was developed (C2). Odorous cyclic acetals emitted from a polyester resin plant at sub- pb concentrations were identified by cryofocusingGC/M#(C3). A selective extraction method was developed to determined lead speciation of particles on air filters collected near a lead smelter (C4). A porous-layer opentubular GC column was coupled with thermoconductivity detection (TCD) and FID and used to monitor light hydrocarbons and noncondensable gases produced during coal coking;high-precision determination of eight coke-oven gases was possible within 10 min (C5). Methyl ethyl ketone peroxide, a t detection limits of 50 pg/m3of air, was monitored during lamination applications in the production of reinforced, unsaturated pol ester plastics; the methyl eth 1 ketone peroxide was co lected on A1203and determine by spec: trophotometry after reaction with 4-tert-butylcatechol (C6). Combustion Sources. Monitorin of or anic and inoranic compounds in the combustion ef uents rom municipal, iazardous, and medical waste incinerators has received attention. Recent regulations in the United States controlling emissions of metals and halogen acid gases from incinerators burning hazardous waste were discussed (C7).Measurement of Clean Air Act hazardous organic compounds by GC using United States Environmen-tal Protection Agency (EPA) method 18 allows some flexibility in the sampling method selected; thus, the advantages and disadvantages of different sampling methods, including the use of a flexible bag, direct interface, dilution interface, and adsorption tube, were discussed (CB). A protocol listing im ortant requirements for the validation of test methods to etermine compounds in a gas stream, includin the use of audit materials, documentation, and procecfures for determining bias and precision by isoto ic and analyte spiking of multiple train samples, was pubEshed (C9). A framework for the interpretation of ambient air monitoring data from areas near municipal solid waste incinerators was proposed, and data from several recent monitoring projects and several modes of analysis were presented (CIO). Several articles described continuous emissions monitoring systems. For the purpose of guiding future research, recommended operating procedures for sampling and analysis of total hydrocarbons (0-2000 p m) were suggested (C11). Extended laboratory and field ev&ations of systemsavailable to measure hydrocarbon emissions from hazardous waste incinerators were performed ((212). In this study, the use of heated and unheated sample delivery systems was investigated; it was possible to operate a heated hydrocarbon monitoring system continuously, for extended periods, with no system maintenance. A system that measured 11gaseous components with three process analyzers in less than 1min and that met, or exceeded, EPA requirements was developed (C13). Infrared (IR) monitoring techniques continue to be developed and im roved. A Fourier transform IR (FTIR) analyzer was usexto determine CO, NO, NO2, S02, CHI, HCl, HF, and NH3(C14). FTIR was used to quantitate combustion products of chlorinated hydrocarbons; the absorbances of the species measured were sensitive to total pressure, unless the optical density was very low (C15). Multicomponent IR analysis, with only one analyzer, was used to measure as many as eight gases; ood selectivity and sensitivity was attainable because inter ering gases could be measured and their interference effects corrected (C16). Several novel monitors were develo ed. A continuous monitoring system based on differenti3optical absorption
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spectroscopy was described for the determination of gaseous pollutants (C17). Part er-billion concentrations of chloroethylenes were measurezby resonance-enhanced multiphoton ionization (C18). As stem, based on absorption spectroscopy in the UV to near-18 range was developed; the transmitter consisted of a high-pressure Xe lamp and the receiver, which could be located up to 2 miles away, collected light and transmitted it via a fiber-o tic cable to the analyzer (C19). Concentrations of 20-50 ppg of various substituted benzenes and PAH with two to six rings were detected using an on-line gas analyzer which monitored combustion products by short column (transfer line) GUMS (C20). PCDD/F and polycyclic aromatic hydrocarbons (PAHs) continue to be a focus of organic analyses. Advances in analytical procedures for the determination of hazardous pollutants, including PCDD/F, polychlorinated bi henyls (PCBs), and PAH, were discussed (C21). A samptr that allowed the determination of PAH with minimal samplin artifacts was developed; the sampler consisted of a heate! stack probe, a dilution tunnel, a residence chamber in which combustion products were given sufficient time for condensation of vapor-phase material onto preexisting combustion particles, and a specialized collection s e (C22). The sampling and analysis of PCDD/F from com ustion sources was the subject of a recent review with 41 references ((223). A modified EPA method 5 sampling train was used to collect PCDD/F (C24). The EPA published additional methods for measurement of PCDD/F collected using glass fiber filters and XAD-2 resin (C25). Five sampling techniques were evaluated for PCDD analysis; total emissions obtained by all methods were comparable, but differences existed in the distribution of these compounds in various compartments (C26). PCDD/F in flue gases a t less than 1000 OC were sampled usin quartz wool and XAD-2 resin in acooled probe (C27). A stuiy on the distributions and recoveries of tetraand octachlorinated dioxin in an MM5 sampling train was performed and areas of improvement were suggested (C27). Methods for inorganic analyses of combustion effluents continue to be improved. Sampling and analysis of municipal wastewater sludge incinerator emissions for metals, metal species, and or anics were discussed (C29). A multiple metals train was usef to Sam le flue as emissions of a variety of metals ((230). A d e n u g r sam 8ng system was developed to study the speciation of volatipe metals released from hightemperature processes (C31). Microwave digestion of dust and ashes was erformed and the advantages and disadvantages of usin Jfferent acid mixtures for this technique were presented ($32). Compound-specific analytical methods were reported. Hexavalent chromium in sludge incinerator emissions was determined usin ion chromatogra h and inductively couiffusion scrubber ion pled plasma- (IEP-)MS (C33). chromatography instrument was used to determine HCl with a detection limit of 5 ppt and a temporal resolution of 5 min; calibration of this instrument was performed using a novel source of gaseous HCl based on the sublimation of NH&l (C34). ICP/MS was used to determine the ratio of 2MPb to 207Pb in order to determine the origin of lead emissions (C35). New methods for the sampling and analysis of mercury continue to be developed. A sam ling method based on the use of activated carbon was deve oped; collection efficiency decreased with increasing tem erature and with increasing flow rate (C36). EPA methotflOlA (Hg specific) and the draft EPA multimetals method for determination of Hg in flue gases produced similar results (C37). Mercury in the urban environment close to emission stacks was measured at ppt detection limits using gold-impregnated sand for collection, followed by desorption and atomic fluorescencedetection
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(C38).
Several references discussed the characterization of fly ash. Trace elements in fly ash have been characterized by proton microprobe analysis and PIXE (C39), various X-ray fluorescence techniques (C40-C42), and y- and a-spectrometry (C41). Methods for the determination of specific elements, including arsenic (C431, beryllium (C44), fluorine (C451, gallium (C46), and selenium (C47), have been published. Biomedicalwaste incinerators received some study. Metals and PCDD/F emissions of eight biomedical waste incinerators were higher than those of other combustion sources (C48). A trapping train consisting of a water-cooled glass probe and ANALYTICAL CHEMISTRY, VOL. 65, NO. 12, JUNE 15, 1993
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impingers containing a neutral phosphate buffer was developed to determine microorganisms in air emissions from medical waste incinerators (C49). Fugitive Emissions (Process Equipment Leaks). Portable FID, photoionization detection (PID),and IR analyzers are typically used to detect fugitive emissions from process equipment. The responses of selected portable analyzers used for EPA method 21 analyses to 80 volatile organic compounds at concentrations of 500 ppm were determined; detector selections for the analyses of specific compounds were recommended (C50). Nuclear Emissions. Two articles considered emissions from nuclear power plants. Accelerator mass spectrometry (AMS) was used to monitor 14Cemissions; AMS was advantageous to @-spectrometrybecause of its ability to overcome interference problems, its requirement for a small, 0.05-m3 sample size, and the ease of its automation for continuous sampling (C51). An on-line measuring system comprised of a sampling head and a portable, high-purity Ge detector coupled to a 4K MCA was used to measure the concentrations of 90Krand 137Xereleased in the gaseous effluents from a research reactor; the concentrations of 90Srand 137Cscould be deduced from the measurements of these precursors (C52). An activated carbon-supported palladium trap held at -120 "C and preceded by a silica gel column was used to collect various forms of I4C, including 14C0, 14C02,14CH4, 14C2H4, I4C2H6,and 14C3H8,emitted from a research reactor and from a radioisotope production laboratory. These compounds were analyzed by a radio-GC, and 0.3 mBq/cm3 for 14C02 was detectable (C53). Emissions from Nature. A few references discussed combustion emissions from nature. Test procedures to determine emissions from open burning of agricultural and forestry wastes were developed (C54). NO,, O3(at
