Anal. Chem. 1997, 69, 251R-287R
Environmental Analysis Ray E. Clement* and Paul W. Yang
Laboratory Services Branch, Ontario Ministry of Environment and Energy, 125 Resources Road, Etobicoke, Ontario, Canada M9P 3V6 Carolyn J. Koester
Analytical Sciences Division, Lawrence Livermore National Laboratory, Livermore, California 94551 Review Contents General Reviews Air Analysis Applications General Comments Reviews Standards and QA/QC Fixed Sources Mobile Sources Ambient Air Air Emissions from Waste and Waste Sites Accidents and Emergencies Atmospheric Chemistry, Transport, and Deposition Biomonitoring/Bioassays and Microorganisms Water Analysis Applications General Comments Reviews and Articles of Broad Interest Surface Water, Rivers, and Lakes Groundwater, Wells, Reservoirs, and Springs Drinking Water Seawaters and Coastal Waters Municipal and Industrial Wastewaters Landfill Leachates, Sludges, Waste Sites, and Runoff Biomonitors, Biological Sensors, Immunoassays, and Chemical Sensors Methods for Water Analysis QA/QC and Related Issues Soil and Sediment Analysis Applications Sampling Inorganic Analytes Organic Analytes Biological Sample Analysis Applications Inorganic and Organometallic Analytes Organic Analytes Radionuclides Quality Control and Reference Materials General Reviews Reference Materials Miscellaneous Miscellaneous Applications Toxicity Testing, Biomonitoring, and Bioindicators Miscellaneous Methods Technology and Analyte Cross-Reference Literature Cited
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This review covers developments in applied environmental analytical chemistry from November 1994 to the end of October 1996, as found in the Chemical Abstracts Service CA Selects for Gas Chromatography, Mass Spectrometry, Inorganic Analytical Chemistry, and Pollution Monitoring. Because of other reviews S0003-2700(97)00010-3 CCC: $14.00
© 1997 American Chemical Society
that appear in this issue, we have excluded most references to the following topics: industrial hygiene, general air and water quality parameters, pesticides and herbicides, greenhouse gases, guidelines and regulations, risk assessment, human levels, modeling, commercial products, and food. We emphasize the determination of trace organics and trace metals and organometallics in real environmental samples. Therefore, we have also excluded most references to the development of new methods where only artificial samples or reference materials are tested. As before, the review is organized by matrix rather than analyte or method used. A few changes in the organization of the review have been made to reflect the increasing importance of some topics and decreased emphasis on others. For example, the section on Toxicity Testing, Biomonitoring, and Bioindicators is now included as a heading under the Miscellaneous category. The authors appreciate any comments on how to make this review more useful to the environmental analytical professional. GENERAL REVIEWS As noted in the previous review in this series (A1), there were many reviews concerning the environmental analysis area. Chung discussed the importance of the analytical sciences in assessing environmental quality (A2). In cases where contaminant concentrations are below the detection limit, many still misinterpret this to mean “equivalent to zero”. Other reviews have summarized contemporary trends in environmental analysis (A3) and produced a handbook of environmental analysis (A4). Sampling procedures, problems with sample inhomogeneity, and related topics with reference to suspended sediment and associated trace elements in water quality studies were discussed by Horowitz (A5). A review of sediment pore water collection methods for trace metals analysis has also appeared (A6). Hodson reviewed available software for environmental professionals (A7). Mass spectrometry (MS) and related techniques were covered in several reviews (A8-A15). The role of MS in advancing environmental research was discussed by Charles (A8). Hites showed the advantages of using electron capture mass spectrometry for trace organics; he discussed the mass spectra of various compound classes with emphasis on the fragmentation reactions common to each group (A9). For liquid chromatography/mass spectrometry (LC/MS) methods, Linscheid reported that the most outstanding configuration was the atmospheric pressure source with electrospray interface and chemical ionization (A10). The use of particle beam LC/MS for agrochemical and environmental applications was also reviewed (A11). MS techniques are becoming more popular for metals determinations, as shown by two reviews on inductively coupled plasma mass spectrometry (ICPMS) Analytical Chemistry, Vol. 69, No. 12, June 15, 1997 251R
applications (A12, A13). An important aspect of environmental applications of MS-based methods is the ability to use stable isotopically labeled analogues of analytes, as shown by Bolt (A14). The recent development of a novel isotope method for environmental soils and sediments, GC/combustion-isotope ratio MS (GC/C-IRMS) was summarized in another review (A15). Several reviews on GC and related techniques as applied to environmental analysis also appeared (A16-A27). The use of multispectral detection (IR, FT-IR) (A16) and atomic spectroscopy detection (A17-A19) for GC analysis have been reviewed. Somsen reviewed the coupling of planar chromatography techniques with spectroscopic detectors such as IR, FT-IR, and fluorescence (A20). The coupling of supercritical fluid chromatography with MS seems to be entering a period of revival, due to the use of atmospheric pressure ionization techniques, according to a review by Arpino (A21). Capillary electrophoresis provides excellent performance for environmental applications, when coupled to MS detectors (A22, A23). High-temperature capillary GC methods seem to present an excellent choice for rapid-screening environmental applications (A24). Trends in purge and trap (A25) and rapid headspace GC (A26) were also reviewed. Krylov reviewed the use of GC, high-pressure liquid chromatography (HPLC), and associated hyphenated techniques for environmental analysis (A27). Field methods are covered in another review in this issue, but we mention here some related reviews (A28-A36). Much work has been performed for the development of field-portable (A28) and mobile (A29) MS instrumentation. One review covered techniques such as GC/MS, microwave-induced plasma-MS, and laser-induced fluorescence spectroscopy for on-site measurements (A30). Considerable research on the use of immunoassay and related techniques has been conducted, as shown by a number of reviews (A31-A35). Lesnik described the regulatory approval process, general guidelines for the development of screening methods, and specific validation criteria for immunoassay methods (A34). Winton reviewed the use of field lysimeter studies for the study of the environmental fate of pesticides (A36). Reviews on the environmental determination of specific compound classes also appeared. The determination of pesticides (A37), triazine herbicides (A38), and toxaphene (A39) were all reviewed. Lau stated that electron capture negative ion MS is the most sensitive and specific method for toxaphene determination (A39). Larsen reviewed the GC separation of polychlorinated biphenyl (PCB) congeners; the state of the art is routine isomerspecific analysis with multicolumn techniques (A40). GC is a rapid method of choice for microbial quantitation (A41). Kataoka reviewed derivatization reactions for the determination of amines in the environment (A42). Speciation continues to be a topic of increasing importance, as judged by a number of reviews (A43A52). Organometallics can be determined by SFC/ICPMS (A43), or by supercritical fluid extraction followed by supercritical fluid chromatography (SFC) (A44). Mach reviewed methods for monitoring metal species in typical utility aqueous discharge streams (A45). Mass spectra of various organometallic species of As, Sb, and Bi (A46) and of organomercurials (A47) have been described. The speciation and determination of Hg (A48), Pb (A49, A50), As (A51), the organotins (A52-A54), and the actinides (A55) have all been reviewed. Dietrich summarized the analytical techniques for the determination of chemical species in natural water, wastewater, and drinking water samples (A56). 252R
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Other reviews focused on the specific technologies and techniques used for environmental analysis (A57-A68). The use of UV irradiation to destroy organic matter prior to inorganic analysis was described by Golimowski (A57). Recent advances for the analysis of individual environmental particles were described (A58). Other reviews covered the use of total reflection X-ray fluorescence (A59), near-infrared spectroscopy (A60), luminescence (A61), fiber-optic sensors (A62), the nuclear microscope (A63), neutron activation (A64), ion mobility spectrometry (A65), biosensors (A66), electroanalytical methods (A67), and microwave radiation (A68) for environmental analysis applications. AIR ANALYSIS APPLICATIONS General Comments. This review focuses on the development of analytical methods and their applications in the analysis of toxic and hazardous air pollutants. Toxic and hazardous pollutants are organic compounds and inorganic metals or ions with defined toxicity, carcinogenicity, and/or mutagenicity. Articles related to nonmetal gases, acid gases, and criteria gaseous pollutants are reviewed in the Air Pollution review in this issue of Analytical Chemistry. The organization of the review is the same as previous ones with some adjustments to reflect current trends in air analysis. For example, there were increased intra- and interlaboratory quality control and quality assurance (QA/QC) activities of air analysis. A new section, Standards and QA/QC, was created to address this important development. Clearly, increased QA/QC activities and laboratory automation lead to the generation of larger data sets with fewer resources. This made data interpretation an even more demanding task because of the time-consuming nature of the process. Effective application of chemometric algorithms to extract information from large data sets has become critical. This is especially the case for optical spectroscopy monitoring of volatile organic compounds (VOCs) where, in a typical real-time monitoring of 15 VOC analytes, spectral data could be generated at a rate of more than 2 × 107 bytes/h. Use of chemometric techniques to update VOC concentration information in real time becomes imperative. This close relationship allowed the expansion of the Data Reduction subsection in the Ambient Air section to include references related to optical spectroscopic real-time monitoring and the application of chemometrics to a large data set for information retrieval. In addition to these adjustments, a new subsection, Source Monitoring/Source Apportionment, replaced the Miscellaneous Stationary Sources subsection of the Fixed Sources section. The Indoor Air subsection of the Ambient Air section was expanded to include topics related to microenvironment air. The section on Miscellaneous Air Analysis Applications has been replaced by Biomonitoring/Bioassays and Microorganisms. Reviews There were 35 reviews published in environmental air analysis. They cover concerns and issues in the following six categories: monitoring methods, indoor and personal exposure, sampling and laboratory methods/results, aerosol analysis, realtime monitoring, and atmospheric deposition. Reviews related to the development of monitoring methods for on-site field monitoring and off-site laboratory analysis of air pollutants include a U.S. EPA-sponsored survey on the status of ambient air measurement methods for hazardous air pollutants analysis that showed the need for continued method development for the Clean
Air Act (CAA) (B1). A review with 987 references on the measurement methods to decide the compliance with ambient air quality standards for suspended particulate was published (B2). A compilation of information on real-time monitoring at the Superfund sites (B3), the status and prospects of environmental health monitoring of air pollutants (B4), and control and monitoring of air pollution (B5) was also published. Sources and concentrations of suspended particulate in ambient air, homes, and buildings (B6) and strategies for monitoring indoor air pollution with specific considerations of climate factors and sampling time (B7) were discussed in two reviews. A discussion on the sampling, analysis, and sources of indoor air pollutants and their contributions to the sick building syndrome was published with 41 references (B8). A summary of air analysis methods used to monitor human exposure, including the direct and indirect determination of Pb, Cr, and VOC exposure (B9); and sources, measurements, concentration, and pollution control of VOCs in indoor air (B10) were reported. The use of molecular techniques, their adaptations to current sampling techniques, and their potential applications in monitoring the microbiological quality of indoor air were reviewed (B11). Issues in biomonitoring studies of heavy metal pollution, including the collection of vascular plant samples, sample pretreatment, seasonal variation, and data assessment were discussed by Djingova and Kuleff (B12). A review with 33 references discussed basic concepts, techniques for the preparation of organic and inorganic gas standard mixtures, and the possibility of interaction of analytes with container walls (B13). Ambient VOC analysis by high-resolution capillary GC (B14), general aspects of ambient air VOC analysis using GC, including column performance, types of analytes, and monitoring strategies (B15), and on-site VOC monitoring using GC and portable GC systems were reviewed (B16). Topics related to the analysis of filter samples for gas and particulates, including filter analysis methods, encompassing mass, elements, and organic targets were reviewed (B17). Correlational studies between insect behavior and atmospheric gaseous pollutants were discussed in terms of effects of gaseous pollutants on plant/insect, likely consequences, and areas in need of further research (B18). Analytical results of methane from rice production (B19) and methane emissions from biomass burning (B20) were documented with 77 and 46 references, respectively. The use of isotopes and tracers to study emission and consumption of trace gases was reviewed with 142 references (B21). The evolution of environmental polycyclic aromatic hydrocarbon (PAH) studies in the last 150-year was reviewed (B22). Applications of GC and HPLC techniques to the analysis of PAHs were discussed in a review with 106 references (B23). Modern analytical methods for the determination of mercury in ambient air were summarized (B24). Taking advantage of the state-of-the-art mass spectrometric technologies, applications of laser desorption mass spectrometry (LDMS) analysis of a single aerosol particle (B25) and in situ, real-time particle analyses to the determination of both particle size and chemical composition of single particles (B26) were reviewed. A review on the application of microanalysis of environmental single particles for source apportionment and threedimensional analysis for intraparticle inhomogeneity was published (B27). Real-time spectroscopic data acquisition followed by computerassisted analysis of monitoring data has been the topic of seven
publications. Reviews on the use of computer software to interpret infrared spectra of atmospheric measurements and their applications to the measurement of methane, HCHO, and VOCs (B28), open-path Fourier transform infrared (OP-FT-IR) measurements of atmospheric gas pollutants with up to ppb sensitivity (B29), and the advantages of infrared gas monitoring, including the sensitivity, consistency, and specificity (B30) were presented. Applications of OP-FT-IR monitoring techniques to the analysis of volcanic plumes (B31) and uses of ground-based, spectroscopic techniques to the measurement of atmospheric trace gases (B32) were discussed. Tunable diode laser monitoring systems that are suitable for the measurement of atmospheric trace gas constituents method were discussed with 164 references (B33). Finally, reviews on optical sensing of fugitive emissions (B34) and optical remote sensing systems for air pollution monitoring, including light detection and ranging (LIDAR), long-path ultraviolet (UV) measurement systems, gas filter infrared correlation techniques, OP-FT-IR measurements, and near-IR tomography in air monitoring (B35, B36) were published. Atmospheric processes governing trace metals in precipitation, sampling, analysis, and concentration of Pb and Hg were reviewed with 95 references (B37). Standards and QA/QC. There were increased activities in interlaboratory comparison, the preparation of reference materials for laboratory calibration and standardization, QA/QC and laboratory accreditations, and the refinement of protocols to assure the generation of data with superior quality. All these works were aimed to improve the quality in environmental air analysis to acquire results with higher precision and accuracy. This section is created to address this important trend to include topics related to data quality enhancement, QA/QC protocols, and the standardization of analytical methods. In the preparation of reference materials, Landsberger et al. developed a suspended particulate standard (PM-10) that consisted of 50 fine and coarse fractions for interlaboratory study activities of the International Atomic Energy Laboratory laboratories (C1). Binstock et al. described the procedures used to prepare a lead-contamination measurement method evaluation standard that can be used for the laboratory accreditation of Pb analysis programs (C2). A complete procedure of calibration and quality control in proton-induced X-ray emission (PIXE) analysis using thin calibration standards and reference materials for the validation of accuracy were also developed (C3). The use of a double-blind quality assurance sample for X-ray fluorescence (XRF), atomic absorption spectroscopy (AAS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES) Pb analysis was implemented for the Urban Soil Pb Abatement Demonstration Project with satisfactory, multilaboratory test data (C4). National Institute of Standard and Technology (NIST) developed a new Rn-in-air standard contained within spherical glass ampules. Interlaboratory comparison results between the new NIST standard and U.S. Bureau of Mines were in excellent agreement (C5). Round-robin and interlaboratory comparison of measurement methods ensure the generation of consistent monitoring data from different laboratories. Publications were reviewed to address this important activity. Colle et al. reported the results from a twoweek international marine-atmospheric 222Rn measurement intercomparison in Bermuda. The concentration of 222Rn during this two-week period ranged from a few hundredths of a Bq/m3 Analytical Chemistry, Vol. 69, No. 12, June 15, 1997
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to about 2 Bq/m3 with the standardization sample covering the range from 2.5 to 35 Bq/m3 (C6). Schroeder et al. reported a comparability study on the sampling and analytical procedures for atmospheric mercury (gaseous and particulate phase) measurement methods in a five-day exercise that involves four agencies from three countries (C7). Lecuyer and co-workers carried out a round robin that involves seven laboratories in the analysis of trace elements [As, Cd, Cr, Cr(VI), Cu, Hg, Ni, Pb, Sb, Se, Zn] in ashes and leachates. The authors found results from Cr, As, and Cd were consistent while those from Cu, Zn, and Ni were very dispersed. No correlation could be found for Se, Sb, and Pb in the samples (C8). Burdette presented a matrix spiking program that can be used to assess the field performance of methods used in the measurement of hazardous air pollutants such as VOCs, SVOCs, aldehydes, and ketones (C9). Liaw and Tso published a standard method for the measurement of ambient non-methane hydrocarbons (NMHCs) using canister sampling and ICP-flame ionization detection (ICP-FID) analysis. Kovats index was used in their method to enhance the identification power of the ICP-FID system (C10). A critical evaluation on the data quality of an on-site fieldportable GC/MS and an off-site permanent laboratory GC/MS system was carried out by Schuetz and co-workers within the laboratory and at a remediation site (C11). A set of criteria used in the design of a new American National Standard Institute (ANSI) standard on the measurement of stationary exhaust emissions and methods that can be used for the measurement was presented (C12). Fixed Sources. Fixed sources of airborne pollutants include both industrial and natural sources. There were minimal publications in Miscellaneous Stationary Sources. As a result, a new subsection, Source Monitoring/Source Apportionment Methods, was created to discuss results and development related to this topic. Publications related to Miscellaneous Stationary Sources were moved to the Section Air Emissions from Waste and Waste Sites. (a) Industrial and Fugitive Emissions. Using a coupled, off-line supercritical fluid extraction (SFE) and SFC, PAHs were found in the crude gas of industrial boiler plants using fuel oil (D1). Particulate-phase-associated nitro-PAHs were found on particles emitted from steel industrial fumes (D2). Chemicals emitted from resin fortified resistance spot welding operations in the automobile industry were identified as PAHs and aldehydes (D3). VOC emissions, including the estimate of VOC emission factors, from the manufacture of inks were studied. In contrast to the EPA’s estimate of 30-lb VOC emissions for each ton of ink produced, the authors estimated a more realistic VOC emission factor at 44.7 lb/ton of ink (D4). The formation and the removal of chloroaromatics from stack emissions at a metal reclamation and an aluminum smeltering plant were published. Reduction of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar PCBs were estimated at a efficiency of >90%, >78% for polychlorinated naphthalenes (PCNs), and >51 and >43% for chlorobenzenes (CBs) and chlorophenols (CPs), respectively (D5). Measurement of CF4 and C2F6 emissions from eight aluminum smelters that represent 11% of the total global production was carried out. The authors determined that 99% of the emissions occurred during anode events (AE) with fluxes for CF4 and C2F6 calculated at 0.5-1 and 0.02-0.08 kg/ AE, respectively, with a standard deviation of 40-70% (D6). 254R
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Cadmium in plastic processing fumes from injection molding of thermoplastic resins was studied. Results obtained from this study shows the cadmium level was below the guideline of 2.5 mg/m3 (D7). (b) Incinerators, Stacks, and Residues. Brown and Mohs discussed the requirement from EPA’s new regulation that requires sewage sludge incineration facilities to measure total hydrocarbon (THC) emissions to demonstrate compliance with three separate flue gas parameters. Instead of using methods suggested by the EPA, the authors developed and applied an indirect method to the determination of THC with data accuracy exceeding that required by the EPA (D8). Lee and co-workers analyzed the concentration of 21 PAH targets during the incineration of three types of waste ion-exchange resins. The total PAH measured from the flue gas and the ash averaged 1782 mg/m3 and 6 mg/g, respectively (D9). Combining several inorganic analysis techniques, Eighmy and co-workers characterized the speciation and leaching behavior of Zn, S, Pb, K, and Cl in electrostatic precipitator ash of a Canadian municipal solid waste (MSW) incinerator (D10). Results from mercury emission monitoring using the amalgamation technique at a waste incineration plant were published (D11). (c) Nuclear Plants. The environmental level of 14C around a Swedish nuclear power plant was measured with accelerator mass spectrometry (AMS) by Stenstroem and co-workers. The study suggested that, for the test of dispersion models, AMS measurement should be carried out on both of an emission source and in the surrounding of the plant (D12). Levels of 238,239,240Pu, 241Am, and 242,244Cm released from four Czech and Slovak nuclear plants were monitored in 1991-1993 with only one of the plants recorded a much higher level of 239,240Pu (3.0-26 Bq/m3 vs an average of 10% relative standard deviation multicomponent analysis of aromatic hydrocarbon emissions using laser mass spectrometry electrothermal vaporizer, ICPMS analysis at pg/m3 sensitivity for vehicle exhaust pulsed tunable laser analysis at 10%) of analytes with large dynamic range of concentrations real-time FT-IR and UV measurements to determine the effect of vehicle emissions on urban air quality hydrocarbon emissions were speciated from the exhaust of a production engine without an active catalyst at 3-s interval
E1, E2
fluorescence (E14) and GC/MS (E15) techniques, respectively. One should pay special attention to the high-activity DRL that was coeluting with 1-nitropyrene. As 1-nitropyrene has low dioxin receptor binding activity, the identity of this DRL remains to be characterized (E15). New procedures for applying ICP-AES for the analysis of volatile metal-containing (iron, chromium, manganese) compounds were developed (E16) for diesel particulate matter analysis. Airborne FT-IR measurement of time-/space-resolved spectra of several species in the exhaust plume of an aircraft jet engine (E17) was reported. Similarly, IR analyses of trace gases of several ground-based jet engines were done for CO2, CO, H2O, HCHO, and other hydrocarbon species. Emission rates at different engine thrust levels were calculated for possible applications of turbine design and on-board engine status control to achieve the least amount of pollution (E18). In situ observation of the use of sulfur-containing jet fuels on the particulate emissions ranging from 0.007 to 1 mm at different cruise heights and ages of the exhaust was made (E19). Ambient Air. Two subsections of this section were expanded and restructured from the last review to reflect analytical trends observed in the last two years. The Data Reduction subsection was expanded to include topics in optical spectroscopy and chemometric analysis while the Indoor Air subsection was expanded to include topics related to personal exposure to 256R
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E3-E5 E7 E8 E9 E10 E11
E12 E13
pollutants in indoor and other enclosed areas, the microenvironment. Therefore, the creation of a new subsection entitled as Personal Exposure. Indoor and Microenvironment Air. (a) Sampling. The collection of representative air samples for laboratory analysis remained the most difficult part of environmental air analysis. Discussed in this subsection are organic sample collection methods using cryogenic concentration (F1, F2), solid adsorbent concentration for VOC and semivolatile organic compound (SVOC) analyses (F3-F12), formation and identification of artifacts during the sample collection (F13-F15), on-line, real-time sampling of VOCs (F16, F17), and miscellaneous sampling methods for SVOC analyses (F18-F22). Noteworthy is the formation of artifacts due to the reaction of O3 with ethene and isoprene using a Horibe cryogenic trap (F13) and the possible reactions of VOC with O3 or with hypoiodite in a KI-based O3 reactant trap (F14). As well, the development of a liquid electrostatic aerosol precipitator for ultra high-volume sampling of SVOC, especially PAH, for time resolution studies (F19); an automated rain collector for PCDD/PCDF (F20) analysis; and a remote-controlled helicopter sampling platform for air sampling in difficult situations (F22) were noted. Methods used for inorganic sampling/monitoring purposes include the application of a multicyclone probe to fractionate particles for scanning electron microprobe (SEM) and ICPMS analyses of stack emissions (F23) and the application of the
Table 4. Monitoring of Ambient Organic Compounds analytes air toxics VOCs
benzene, toluene, xylene halocarbons and radiative trace gases HCFC-142b, HCFC-141b hydrazine formic and acetic acids C3-C5 alkyl nitrates PAH PCDDs, PCDFs, coplanar-PCBs, PAHs PCDDs, PCDFs particle size distribution of aerosols aerosols containing Ca, Si Na, Mg, Al, Cl, Se, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, As, Sc, Br, Rb, Sr, Mo, Cd, Sb, Cs, Ba, La, Ce, Sm, Yb, Lu, Hf, W, Hg, Th 137Cs methanesulfonate, nitrate, sulfates, Ba, Cu, Pb Cr, Pb, and Zn-containing aerosols Hg
location and comments Gulf Coast, TX, where industry produces over 50% of the nation’s synthetic chemicals but discharges less than 8% of of the nation’s toxic emissions GC/MS analysis in the remote troposphere at the Manua Loa Observatory, Hawaii; purge-and-trap GC/MS analysis from the Guaymas Basin (Gulf of California); serial GC/MS analysis in the arctic atmosphere during the 1992 Polar Sunrise Experimnt passive sampling and analysis at urban, suburban, rural, and alpine sites in Switzerland long-term trends (1987-1994) reported for air masses advected to the Mace Head station, Ireland air archive samples (1978-1993) collected from Cape Grim, Tasmania, were analyzed and reported fiber-optic chemical dosimeter network monitoring results at Cape Canaveral Air Force Station airborne tandem mass analysis over the western North Atlantic measurement and mixing ratios were reported for a South Africa station concentration of PAHs at underground mine adjacent to diesel vehicles equipped with different type of emission control hardware Mississippi Sandhill Crane National Wildlife Refuge, Jackson County, MS, duplicate high-volume sampling during May-September 1991 ambient levels of dioxins were measured and reported in a pulp and paper mill X-ray electron microprobe (XEM) analysis of single aerosols in Central Siberia and their contributions to Arctic pollution SEM, XEM, and X-ray diffraction analysis of museum aerosols at the Correr Museum, Venice detailed description and results obtained from upstate New York ambient trace metals monitoring program high-volume sampling and analysis in New Zealand high-volume sampling and laser microprobe mass spectrometry (LAMMS) analysis of Antarctic aerosols at the Syowa station in February-December 1991 aerosols were collected and analyzed above the North Sea real-time, continuous monitoring of atmospheric concentration in rural areas of southern Quebec; description and field tests for a regional deposition network; total gaesous mercury measurement project and results in central and south Florida
denuder technique in filter sampling of airborne chromates analysis (F24). Sampling of volcanic gas for neutron activation (NAA) analysis (F25) and a quasi-on-line automated sampling system for heavy metal analysis in gaseous HCl were described (F26). (b) Monitoring Programs and Field Measurements. There were 14 publications where airborne organics were monitored in urban centers, rural areas, a rocket launch facility, and underground mines. Analytes ranged from VOCs (F27-F31), HCFC (F32, F33), hydrazine propellent (F34), and formic and acetic acids (F35) to PCDDs, PCDFs, PCBs, and PAHs (F37-F39). Results from airborne inorganic pollutants monitoring programs were reported in nine publications with analytes ranging from particle size distributions to Hg to heavy metals. Table 4 summarizes these activities according to the analytes measured in the programs. Noteworthy was the renewed interest in Hg monitoring in urban (F46), deposition (F47), and rural areas (F48). (c) Optical Spectroscopy, Data Reduction, and Chemometric Analysis. Technological improvement in spectroscopic measurements in the IR and UV regions allowed field measurement in harsh industrial conditions and Superfund sites on small portable equipment. Benefiting from the development of MS-DOSbased computing power, real-time signal processing capability has been used to implement complex measuring principles to remove background interference effectively. This subsection focuses on
refs F27 F28, F29, F30
F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 F41 F42
F43 F44 F45 F46, F47, F48
the application and development in optical spectroscopic monitoring of air pollutants and computer algorithms for the extraction of information from, but not limited to, spectroscopic data sets. Field applications of FT-IR including the validation of precision and accuracy of OP-FT-IR measurement has been done at Calvert City, KY, using certified VOC standards and side-by-side measurement with a GC/MS system (F49). A three-day, on-site OP-FTIR measurement of emissions during the remediation at a former gas manufacturing plant found concentrations of benzene correlated with site activities well. Off-site laboratory analysis of field data showed on-site monitoring of ammonia and toluene was possible (F50). A ground-based FT-IR system has been applied to the measurements of stratospheric ClO, ClONO2, HCl, and HF (F51) and HF and SiF4 emissions from firing clay ceramic (F52). In the method development area of monitoring techniques, the combination of near-IR diode lasers and optoacoustic detection (OAD) was demonstrated to have a sensitivity about 3 orders better than that achievable in a 1-m single-pass cell for gaseous sample analysis (F53). A gas filter correlation infrared spectrometer has been used to collect reliable stack gas HCl information that may be used for emissions reporting to the U.S. EPA following the CEM Guidelines in 40CFR part 60 (F54). There were good examples on the use of data reduction and chemometric techniques to obtain advanced information from the data set. For example, using the PAL (point, area, and line source) plume dispersion model and mobile OP-FT-IR data obtained from Analytical Chemistry, Vol. 69, No. 12, June 15, 1997
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a petroleum park, it was demonstrated that concentration and emission rate information of 25 air toxics could be derived (F55). The effect of different quantitation methods, libraries, and background spectra obtained under varying environmental conditions was evaluated in a simulator for OP-FT-IR measurement using toluene as a benchmarker (F56). As well, the training and the application of artificial neural networks for automated real-time identification of radioactive isotopes using γ-ray spectroscopic data was published (F57). Using regressional analyses, Lipfert studied 31 epidemiologic reports linking air pollution with premature mortality and calculated mean mortality responses of air pollution parameters such as fine particulate, SO42-, NO2, SO2, CO, H+, O3, and coarse particles (F58). Principal component analysis of ICPMS data from moss samples collected from a Norwegian survey on atmospheric deposition showed that classifying elements into long-range transported elements, windblown minerals, local emissions, marine sources, and contributions from plants is possible (F59). A statistic analysis package has been developed and applied to determine site representativeness for PM-10, NO2, NOx, NO, SO2, CO, O3, THC, and NMHC sampling purposes (F60). Hierarchical clustering and correspondence factor analysis were used to classify aerosol analytical data obtained from ion chromatography (IC), AAS, and opticothermal analyses (F61). The use of numerical procedure and OP-FT-IR data to construct a twodimensional tomographic map of air pollutants (F62) and the application of partial least-squares (PLS) analysis to separate anthropogenic sources from natural anomalies in environmental geochemistry (F63) was discussed. (d) Methods. This section is devoted to publications where sample preparation and/or instrumentation techniques were improved to resolve existing analytical problems and were demonstrated by the measurement of real-world samples. Publications where novel analytical techniques were used to enhance sensitivity, operating efficiency and, above all, the data quality, though without real-world applications, could be included in this section because of their potential contributions in environmental analysis. Like prior reviews, methods are divided into organic and inorganic subsections where Table 5 and Table 6 are used to summarize organic and inorganic applications, respectively. Table 5 summarized organic methods in five categories according to analytical technologies: GC-, GC/MS-, and MS-based analysis, HPLC/SFC, ion mobility spectroscopy (IMS), and sensors and miscellaneous methods. Efforts were made in the organization of the table such that subgroups were created under each category according to analytes and specific methods used in each publication. There was renewed interest in the application of solid adsorbent sampling, not only for VOC (F67, F71-F73, F86, F87, F90) but also for a variety of SVOC analyses (F74, F80F84). Methods and applications of automated GC-FID (F67) and GC/MS (F90) systems that met the requirement of the photochemical assessment monitoring station (PAMs) program for the determination of ozone precursors in urban and rural areas were published. The application of the derivatizing reagent 2,4,6trichlorophenylhydrazine, for the first time, to the analysis of atmospheric aldehydes and ketones using GC (F82) and new cleanup method where porous graphite carbon or activated carbon was used in place of the Florisil adsorbent for PCB analyses (F95, F98) was discussed in three separate publications. Table 6 summarized inorganic methods in five categories according to analytical technologies and analytes. There was 258R
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renewed interest in Hg monitoring as shown by the development of several new real-time Hg measurement systems (F118-F120). Real-time, direct MS analysis of single atmospheric particles for trace metals (F108, F109) and the combination of complex and solvent extraction for sample preparation and cleanup were reported also (F117). (e) Personal Exposure. Indoor and Microenvironment Air. This subsection covers publications in the area of sampling, method development, and studies of organic and inorganic pollutants in indoor and microenvironment air. The purpose of these studies was for personal exposure monitoring and would include samples collected from home (indoor) and other microenvironments such as the automobile, public transportation, workplace, bingo hall, restaurant, and shopping centers. In the area of sampling and new method development, Foster et al. discussed the possible migration of potentially toxic chemicals from distant sources into a house basement (F121). The U.S. EPA published personal air sampling and air monitoring requirements under 29 CFR 1910.120 (F122). Sampling and analytical artifacts caused by elevated indoor PCB concentrations were discussed (F123). Indoor VOC monitoring using TenaxTA sampling and portable ICP-PID (F124) analysis, whole-column trapping GC/MS analysis (F125), and ion mobility analyzer arrays, coupled with selective chemical ionization using different reagent gases for VOC monitoring (F126), were published. In the indoor SVOC analysis area, a trace of PCB/PCDD/ PCDF in indoor air due to elastic sealants and coated particle boards was reported (F127). As well, adsorbent sampling followed by thermal desorption (TD)-GC/MS analysis of gaseous PAHs at 300 °C was also reported (F128). Noteworthy was the possibility of transport of lawn-applied herbicide acids from turf to home as measured from carpet dust and carpet surface residues (F129), and measurement methods for 19 PAHs (naphthalene to coronene), and their respective distribution in house dust and track-in soil, were published (F130). The use of Chlorophytum elatum (spider plant) as a biomonitor for qualitative and semiquantitative PCB analysis of indoor air was also published (F131). There were field studies of indoor environment where continuous photoacoustic spectroscopy (PAS) monitoring of CO, CO2, formaldehyde, and total VOCs and comparisons of results of total VOCs with ICP-FID techniques (F132), field validation of a membraneless passive VOC monitor that can provide quantitative data ranging from 1 to 20 mg/m3 for a variety of VOCs (F133), the measurements of organic acids, aldehydes, and ketones and their relation to O3 in an indoor environment (F134); and a study on the volatization of VOCs from drinking water to indoor air (F135) were reported. The design, characterization, and application of a small environmental chamber for emission monitoring of household and office items, including those that can be used for the evaluation of the irritation potential of product emission using ASTM E981 mouse bioassay, were done (F136). VOC emissions from a vinyl floor covering (F137) and textile floor covering (F138) were also studied under dynamic and static conditions, respectively. Microenvironment air monitoring results from a 104-participant environmental tobacco smoke (ETS) exposure study for 33 VOCs, respirable suspended particulate (RSP), and ETS-RSP in New Jersey and Pennsylvania homes and workplaces were reported (F139). Other studies include indoor air quality in ice skating rinks (F140), levels of volatile haloforms in indoor swimming pool
Table 5. Organic Pollutants Analytical Methods analytes
VOCs or TO-14 tragets ozone precursor hydrocarbons (PAMS) VOCs , oxygenated VOCs Clean Air Act (CAA) targets, including vinyl chloride and benzene, toluene, xylene, and ethylbenzene chlorophenols nitro-PAHs hydroxy-PAHs peroxylacetyl and peroxylpropionyl nitrate trifluoroacetic acid diethylene glycols butyltin aldehydes, ketones aromatic amines
haloacetates VOCs vinyl acetates benzene, alkylbenzes VOCs
odorous VOCs particulate-phase PAHs, nitro, alkyl, and oxygenated PAHs particulate-phase PAHs particulate-phase nitro-PAHs coplanar PCBs, PCDDs, PCDFs PCDFs, PCNs PCBs Me3PB+, Et3PB+, PB2+, PAHs organometallic compounds benzene, toluene, xylene PAHs, phthalates, phenols, OCs, PCBs odorous compounds phosgene acetaaldehyde, acrolein, Me-t-Bu, Et t-Bu ether, propionaldehyde, propene, benzealdehyde, p-tolualdehyde, MeOH
methods/comments GC Methods canister or cryogenic sampling followed by GC-FID analysis; portable GC analysis adsorbent sampling followed by thermal desorption GC-FID analysis headspace GC-FID analysis on-line membrane extraction microtrap GC FID analysis thermionic detection EPA documentation identified analytical methods for all but 10 of the 189 CAA targets adsorbent sampling followed by TD-GC analysis description of a manual and an automated continuous GC-FID analysis Porapak-N sampling, MeOH elution, derivatization, followed by GC-ECD analysis HPLC cleanup followed by GC and surface ionization detection (SID) pentafluorobenzene bromide derivatization followed by GC-ECD or GC/NICI-MS analysis airborne GC-ECD analysis of PAN and PPN HS-GC (headspace GC-ECD or HS-GC/MS analysis activated silica gel sampling followed by GC-FID analysis Porapak-N cartridge sampling followed by GC-FPD analysis cartridge sampling, 2,4,6-trichlorophenylhydrazine derivatization, and GC-ECD analysis N-dimethylthiophosphoryl derivatization followed by GC-FPD analysis GC/MS, LC/GC/MS, MS/MS, and FT-MS Methods 1-(pentafluorophenyl)diazoethane derivatization followed by GC/NICI-MS analysis GC/ITMS VOC analysis with 0.01-0.03 ppb detection limits adsorbent sampling, tetrachloroethylene:acetonitrile (91:9) extraction, GC/MS analysis adsorbent sampling, microwave desorption, GC/MS analysis direct membrane introduction MS analysis with ppb detection limits solid-phase microextraction, GC/ITMS analysis automated adsorbent sampling, closed-cycle cryofocusing, GC/MS analysis TD-GC/MS and FID analysis of VOCs and odorous VOCs direct LC/GC coupling followed by ITMS analysis SFE followed by GC/MS analysis direct LAMMS and FT-MS analysis and indirect GC/MS analysis HPLC cleanup using porous graphite carbon and GC/MS analysis GC/MS analysis with peak mass profile monitoring to remove chlordane interference SFE of dusts (street, urban, highway) followed by GC/MS analysis Carbosphere-activated carbon cleanup followed by GC/MS analysis at 0.01-0.08 pg/m3 sensitivity Florisil/silica gel/alumina cleanup followed by GC/MS analysis HPLC and SFC Methods SFE/SFC analysis of particulates collected near a coke oven and a traffic island micellar mobile-phase HPLC/fluorescence analysis HPLC/ICP-IDMS analysis of rainwater samples Mobility Spectrometry continuous drift tube photoionization-based ion mobility spectrometry direct IMS analysis Sensors and Miscellaneous Techniques development of semiconductor sensors that can achieve an R2 of 0.95-0.96 when compared to human sensory values 4-p-nitrobenzylpyridine-impregnated porous cellulose tape with 3-month desiccator storage life pulsed molecular beam Fabry-Perot cavity FT-microwave spectrometric analysis in the low-ppm to ppb range (Ar or N2 carrier gas)
air (F141), ambient concentration of perchloroethylene in drycleaners’ home (F142), NMHC, PAHs, and VOCs in a traffic tunnel in Antwerp, Belgium (F143), and in-vehicle benzene level monitoring while driving in traffic (F144).
refs
F64-F66 F67 F68 F69 F70 F71 F72 F73 F74 F75 F76 F77-F78 F79 F80 F81 F82 F83
F84 F85 F86 F87 F88 F89 F90 F91 F92 F93 F94 F95 F96 F97 F98 F99 F100 F102 F101 F103 F104 F105 F106 F107
Organic pollutants measured from other microenvironments include levels of nitrosamines in a rubber vehicle sealing plant (F145), HCN, phenol, benzene, and naphthalene levels from the heating of a tar expoxy resin paint (F146), VOC levels in the Analytical Chemistry, Vol. 69, No. 12, June 15, 1997
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Table 6. Inorganic Pollutants Analytical Methods analytes
methods/comments
refs
single potassium nitrate particles
Direct MS Analysis real-time, direct ion trap MS analysis of potassium nitrate particle (15 µm) real-time, direct laser ablation and time-of-flight MS analysis
F108
chromium speciation Cd, Cr, Cu, Ni, Pb manganese speciation of arsenic compounds
As, Ba, Br, Ca, Co, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Sb, Se, V, Zn As, Ba, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, S, Sb, Si, Sr, Ti, V, Zn isotopic composition of U As, Ag, Ba, Be, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Se, Tl, V, Zn Ni, Cu, Zn, Cd, Tl, Pb
Hg
AAS cellulose acetate filter sampling, electrothermal atomization (ETA)-AAS analysis of particulates collected from industrial area coal fly ash using monothioxo-β-diketone chelating agent and ETA-AAS analysis cellulose membrane sampling, followed by specific sample preparation procedures, AAS analysis of arsine, As3+, As5+, monomethylarsenic acid, dimethylarsenic acid, and their salts XRF and NAA Analysis a 1-year comparative analytical methods study using air dust filter and grass samples direct XRF measurement followed by NAA or microwave digestion ICPMS analysis of PTFE samples for receptor model use ICPMS ICPMS analysis of 235/238 and 233/238 ratios for filter samples containing >10 ng of U acid digestion ICPMS analysis with a method detection limits less than 5 ng/m3 complexation/solvent extraction as a cleanup step for isotope dilution ICPMS analysis Hg Measurement Method ICP-AES photodiode array detection of Au-coated wire sampling and in-torch vaporization iodated carbon sampling, acid digestion, and cold vapor atomic fluorescence spectrometry Au trap sampling, cold vapor atomic absorption spectrometry-based real-time, portable analyzer
habitable environment of the space shuttle (F147), nitro-PAH from workplace air contaminated by diesel engine exhaust (F148), and hydrofluorocarbon levels in buildings that had refrigerant leakage (F149). Lead contamination of indoor air has been the effort of several publications. These include a study where dust collecting methods (a wipe and two vacuum methods from predetermined areas) were used in 205 homes collecting dust for Pb analysis (F150) to set a standard for lead-contaminated dust. Analytical results of Pb obtained from a wipe and a cyclone dust collecting methods (F151), a direct Pb and Fe analysis of contaminated carpet surfaces using a portable XRF spectrometer (F152), and adhesive tapes sampling of house dust followed by XRF analysis (F153) were published. The impact of heavy metals such as Cd, As, and Sb from ETS on indoor air quality was evaluated using filter sampling and Compton suppression NAA (F154). Other microenvironment air studies include the particle size distribution analysis using SEM in a wool textile mills (F155), sampling and AAS analysis of Ni in workplace air (F156), and the determination of Th and W air concentrations in the manufacturing process of discharge lamps using direct R-spectrometry and filter sampling followed by NAA method (F157). Air Emissions from Waste and Waste Sites. Similar to the last review, there were fewer publications related to this section’s title. Publications related to emissions from Miscellaneous Sources of the Fixed Sources section were therefore combined in this section. Methods for the analysis of landfill gas were developed for the analysis of vinyl chloride and dichloroethene using vinyl bromide as an internal standard (G1) and for an automated 260R
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F109 F110 F111 F112
F113 F114
F115 F116 F117
F118 F119 F120
thermal desorption GC/MS system for the analysis of 125 VOCs (G2). VOC emissions from a municipal sewer interceptor (Austin, TX) were analyzed for benzene, toluene, xylene, ethylbenzene, and tetrachloroethene. Emission rates of aromatic VOCs were calculated and compared with those available data from four large southern Ontario operations (G3). A GC/ICPMS method was developed for the analysis of Cd, Sn, Hg, Sb, Bi, and Pb in landfill and sewage gases (G4). Field sample validation showed the sensitivity for Cd, Sn, Hg, and Pb was at the nanogram per cubic meter level and was at the milligram per cubic meter level for the rest of the targets. Accidents and Emergencies. Fourteen publications discussed topics related to this section and are summarized in three categories: identification of pollutants from volcano eruption (H2H4), monitoring of fallouts from Chernobyl nuclear facility (H5H8), and the effect of the Kuwait oil fires (H9-H14) on the environment. Eckardt presented a direct postaccident atmospheric pollutant sampling system required by the German Reactor Safety Commission to acquire information on the condition of the core and on potential hazards to the environment (H1). Jaeger presented data obtained from a three-year LIDAR study of Mt. Pinatubo since the mid-June 1991 eruption. These data form the basis for aerosol extinction, mass, and surface area (H2). Using NAA, real-world samples from volcanic gases at 269-635 °C were sampled and analyzed for Cl, Br, I, As, Sb, Se, Te, and Hg (H3). Using XRF, composition, crystal SiO2 structure, and particle size from the eruption of Hudson Volcano (Argentina, August 1991) was obtained and compared with those from the Lonquimay (Chile, 1988) and Mt. St. Helens (United States, 1980) (H4).
Table 7. Monitoring of Chernobyl Fallouts and Kuwait Oil Fires analytes hot particles such as graphite, UO2, and zirconium carbide 90Sr and 238,239,240,241Pu 235,238U, 239Np, 99Mo 89,90Sr
SO2, CO, H2S, CO2, NOx, partially burned hydrocarbon/metals TSP, soot, organic carbon, SO42-, Cl-, SO2, CO, CO2, NO2, B[a]p PM-10 and suspended particulates Ni, V, dibenzo[a]pyrene U
Pb, Ti, Zn
methods/comments Chernobyl Fallouts Raman scattering spectroscopy
H5
deposition samples from 11 stations in Japan were measured to clarify environmental effects of the long-lived Chernobyl activities neutron activation analysis of hot particles from the Chernobyl region colliner reasonance ionization spectroscopy analysis was developed and applied to the air analysis of 89,90Sr at a 100 ppt sensitivity Kuwait Oil Fires real-time measurement in May 1991 with data compared to those measured before the fire air pollution monitoring was done from April 28 to May 5, 1991; relative low concentrations for SO2, CO, NO2, and B[a]p measurement during the Kuwait oil fire revealed a TSP value of > 340 µg/m3; TSP values can be correlated to PM-10 data via linear regression analysis TSP and PM-10 filter samples were collected from May to December 1991; analysis was done on these filter samples and archieve samples collected in 1982 ICPMS analysis of U in soil and particulate samples were analyzed; U concentration in particulate (1.4 µg/m3) was more than double of those in soil (0.7 µg/m3) and decreased to about 1 µg/m3 in 1993/1994 Winter ICP analysis of particulate and PM-10 samples collected during the Kuwait oil fires
Analytes and methods/comments used to monitor fallouts from the Chernobyl nuclear facility and the effect of the Kuwait oil fires are summarized in Table 7. Atmospheric Chemistry, Transport, and Deposition. (a) Wet Deposition, Including Rain, Snow, and Fog. The performance characteristics of an automated wet deposition collector were examined, and its effect on computed annual deposition was discussed (I1). Optimization of parameters used in solid-phase extraction for the sample preparation of precipitation PAHs was developed and validated using real-world samples (I2). Several investigations revealed that the concentration of organic compounds in fogwater would have been higher than that predicted by Henry’s law constant. An adsorption mechanism was used to predict/explain this phenomenon and supported the theory that surface adsorption may be the reason for the higher than expected enrichment (I3). Monitoring of inorganics in wet deposition include the publication of results obtained from a National Atmospheric Deposition Program pilot test for metal in a precipitation (Mg, Cu, Cd, As, Pb, Zn) sampling method (I4); studies of the solubility of polyvalent cations (Mg, Ca, Fe, Mn, Zn, Al, Cd) in fogwater at an urban site (Strasbourg, France) (I5). ICPMS of precipitation samples collected at a Norwegian background site was analyzed for trace elements and correlated to anthropogenic activities (I6). Analysis and temporal variations of trace metals in precipitation at an Atlantic station also showed a high correlation for the anthropogenic metals Cd, Cu, Ni, Pb, and Zn (I7). Dissolved chromium pollution in rainwater and surface water in mid-Wales was monitored during the mid-1980s and showed general improvements in emission controls for U.K. industry (I8). Electron microscope analyses of insoluble components in acid rain samples collected at Guilin, China, found a total of 12 elements: Ar, Mg, Al, Si, P, S, Cl, Ca, Fe, Ni, and Cr (I9). Capillary zone electrophoresis methods for a single rain drop (10-9-L range) sample analysis was developed for cations, anions, aldehydes, and mono- and dicarboxylic acids (I10). Application of a γ-ray detector for in situ measurement of 137Cs radioactivity in snowfields and glaciers was developed (I11).
refs
H6 H7 H8
H9 H10 H11 H12 H13
H14
A laser-excited atomic fluorescence spectrometric analysis of Bi in Greenland snow was done (I12). (b) Dry Deposition. Using ICPMS, a method was developed for the measurement of 99TC in dry depositions (I13). Field evaluation of a modified Swedish IVL (The Swedish Environmental Research Institute) passive Hg deposition monitor was done (I14). A critical field evaluation of three Hg measurement methods was reported at a site in north-central Wisconsin (I15). (c) Atmospheric Chemistry. UV spectra of tert-2-hydroxycyclopentyl-1-nitrate, 2-oxocyclohexyl-1-nitrate, and tert-1-methylcyclohexyl-1,2-dinitrate and their reaction rate coefficients with OH radicals were determined in synthetic air, and estimates of their tropospheric lifetimes were reported (I16). Sources and reservoirs of FO, ClO, BrO, and IO, especially their precursors (I17), and rate constants of reaction of indole, quinoline, and isoquinoline with radicals of OH, NO3, NO2, and O3 were measured along with a detailed discussion of their possible reactions and fate in indoor and atmospheric environment (I18). Flash photolysis resonance fluorescence measurements of reactions of CH3CF3 and CHF2CH2CF3 with OH radical, their reaction rate constants, and their estimated atmospheric lifetimes were reported (I19). The infrared band intensities of CF4, C2F6, C3F8, C4F10, C5F12, and C6F14 were measured and relative radiative forcing calculations were performed to determine the global warming potential of these species (I20). Biomonitoring/Bioassays and Microorganisms. This subsection has been rearranged to include publications where biological materials or living organisms were used as an integral part of environmental analysis, i.e., biomonitoring. Bioassays are the measurement of toxicity and/or mutagenicity of an isolated material screened, usually, by bacteria. Articles reviewed here are divided into three categories: biomonitoring, bioassay, and microorganism. (a) Biomonitoring. Chlorinated short-chain aliphatic hydrocarbons in pine needle samples collected in central Finland and trichloroacetic acids (TCA) in conifer needle samples in Finland were analyzed using purge-and-trap GC/MS (J1) and methylation of TCA and GC/NCI-MS (J2), respectively. Pine needles were Analytical Chemistry, Vol. 69, No. 12, June 15, 1997
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demonstrated to be inexpensive and natural sampling devices for atmospheric pentachlorophenol contamination at Saskatchewan (J3). Using airborne HCB and PCB concentrations from an expected source, treating concentrations of PAH, HCB, and PCB in mosses and humus as short-term and long-term exposure indicators, respectively, atmospheric exposure of coniferous forests to PAH, HCB, and PCB was studied in central Sweden (J4). Distributions and concentrations of OCs, coplanar PCBs, PCDD, and PCDF in spruce needle samples collected from Finland in 1991 and 1992 were studied using ICP-ECD and GC/ MS techniques (J5). Umlauf et al. carried out a nine-month study monitoring atmospheric SVOC deposition such as OCs and PCBs on spruce needles and determined the contribution of each pollutant to dry gaseous deposition, particle-bound deposition, and wet deposition (J6). A new method was developed and validated for the biomonitoring of OCs and PCBs in pine needles with superior precision (4-12% standard deviation) and good recovery (65-90%) (J7). Strategies in sampling and sample storage were discussed in large-scale plant biomonitoring surveys of trace element air pollution (J8). Cadmium and lead deposition in oak tree rings were analyzed around a Swedish battery plant and compared with the company and official emission statistics (J9). Ombrotrophic peat bogs were used to study temporal and spatial trends of heavy metal (Zn, Se, Sb, Br) air pollution in Norway. This study is useful to evaluate the impact of long-range atmospheric transport to different parts of Norway (J10). Using lichens and tree foliage, vanadium contamination near three oil-fired power plants in eastern Canada was monitored and the result reported (J11). A 12-month study at eight Netherlands stations was carried to determine the accumulation factors for Co, Se, and Zn in lichen and the possible uptake mechanism of deposition pollutants in lichen (J12). Sampling of lichen and moss species for trace elements analysis (Cd, Co, Cr, Cu, Mn, Ni, Pb, Ti, V, Zn) was discussed as different parts of the plant will result in different concentration information (J13). Plutonium concentrations in lichens collected from Rocky Flats environments (J14), trace metals in lichens, moss, and pine needles at Franz Josef Land the Kola Peninsula and in the Tver region (Russia) (J15), and deposition of heavy metals in moss around an iron smelter complex were reported (J16). (b) Bioassays. In situ monitoring of the genotoxicity of gaseous emissions from a closed landfill site and incinerator using the Tradescantia-micronucleus and Tradescantia-stamen-hairmutation bioassays was carried out (J16). Using Salmonella typhimurium forward mutation assay, the mutagenicity of urban organic aerosols (source specific) was compared with that collected from ambient samples. Results obtained for the Los Angeles area showed that the mutagenicity of the source composites and ambient samples were of the same magnitude (J17). (c) Microorganisms. GC/MS quantitation of muramic acid, a marker for bacteria peptidoglycan, from dusts collected from hospital air conditioning intake systems (which filter outdoor air and recirculated indoor air) and dusts from secondary room filters (which filter primarily indoor air) was used as a measure of bacterial contamination (J18). WATER ANALYSIS APPLICATIONS General Comments. As with the last review, the scope of this section has been limited to the analysis of trace pollutants in 262R
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environmental waters. This review does not include general methods for the assessment of water quality or analytical techniques for the determination of nitrates, nitrites, ammonia, dissolved gases, conductivity, or pH. A review of these subjects is found in the Water Analysis review in this issue of Analytical Chemistry. Reviews and Articles of Broad Interest. Reviews concerning the design of experimental measurements and analytical methods (K1) and modeling the transport (K2) of pesticides were published. National standards for pesticides in water, sediment, and aquatic biota, including United States, Canadian, and WHO standards and regulations, were reviewed with 109 references (K3). Many methods to determine volatile organic compounds remain of interest (K4). Developments in PCB analyses (in water) over the past 10 years were presented (K5). Trace elements in oceans, with 209 references, (K6) and lakes, with 152 references, (K7), including analytical methods used for their determinations, were reviewed. GC continues to be a standard method for the analysis of organic compounds. GC coupled with on-line sample enrichment and large-volume injection (K8) and with solid-phase microextraction (K9) were reviewed. GC and LC were reviewed, with 249 references, for the determination of polar pesticides (K10). Several discussions of LC/MS were written, including analyses of pesticides (K11), hazardous waste leachates (K12), and surfactants and their metabolites (K13). Anodic stripping voltametric titration for the study of trace metal complexation was described (K14). Suppressed ion chromatography was used to analyze low concentrations of anions in the presence of high concentrations of matrix ions (K15). Ir in natural waters was used as a tracer of extraterrestrial material (K16). Methods to study the speciation of organotins were reviewed with 200 references (K17). Surface Water, Rivers, and Lakes. (a) Sampling Techniques for Inorganics. Strategies of sampling, fractionation, and analysis of natural waters were reviewed with 152 references (L1). The effect of river transport characteristics on contaminant sampling was studied (L2). SF6 and 3He were used as tracers to determine longitudinal dispersion in rivers (L3). The effects of four different filter membranes on concentrations of 28 “dissolved” elements in five matrices were reported (L4). A brief (16 references) review of sample storage and preservation was presented (L5). Solid phase techniques to preconcentrate metals were reviewed (85 references) (L6). (b) Determination of Inorganics. Metal speciation remains of interest; the speciation of Sb (L7) and Se (L8) has been reviewed. An automated ion-exchange system coupled directly with a flame AAS was used to study Cr speciation (L9). The speciation of Fe and Mn was studied with electron spectroscopy (L10). Spectroscopy continues to be an important technique for the determination of inorganics. Cr(VI) was determined indirectly based on its reaction with the iodide ion; the absorbance of the complex of triiodide ions and hexadecylpyridinium can be measured to detection limits of 10-100 ppb (L11). P and Si, at low ppb concentrations, were complexed and determined by absorption spectroscopy (L12). Tl was extracted as a chlorothallate ion-pair complex of a cationic surfactant and determined at concentrations of 20 ppb by complexation with Brilliant Green (L13). Brilliant Green was also used to complex I2Cl- to determine 4 ppb iodide in water (L14). Atomic absorption
spectrometry was used to determine ppt concentrations of lead (L15). Electrothermal AAS was used to determine Cr in water with detection limits of 30 ppt (L16). Hg, at a detection limit of 0.1 ppt, was determined by an automated cold-vapor/gold amalgamation atomic fluorescence method (L17). A total of 3.7 nM Al was determined by flow injection analysis followed by fluorescence detection (L18). Laser-excited atomic fluorescence spectrometry was used for the direct detection of Tl and Pb in waters; detection limits were
