Anal. Chem. 1995, 67,221 R-255R
Environmental Analysis Ray E. Clement*
Laboratory Services Branch, Ontario Ministry of Environment and Energy, 125 Resources Road, Etobicoke, Ontario, Canada M9P 3V6 Gary A. Eiceman Department of Chemistry, New Mexico State University, Las Cruces, New Mexico 88003
Carolyn J. Koester Analytical Sciences Division, Lawrence Livemore National Laboratory, Livemore, Califomia 94551 Review Contents
General Reviews Air Analysis Applications Reviews Fixed Sources Mobile Sources Ambient Air Air Emissions from Waste and Waste Sites (Landfills, Wastewater) Accidents and Emergencies Atmospheric Chemistry, Transport, and Deposition Biomonitoring/Bioassays Miscellaneous Air Analysis Applications Water Analysis Applications General Comments Reviews and Articles of Broad Interest Surface Water, Rivers, and Lakes Groundwater, Wells, Reservoirs, and Springs Drinking Water Seawater and Coastal Waters Municipal and Industrial Wastewaters Landfill Leachates, Sludges, Waste Sites, and
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Biomonitors, Bioassays, Biological Sensors, 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 Quality Control, Standards, and Data Analysis Toxicity Testing, Biomonitoring, and Bioindicators Radionuclides
Miscellaneous Applications Technology and Analyte Cross-Reference
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This review covers developments in applied environmental analytical chemistry from January 1993to October 1994, as found in the Chemical Abstracts Service CA Selects for Gas Chromatography, Mass Spectrometry, Inorganic Analytical Chemism, and Pollution Monitoring. Some 20 OOO abstracts were reviewed to select the ones included here. Because reviews of Industrial Hygiene, Water Analysis, Air Analysis, and Pesticides also appear 0003-2700/95/0367-0221$15.50/0 0 1995 American Chemical Society
in this volume, we have excluded most references to severaltopics that are well-covered in these other reviews. This includes the following: pesticides determination,general air and water quality parameters, inorganic gases, most greenhouse gases, workplace monitoring, guidelines and regulations, risk assessment, modeling, human levels, commercial products, and food. Indoor air, which was excluded in the previous review of this series (AI),has grown in importance and is included this year. We emphasize the determination of trace organics and trace metals in real environmental samples. Therefore, we have also eliminated most references to applications where only artificial samples are tested. Where several references to similar applications are reported, or where a single group has contributed several publications to an ongoing line of research, we have endeavoured to cite only one or a few we consider to be the most significant. As before, the review is organized by matrix rather than analyte or method used. GENERAL REVIEWS There were many reviews related to the environmental analysis area. A test method overview of field testing methods was presented by Holcombe 0.A guide to environmental sampling was presented (A3). Sample preparation by using solid-phase extraction (SPE) was the topic of a recent symposium (A4,and matrix solid-phasedispersion was discussed along with SPE and supercritical fluid extraction (SFE) as improved alternatives compared to classical extraction methods for the determination of chlorinated pesticides in aquatic samples (As). Three large reviews of SFE methods as applied to environmental analysis have appeared (A6-A8). General sample preparation for GC FT-IR analysis was reviewed by McClure (AS). Specific analyte methods reviewed include the use of enzyme immunoassays for pesticides (AM), liquid chromatographymethods for N-methylcarbamate pesticides (All),LC/MS for polar pesticides (Ala,and the use of coupled chromatographicsystems (Al3)and thin-layer chromatography (A14for pesticides. Methods for herbicides in environmental samples were also reviewed (Al5). Reviews of the determination of polycyclic aromatic hydrocarbons by liquid chromatography (AI@ and in the field (AI 7) have appeared. Recent advances for the determination of polycyclic aromatics and fullerenes (Al8) and of the benz[clacridines (AD)in the environment have also appeared. Other reviews have focused on the determination of chlorinated aromatic pollutants such as the chlorinated dioxins (A20, A2l) and PCBs (A22). Sikkonen reported on the environmental analysis of chlorinated aromatic thioethers, sulfoxides, and sulfones W3). Analytical Chemistry, Vol. 67, No. 12, June 75,7995 221R
Reviews for the environmental determination of inorganic species uranium include fluoride 0 , organometallic compounds and lanthanides by kinetic phosphorescence analysis (AZ6), and total arsenic and arsenic compounds by using electrochemical methods 0 . Gas and liquid chromatography and chromatography/mass spectrometry methods are still among the most important for environmental analysis applications. A review by Grosser discussed chromatographicmethods as applied to major monitoring programs driven by US.regulations (A28). The use of GC with photoionization and electron capture detectors for field screening of semivolatiles was reviewed by Driscoll (A29),and a recent book was dedicated to the use of GC for environmental analysis (430). Environmental analysis by using gas and liquid chromatography was also reviewed by Grob (A31). Reviews on the coupling of LC and GC (A32),and the use of diode array detection in HPLC (A33) for environmental applications have also appeared. Reviews on coupled chromatography/mass spectrometry systems for analysis of environmental samples include the use of LC/MS ( 4 3 4 , chemical ionization MS (A35), membrane inlet mass spectrometers (A36), and field mass spectrometers (A37). The use of external and internal standards (A38) and isotope dilution mass spectrometry (A39) have also been reviewed. Reviews of the determination of trace metals and other inorganic species in the environment have also appeared. Atomic spectrometry methods for the environment were reviewed in an extensive article by Cresser (A40). Tsalev discussed a decade of development of electrothermal atomic absorption spectrometry (A41). Problems and trends in ultratrace elemental analysis were reviewed by Toelg (A42),while Evans discussed interferences in ICPMS (A43). Other inorganic methods reviewed included advanced electroanalytical techniques (A44, activation analysis (A45), ion beam analysis (A46), and sampling and sample preparation for EDXRS analysis (A47). Other reviews on environmental analysis applications include the use of chemical transducers based on fiber optics (A48), electrochemical sensors (A49),gas sensors (A50), and luminescence c451).Applications based on monoclonal antibodies (A52) and laser-based fiber-optic immunosensors (A53) were also reviewed. Analytical methods for hazardous waste were discussed in other reviews (A54,A55). AIR ANALYSIS APPLICATIONS
In this section, discussion is centered on the development and application of analytical techniques for the determination of toxic and hazardous materials in air. Treatment has been restricted in this review to organic compounds and metals or ions with some toxicity to the exclusion of non-metal gases, acid gases, and so forth. The organization is the same as the prior review with a few minor adjustments: fugitive emissions have been consolidated with the Industrial heading in Fixed Sources, the section on Combustion Sources has been combined with Incinerators,Stacks, and Residues (further subdivided by fuel stock), and the Miscellaneous Air Topics has been shortened with the removal of nonmetal oxide gases and with the integration of subjects into the main headings. The subject of pathogenic organisms in air was added. The section on Ambient Air has been reorganized to stress actual field studies and the section on methods development is 222R
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presented in tabular form. Aerosols have been included this year when the emphasis has been on heavy-metal content of the samples. Reviews. Thirty-six reviews on analysis of atmospheric environmental samples ranged over seven major subcategories including the following: sample collection, radon measurements, airborne microorganisms, site-specific assessments, methods of analysis, field instrumentation, and composition of aerosols. The subject of collecting samples of air was reviewed with respect to particulate sampling technology @I), consideration of sampling specifics for compliance to OSHA standards (BZ),and sampling indoor atmospheres in workplace air monitoring (B3). A review in sampling air was also prepared for the specific techniques of diffusion or passive samples where the emphasis was on adaptation of workplace monitoring to environmental venues (B4)and on moisture control with sorbent methods (B5). Analysis of carbonyl compounds, which can be challenging in terms of reactivity and losses during sampling, was reviewed in terms of the initial sampling event where derivatization techniques were used to trap carbonyl constituents and prepare analytes for later liquid chromatographic determinations (B6). Other specific pollutants that were subjects of reviews were radon (B7,BS), airborne microorganisms (B9, B10), and aromatic hydrocarbons in indoor air (B11).In the last article, methods for time-averaged determinations of volatile aromatic hydrocarbons using charcoal traps with gas chromatography were discussed. Reviews were also created to describe aspects of air analysis at specitic sites, including emphasis on monitoring plans at hazardous waste disposal facilities (BIZ). Others were interested in the technologies suited for continuous monitoring of emissions of toxic and hazardous substances from incinerators (B13) where mixed waste (Le., nuclear and organic chemicals) was the feedstock. A general review of odors was directed toward industrial odors and control of odors (B14). Substantial interest was shown in reviews of actual methods of analysis for indoor air monitoring of environmentalcarcinogens (B15),organic vapors (B16),and tracer gases for ventilation studies (B17).Noteworthy reviews from India (B18)and from China (B19)were used to describe modern instrumental methods of atmospheric pollution analysis for toxic compounds. The specific method of GC/MS with Tenax-GC for detecting organic atmospheric pollutants included discussion on principles, reagents, hazards, and data reduction (B20). Methods for non-methane hydrocarbons in ambient air were reviewed (B21) as were procedures for data treatment in air monitoring (B22). Field methods where analytical capabilities are removed from the laboratory to sites of environmental pollution are becoming compelling as traditional approaches become economically and logistically fragile. Reviews were given for field-deployable gas chromatographs (B23),for multiple gas monitors (B24),and for the realities of conducting analytical studies in field venues (B25). Extensive coverage was given in reviews of aerosols (B26B33). Especially relevant here was the review of aromatic isocyanate sampling (B31), chemical composition of aerosols (B32),and trace elements in indoor/outdoor dust (B34). Fixed Sources. In the category of fixed or stationary sources of airborne environmental pollutants, a broad range of trpes and kinds of sources encompasses industrial to natural sources. A section on incineratorshas been featured with further classification based upon feed stock. The discussion in this section has been
Table 1. Industrial and Fugitive Emissions analyte
method
PAHs vocs
GCNS APCI-MSMS
polychlorinated phenols
GC-ECD
C5-C 2 hydrocarbons VPCS
GC with cyrogenic sampler long-path FT-IR
CF4 30 elements Cr(V1) radionuclides trace metals
FT-IR neutron activation analysis LAMMA a-spectrometry X P S and SIMS
industry or comment
ref
PAHs arise from coal tar pitch used as a binder in Soderberg (Quebec, Canada) anodes vapors arose from an activated carbon recycling plant and from a steel casting foundry near Beaver Falls, PA from air near pulp-bleaching plants. Samples collected with XAD-2 and derivatized in pretreatment field studies near a petroleum industry site detection limits of 100pg/m3 for aromatic hydrcarbons near a automobile industry and 10 pg/m3 for butyl acetate aluminum smelting plant ambient air dust particles from around a cement factory in central India in dust emissions from iron and steel industry in dust clouds generated in a uranium mill in airbome dust from a cast iron foundry
c1 c2
presented by pollutant class, organic compounds or metals. Fugitive emissions have been included in the section on industrial sources since the emphasis on fugitive emissions has originated, in general, from industrial sites. Industrial and Fugitive Emissions. The range of industries examined in studies can be seen in part in Table 1and extends from cement factories to uranium mills (CI-C15). The range of analytes is also broad, running from chromium in particles in an iron industry (C13) to odors from a petroleum industry site (C4). Noteworthy was a field method using tandem mass spectrometers with direct air sampling for odors from an activated carbon recycling facility and from a steel casting foundry (C2). This paper and a number of others originated with a annual meeting of the Air Waste Management Association and appeared as proceedings, included here due to the importance of the kinds of studies reported. Several reports involved industrial site monitoring without actual field data and these included accounts of field experiences with EPA method 301 (C5). Elsewhere, construction sites were recognized as physically large point sources for PAHs when capped with asphalt (CS). The hexenes potentially emitted into ambient air from a gasoline or filling station were characterized by using ion trap mass spectrometry (C7). A geographicallylarge source of pesticides in the air of southern Ontario was identified as land masses in the southern United States (C8). An annual cycle of warming during the summer months was attributed for increased vapor pressures for polchlorinated bornanes or camphenes, deposition in southern Ontario, and a plan for sector sampliig for VOCs near an industry (C9). Miscellaneous Stationary Sources. Miscellaneous stationary sources of airborne organic pollutants included volatile organics in emissions and soot from a hazardous waste burner (CIS),polar polycyclic aromatic hydrocarbons in effluents from brown coalfired residential stoves (C17), and PAHs from open burning of scrap tires (C18). In all of these methods, GC or GC/MS was employed for chemical characterization of the emission samples. Fluorinated PAHs were proposed as internal standards for quantitative determinations of PAHs in chimney ash samples (C19). In an EPA report, section 3.17 of method 25 for total gaseous non-methane organic compounds using GC-FID was described (CZO). A catalytic flame ionization detector was explored as a prospective modfication to EPA method 25 (CZ1). Metals were the interest of other studies regarding miscellaneous reports and many of these involved experimental assessment of governmental procedures based on actual field trials. For example, EPA method l O l A was applied to the determination of Hg vapors in sewage sludge incinerators (C.22) while the effects
c3 c4 c10 c11 c12 C13 c14 C15
of ammonia on Hg determinations were shown not to affect recoveries in the same method (C23). A last pollution source in the miscellaneous category was a welding unit where vapors and fume dust near to the welding site were characterized for Fe, Mn, Cu, and Ti (C24). Incinerators, Stacks, and Residues. Municipal incinerators are those in which the fuel or feedstock principally originates from domestic waste including paper, wood, kitchen scraps, and so forth. Interest in the atmospheric pollutant burden from the stack effluents arises from several special classes of chemicals such as the polychlorinated dibenzo-pdioxins (PCDDs), the polychlorinated dibenzofurans (PCDFs), and the PAHs identified in stack gases and fly ash in the late 1970s. The proximity of such incinerators to densely populated regions has increased the concerns and management of such incinerators. Consequently, large efforts have been devoted through the years to the analytical environmental chemistry of these and this continues to be true even in the years bracketed for this review. The PCDDs were the subject of at least 11studies (C25435) as shown in Table 2. Noteworthy are methods based upon rapid, simple GUMS (C32) and at the other extreme HRGC/HRMS with peak monitoring (C31). However, the issue of sampling continues to require attention as shown in several articles (C25, C23, C28, C29). Some effort was given to sample preparation (C34) while others directed efforts to the determination of toxicity equivalents (C35). The second chemical class of importance in incinerator effluents were the PAHs and other aromatic hydrocarbons where GC/MS was again the method of choice (C36-C40). However, some innovations for continuous monitoring, not possible with conventional GC/MS, were described for PAHs in coal stack ash using optical probe methods (C38). Biotoxicity directed characterization of fly ash from coal showed the PAH fractions as toxicologically active (C39). Continuous monitoring was also the interest of a methods development report where a laser-based time-of-flight mass spectrometer was used to monitor stack gases for 13 hazardous species (C41). Other chemicals in flue gases subjected to careful analysis included chlorinated aromatic sulfur compounds (C42), nitroPAH in ash (C43), small chlorinated hydrocarbons (C44, and chlorinated benzenes (C45). In contrast to the strong interest in organic compounds in emissions from municipal incinerators, few reports were found on the subject of metals, especially toxic metals, in the flue gases from such incinerators. The interest in metals in such effluent or flue gases was exclusively for mercury (C46-C49). Some work was concerned with examining standard EPA methods (C467, and Analytical Chemistry, Vo/. 67, No. 12, June 15, 7995
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Table 2. Analysis of Municipal Incinerators Effluents for PCDDs and PAHs analyte
comment
ref
PCDDsPCDFs
methods for sampling waste gases with two-stage filtration showing the low levels of analytes in ash from coal-buming works potential artifacts that arise during sampling comparative sampling trials in the UK to assess precision of samplers long-term (4 weeks) sampling of flue gases levels at several points within a solid waste incinerator high-resolution GChigh-resolution MS method for mass peak profile method to reduce interferences rapid method with rapid simple sample preparation for G C N S toxicity correlations between pentachlorobenzene and heptachlorobiphenyl and PCDD/F report of improved precision with supercritical fluid extraction of fly ash vs traditional Soxhlet extractions estimate of doxin like toxicity using theoretical model in soot samples produced by combustion of benzene, toluene and others at 590 "C with GCMS screening of products ultrasonic extraction recovery of PAHs from coal stack ash shown to yield lower recovery than Soxhlet extraction innovative optical approaches to continuous monitoring of stack gases for PAHs toxicity directed analysis with toxicity localized in PAH fraction generation of PAH from combustion studies with alkylated benzenes and ethers
C25 C26 c21 C28 C29 C30 C3 1 C32 c33 c34 c35 C36
PAHs
C31 C38 c39 C40
Table 3. Methods for Automobile Emissions Automobile Exhausts carbonyl sulfide in automobile emissions aldehydes in automobile exhausts high-resolution GC characterization of reaction hydrocarbons in engine out-exhaust aliphatic amine emissions speciation hydrocarbons by carbon number groups Diesel Engine Exhausts TMS-derivatized polar extracts of diesel particulate matter (PM) polycyclic aromatic hydrocarbons in diesel PM personal diesel particulate sampling unit time-of-flight mass spectrometry for anthracene on diesel soot 1-nitropyrene in diesel particulate matter 2-amino-l-methyl-6-phenylamindazo[4,5-b]pyridine in diesel PM
others were interested in creating new approaches to sampling and monitoring stack flue gases for Hg (C47, C49). These latter two works involved capturing the mercury on gold-coated wires that were placed into the flue stream. On the whole, the principle constituents sought for emissions from coal-fired incinerators were trace metals, and the methods used were based upon atomic adsorption spectrometry (M), neutron activation, particleinducedX-ray emission (PIXE) analysis (C50-C52). Direct solid sampling with M was matched favorably to NISI materials for Ag, Cd, Cu, and V in coal fly ash (C50) while in an alternate approach digestion using concentrated mineral acids was used for sample pretreatment prior to AAS measurements (C51). Cadmium was selectively determined in several matrices including coal fly ash using chelation-based methods (C52). The final methods were directed toward sampling of flue gases (C53) and size fractionation of aerosols from coal combustion (C54). Nuclear Plants. As with the last review, little attention was given to nuclear plants as fixed sources of pollution and only a few reports on related airborne environmental analysis were found. In one report, the release of transuranium elements in airborne effluents from a nuclear power plant at Jaslovske Bohunice in Czechoslovakia showed annual discharged activities of five elements between 9 and 44 kBq (C55). In a second report, plutonium-241was compared to americium-241in air and deposition samples taken at Neuherber, near Munich, as fallout from Chernobyl incident (C56). Natural Sources. Key interests with natural sources were associated with isoprene and terpene emissions from trees. Isoprene was detected in the sub-ppb levels in oak forests of northeastern United States with a detection limit of 300-500 ppt with a reduction gas chromatograph (C57). The sampling of 10 224R
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D1 D2, D3 D4 D5 D7, D8 D9 D10 D12 D13 D15
D14
monoterpenes was refined and then applied to air sampling in European spruce stands (C58). Monoterpenes were also the analytes for sampling studies in a Scots pine forest in central Sweden where nine terpenes were separated and identified by GC/MS (C59). Mobile Sources. Mobile sources, particularly vehicles with internal combustion engines, have been examined during the last three decades for chemical composition of exhausts. There has been a sustained level of interest in this subject, and as might be expected, the studies have been narrowed to highly specific questions as the survey-level studies were completed. Various mobile sources were targeted for chemical characterization of airborne pollutants and these included exhausts from combustionbased engines with gasoline (01-08) and with diesel fuels (09019,jet aircraft engines (017,018), and cigarettes (019,020). A few true environmental studies (021-023) were reported, and a report largely devoted to methodology was published (024). Some of these are shown or summarized in Table 3. Though some interest existed in broad chemical screening for hydrocarbons (04, 0 7 , 08), characterization of exhausts for spec& chemicals or chemical classes was pronounced (see Table 3); noteworthy was the attempt to characterize amines in emis sions from automobile exhausts (05)and polar components in diesel particulate matter (09). Interest in analysis of emissions from jet aircraft engines was devoted to sampling aerosols (016) which, once collected, could be chemically characterized. An alternate approach based upon real-time characterizationswith a mobile unit is noted here with emphasis on the sampling step rather than chemical characterizations (017). Cigarettes can be regarded as a type of mobile airborne pollutant source, and tobacco smoke condensate was analyzed in large part as an indoor air pollutant. Chemical interest was
Table 4. Organic Compounds in Urban Locations analyte C2-Clo nonmethane hydrocarbons PAHs 25 targeted VOCs aliphatic and aromatic hydrocarbons formaldehyde and acetaldehyde chlorinated PAHs 39 pesticides hydrocarbons PCDDs, PCDFs, PCBs, and PAH 24 selected VOCs C5-C12 hydrocarbons
location or comment
ref
Lost Mountain, GA, near Atlanta, GA, where isoprene was seen as the dominant hydrocarbon at the semiurban site monitoring of vehicle emissions as effluent at traffic tunnels benzenes and substituted benzenes were found most often in Chicago, Houston, Seattle, and Boston over a 2 yr study GCMS study of ambient air aerosols in Barcelona for 108 constitutents using a GCMS procedure ambient air aerosols in Salvado, Bahia, Brazil contained 7-27 and 9-55 ng/m3 HCHO and acetaldehyde, respectively 2-D HPLC was used to isolate Cl-PAHs for GCMS determination. 1-Chloropyrene was -10 pg/m3 in streets and 40 pg/m3 in road tunnels broad screening of air in Kitakyushi, Japan found 23 pesticides in summer and 21 in spring changes in composition of samples of urban aerosols during storage exploited for analytical purposes survey study screenings at two California sites and locations in Denver, CO and Houston, TX field studies near a petroleum industry site were used to assess a cryogenic sampling system
El E2 E3 E4 E5
E6 E7 E8 E9 E10 El 1
Table 5. Metals in Urban Locations analyte
location or comment
ref
28 trace elements lead lead lead radon daughters hexavalent chromium
5 yr study in Milan, Italy, with sourcing of pollutant using PIXE X-ray fluorescence measurement of Pb sampled at three sites in Debrecen, Hungary, over 3 yr north suburb of Shanghai, China; samples taken for 3 yr near a Pb-Zn smelter In air near motorways in Nigeria by PIXE and EDXRF studies at Munich-Neuherberg, Germany, to measure 214Pb,%o, I3lI, and I3’Cs sampling of 25 industrial sites in Hudson County, NJ, where soils contain ore processing waste
E18 E19 E20 E2 1 E22 E23
directed toward heavy metals As, Cd, and Pb at toxicologically relevant concentrations (018)and Se (Dl9). No references were found on organic compounds in tobacco smoke, likely due to extensive studies in the 1960s and 1970s. In several studies, actual environmental atmospheric studies were made using mobile sources as targeted items and this was contrasted with either simple laboratory studies or undirected ambient air surveys. In this category of reports, biological inputs to air quality in the Los Angeles Basin were identified as a major source of small organic chemicals between April and July (020). In the Boston, MA, region, benzene, toluene, and xylenes (BTX) were examined using a automatic GC with concentrator and photoionization detector and BTX values were correlated with COZ well during rush-hour traffic (021). In Tokyo, Japan, brake friction was targeted as a source of phenolic resin concentrations in particulate matter as an indirect measure of asbestos (022). Methodologies were noted for tetraallryllead compounds in air (023)and mutagens including nitroazabenzo[alpyrenein airborne particulate matter (024). Ambient Air. This section is expanded and restructured from the last review. For example, the subject of data reduction in air analysis is included in this section rather than in the miscellaneous section (below) since most data reduction exercises occurred using actual ambient air monitoring studies. The section on sampling techniques is retained and has been divided into organic compounds versus inorganic compounds. A section on indoor air,an attactive prospective addition here with potentially redundancy with the review on Industrial Hygiene in this issue, was added but restricted to studies at nonindustrial venues. The section on monitoring was expanded to emphasize actual field measurement studies. This was further divided into organic versus inorganic analytes, each further divided into urban/ industrial versus nonurban or natural. Monitoring Programs and Actual Field Measurements. Several studies were reported where ambient air in urban centers was monitored for organic compounds, and these are summarized in
Table 4 (El-Ell). The studies, completed almost exclusively with GC or GC/MS methods, were directed toward volatile organic compounds including products of combustion processes, pesticides, and hydrocarbons from industrial activities. The constituents sought were in general found as might be expected in complex mixtures necessitating chromatographic methods. In contrast, studies with nonurban or natural atmospheric environments were directed toward biogenic materials such as terpenes with occasional interest in the intrusion of anthropogenic materials into nonurban zones. Terpenes (El2, El3), acetone (El4), dimethyl suEde, and bromoform (El5) were found in natural environments and involved, in one instance (El4), an airborne tandem mass spectrometer. A forest was used as a location for the identification of more than 100 VOCs that were identified or classified as natural or man-made in northern Europe, in the Mediterranean basin, and in the Himalaya region (El@. In rural locations in Germany, PCDDs and PCDFs were characterized in airborne particulate matter as a function of particle size, suggesting widespread distribution of such matter even to rural locations (El7). Analysis of air in urban and industrial settings for inorganics (El8-E23), principally metals, was accomplished using several methods as summarized in Table 5. As with the monitoring of organic compounds in air, the sampling method of choice for practical applications was high-volumefiltering of air with trapping and later analysis of the particles. A comparatively high level of interest was seen with metal determination in nonurban or natural locations and included the content of giant marine aerosols for ?I, Cr, Fe, and Ni (E24); transition metals in aerosols at the Brazilian Antarctic Station and at a biomass burning site in the Amazon basin (E25);metal ions in the auroral lower E-region (E26); and atmospheric aluminum in air at the French Riviera versus Pb, Cd, Du, and Zn and Saharan dust (E27). Sampling. The collection of samples may constitute, at this writing, the single most dif6cult technical issue in environmental analysis when laboratory-based analytical techniques are employed. The djf6culty arises from the interpretation of the findings Analytical Chemistry, Vol. 67,No. 12,June 15, 7995
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in view of inhomogenity of environmental systems, integration of sampling over time, losses of analyte during storage or chemical changes that may occur during or after sampling, and more. The level of interest then, is not surprising, in finding solutions to the collection of a representative sample that reflects the true composition of an atmospheric environment. The methods for organic compounds can be classified according to the principle of sampling and include cryogenic (E28-E34), sorbents (E35E49),passive or diffusion methods (E35-E59), and fractionators or denuders (E60-E68). Other reports involved studies on the influence of materials of containers with contamination of surfaces by PCBs scavenged from the atmosphere onto Teflon containers planned for water studies (E69). Field blanks were unexpectedly high during a study at the ppt level, and bottles could be made suitable with solvent washes. Tedlar bags were compared to stainless steel canisters which showed higher stability for samples and lower trip contamination than Tedlar bags (E70). A mathematical model was developed to describe losses of VOCs in stainless steel canisters and was tested using experimental results (E71). One alternative to sample storage is the use of grab samples (E72); however, vapor adsorption artifacts can occur during sampling in the instance of organic vapors (E73). Reactions during sampling can be exploited in the instance of reactive analytes with reactive adsorbents. For example, formaldehyde can be chemisorbed on glass filters impregnated with a hydrazine reagent (E74). Sampling of pollutants for the Clean Air Act Amendment was validated using method 301 (E75). The methods for sampling inorganic pollutants, mainly metals, are fewer in number and range than those for sampling organic pollutants. Filters for particulates were common (E76-E78) for airborne lead while various sorbents were evaluated for tetraalkyllead compounds (E79). Porapak and Tenax were favored over other sorbents on the basis of retention efficiencies which were 92 and 96%, respectively. Impingers were described to trap airborne hexavalent chromium in a three-stage configuration (E80). A pair of Warren Spring M-type samplers were used to determine reproducibility of field measurements for lead and particulate matter (E81). Radioactivity was largely restricted to zzzRn,where both charcoal canisters (E82,E83) and flow-through cells were described (E84). Data Reduction. Studies associated with data reduction spanned a broad range of interests encompassing data validation procedures for ambient air monitoring (E89 to the extraction of information from complex chromatograms (E86'). In the latter study, samples were classified from GC-FID chromatograms using pattern recognition, thus avoiding peak recognition and identifkation as necessary details for sourcing a measurement. The measurement of contamination (E87) and the role of controls in data reduction were discussed and defined in an attempt to standardize methods and terms. Apart from contamination, attempts were made to glean information from results using statistics when levels of specific pollutants were very low (E88). Multiplexed sampling with a continuous radon monitor was approaihed or treated using Monte Carlo simulations (E89). Methods. A large number of works are published yearly on the subject of method development where procedures, instrumentation, or techniques are refined and described without immediate demonstration of the methods in actual environments. Reports in which field monitoring occurred have been treated in 226R
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a section above; however, some methods, without immediate application, deserve mention in this review. This section is devoted to such reports and has been truncated in both scope and discussion; thus, this treatment should be regarded as a sampling of methods and not a comprehensive discussion. Tables are used as the principal means to summarize the field of study. Methods for organic chemicals were expansive and varied in keeping with the high volatility of many important chemicals and the environmental importance of such chemicals (E90-E135). A summary of the methods, divided into GC and GC/MS; E, HPK, and TLC; MS and MS/MS spectrometry and colorimetric methods; and sensors, is shown in Table 6. Several noteworthy trends may be gleaned from the table. In most methods, the state of the technology is well developed and procedures are being created for narrow applications to targeted chemicals. General procedures often already exist, and these reports seek to make methods free of interferences or complications not addressed by general methods. With exceptions, methods still remain rooted to traditional methods where samples are collected on-site and returned to the laboratory for analysis. Exceptions were seen in the section on MS and MS/MS where the emphasis was in moving the mass spectrometers to field-monitoring situations. The number and types of methods applied for inorganic substances are shown in Table 7 (E136-EI42) and illustrate a surprising lack of activity in this subject. Moreover, applications were largely directed toward analysis of airborne particulates. Indoor Air. Monitoring of indoor air is included in industrial hygiene in the instances when the subject is relevant to occupational hygiene. The topic was further subdivided into VOCs and semivolatiles. Interest in volatile organic compounds could be grouped into the subject of sampling methoddmaterials and field analysis with emphasis on identifying sources of vapors. Sampling by passive samplers was evaluated or characterized for aldehydes and ketone (E147), for VOCs (E148), for effects of long-term sampling (E149),and for total performance with two materials (E150). Actual monitoring exercises occurred with air in the space shuttle for hydrazines (E151)and for a well-ventilated building with an attempted link between occupant symptoms and composition of the local region (E152). This last study was aligned with current interest in the sick building syndrome, which also motivated three other reports. The VOCs emitted from PVC flooring were identified and monitored over time (E153). A major component was 2-ethylhexanol, which came from hydrolysis of esters in the glue. The tools to measure the contributions from carpets to air were described, were found to be reproducible within 12% relative error, and could be used to rank the emission properties (E154). The longevity of fumigants and odor additives was evaluated using two homes of diflerent age (E155),and the newer home showed higher retention versus the older home against time. Studies with semivolatiles included determinations of PAHs (E156) in indoor air and in air from homes and white-collar workplaces (E157).Pesticides and PCBs (E158-EI61) were also sought in samples from indoor air, and PCBs were linked to sealant material (E161). Procedures for chlordane based upon Tenax traps and selected ion monitoring by GC/MS was used for indoor and outdoor air in Japan (E162) and were rated at 5 pg limit of detection.
Table 6. Methods for Organic Pollutant Determinations analytes n-alkane hydrocarbons general screen of VOCs PAHs and derivatives of PAHs nicotine organobromine compounds bromoform, 1,1,3-tribromopropane nitrodibenzopyranone PCDDs and PCDFs sulfur-containing VOCs complex mixtures stable isotope standards PAH chlorinated PAH nitrated PAH azaarenes toluene diisocyanate cyanuric acid, trichlorocyanuric acid dimethyl sulfoxide dimethyl sulfone vocs bromobenzene-d5 as internal standard formaldehyde methyl nitrite vocs volatile chlorinated compounds isocyanate species benzene hydrazine, monomethylhydrazine nitrobenzene fluorocarbon perchloroethylene trace gas contaminants
ref
comments GC and GCMS capillary GC with FID methods comprised typically of sample prefractionation before GC analysis extensive sample precleanup for derivatives of PAH such as nitrated or chlorinated PAH method based upon capillary GC for separation of nicotine and minor alkaloid or packed column for determination of only nicotine GC method for seeking flame retardant compounds in air; 20 L sample volumes are required isomer-specific separations complete method directed toward practical monitoring of compounds in air based on GCMS use of adsorbent and inlet device high-speed GC with analysis times of 8-100 s and up to 950 theoretical plates description of stable isotope permeation tubes for on-line air enrichment with internal standard LC, HPLC, and TLC on-line LC/GC for PAH in air selective cleanup for PAH coupled LC/GC/MS for on-line cleanup, separation, and identification HPLC with electrochemical detector TLC method column chromatographic cleanup with TLC separation description of routine method based on micro-LC method with air sampling with PVC membranes MS and MSMS real-time monitoring by atmospheric pressure chemical ionization (APCI) mass spectrometry study of the feasibility of using an ion trap for atmospheric pollutants monitoring internal standard method for APCI-MSMS monitoring of air Spectrometry and Colorimetric Methods monitoring tape with hydroxylamine sulfate and methyl yellow real-time monitoring with nitrogen oxide indicating tubes with IR detection IR-based method for on-site analysis fiber-optic emission sensors based on atomic emission of chlorine chemiluminescent technique for general monitoring for all volatile isocyanates photoionization detector for on-line monitoring Electrochemical and Other Sensors Coulometric method intended for use with impinger solutions piezoelectric sensors metal oxide sensors quartz microbalance and calorimetric transducer multiple sensors with pattern recognition
E90-E94 E95-E98 E99-E102 E103 E104 E105 E106 E107, E109 E108 E l 10 e111 E112 E113 E l 14 E l 15 E l 16 E l 17 E118 E l 19 E120, E121 E122 E123 E124 E125 E126 E127, E128 E129 E130 E131 E132 E133 E134 E135
Table 7. Inorganic Methods analytes arsenic As, Fe, Mn Sb, Ni, V trace metals
Zn, Pb Be, Co, Cd, Pb
trace metals Cu, Cd, Ni, Co chemical pollutants review vocs
comments AAS hydride generation AAS method study of procedures for analysis of fly ash from power station microdigestion procedure for filters loaded with particulate matter method for indoor airborne particles dissolution method for impactor-based sampling ICP femtogram amounts of metals in individual airborne particles real-time detection of metallic aerosol concentrations Electrochemistry stripping voltammetry and ion-selective electrodes with AAS adsorptive cathodic stripping voltammetry electrochemical sensor catalytic electrochemical gas sensor
Air Emissions from Waste and Waste Sites (Landfills, Wastewater). This year there were few reports of activity in air analysis at or near waste sites, which is surprising in view of the pressing needs nationally and worldwide in hazardous waste site management and remediation. Prospective real-time air monitors at Superfund sites were rated or evaluated in terms of commercial availability, analytes, and technologies and ranged from GC or GC/MS to electrochemical systems (F1). Meteorological data were merged with remote sensing of VOCs during remediation of hazardous waste sites to form an alarm system for those downwind from the site (FZ). Field-portable GCs for
ref E136 E137 E138 E139 E140 E141 E142 E143 E144 E145 E146
analysis of ambient air for volatile organic compounds were evaluated under laboratory conditions for standard analytical performance features and then were tested later at the French Limited Superfund site near Houston, TX (F3). Elsewhere, interest was directed toward characterization of airborne substances for toxic metal content or radioactivity. Total and hexavalent chromium were determined by XRF in respirable soil particles from several contaminated sites in New Jersey (F4). Volatile metal species were determined in gases from municipal waste deposits via ICPMS ( F a . The results suggest a biogeochemical pathway for transport of metals including Si, V, As, Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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Table 8. Analysis of Rainwater analytes inorganic iodine AI
Cd, Cu, Pb, AI, Zn Na, Mg, Ca Fe, Mn,Cu, Ni, Pb, Cd particles alkali metals ’Be, I3II
comments
ref
method based on catalytic effect of I on thiocyanate ion oxidation by nitrite ions with LODs of 0.4 pg/L improved graphite furnace AAS method with data set for AI in rainwater at French Riviera ICP-emission spectrometry method for using ion exchange preconcentration micro-HPLC for analysis of individual raindrops comparison of AAS with anodic stripping voltammetry with reference and true samples light scattering sizing of colloid rainwater samples multivariate statistical analysis for source identification near Cubatoao, SP, Brazil assessment of long-standing paper collector network for radioactive contaminants
H6 H7 H8 H9 H10 H11 H12 H13
Sn, Sb, Te, Hg, Pb, and Bi from the soil to the atmosphere. A community radiation monitoring program near the Rocky Flats Plant near Denver, CO, for airborne radioactivity was described (F6)and was based on five separate monitoring instruments or weather instruments. Accidents and Emergencies. As in the last review, air monitoring during accidents or emergencies received little attention, presumably due to the unplanned or unscheduled nature of an emergency and the speed at which events can overtake systematic sampling and analysis. The fallout and environmental poisoning from the Chemobyl nuclear facility figured prominently in terms of 235U in soil particles as a source of dust (GI), of WSr in air filters in the late postaccident period using y-spectroscopy (G2), and of I4’Pm, and 137Csin air filters several years after the accident (G3). Other reports were not included here since the emphasis was on soil and water content in the region surrounding Chemobyl. Vehicle fires in traffic tunnels, a special type of emergency, were considered in terms of sampling strategies with a mixture of passive and active collectors (G4). The strategies were also considered in terms of personal protection and tunnel construction and were tested using a car and a subway train fire. Elsewhere, short-lived reactive species in air samples from structural fires were examined (GS). Atmospheric Chemistry, Transport, and Deposition. Wet Deposition, Including Rain, Snow, and Fog. Wet deposition includes the collection of airborne pollutants in condensed, rather than vapor, form within rain drops, snow, or liquid aerosols. The emphasis during the last few years was on the essential step of sampling,where attention was given to elementary questions such as mass losses and reliability of sampling. This falls into the overall category of representative collection of samples. For example, mass losses for trace elements to funnel surfaces was explored in samplers (HI) and for Hg in bottles used to contain samples (H2). The issue of chemical content of individual raindrops as a function of size showed that concentration decreased with increasing drop size (H3). A technique for pollution monitoring, though not for toxic metals or organic compounds, was noteworthy for the characteristics of operation with cloudwater at high and remote elevations (H4).Methods were described to collect and chemically analyze cloud condensation nuclei (CCN) and were suitable to isolate CCN from background aerosols (H5). Rainwater was the subject of several articles (H6-HI4) as summarized in Table 8. The range of topics included heavy metals in rain at Easter Island (HIO)and aluminum in rainwater at the French Riviera (H7).Chemometrics was applied to identify sources of trace elements in rainwater including smelter signatures and natural sources (H14).A few reports have been included in Table 8 on the strength of sampling or sample characterization without direct importance to toxic analytes. 228R
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Dry Deposition. The deposition of pollutants from a dry condition through particulate or vapor phases was examined versus wet deposition for polycyclic aromatic hydrocarbons (HI5) at two sites in northwest England, where a local point source could account for seasonal variations. A method based upon HPLC preparation of samples and GC/MS determination of 41 chlorinated aromatic compounds such as PCBs and PCDDs was evaluated (HI6).Results were presented for a 30 day sampling episode. The National Dry Deposition Network, established in the United States in 1986, was described though deposition was not measured but estimated for a limited number of chemicals, none toxic organic or heavy metals (HI7). Atmospheric Chemistry. The reaction of chemicals in the atmosphere is an essential facet for a complete understanding of the significance of findings from air analyses. For example, the transformation of malathion was followed for 9 days after an aerial application in California in 1990 (HI@. The dynamics and kinetics for the transformation from malathion to malaoxon via hydrolysis to diethyl fumarate were described. Work occurred in the area of photolysis of CF3H with Fz and 02 to form bis(trifluoromethy1) trioxide (HI9). Aldehydes, organic hydroperoxides, and carboxylic acids were characterized around Mauna Loa (H2O), where maximum concentrations of HzO2, ROOH, and CHzO were highest during a 2 day photochemical haze episode. A description of methods and instrumentation for studying atmospheric transformation by GC was given (H21). Actual field studies were reported for toxic organic compounds in the Los Angeles, CA, area (H22), where photochemical generation of formaldehyde, acetaldehyde, acetone, and acrolein was noted, The formation of nitro derivatives of fluoranthene and pyrene in Milan, Italy, was reported to occur through gas-phase atmospheric reactions with day/night contrasts to indicate photochemical contributions to the transformations (H23). Biomonitoring/Bioassays. In biomonitoring, biological materials or living organisms are used as integrated continuous samplers or adsorbents for the selective enrichmentfrom ambient air in this section of toxic or hazardous analytes. In contrast, bioassays are usually measurements where isolated materials are screened for toxicity or mutagenicity using, for the most part, bacteria. Biomonitors. Several biological materials or organisms were used as biomonitors of atmospheric pollutants after sustained exposure to ambient air. Harvesting of the materials is followed by appropriate analytical methods including sample treatment and determination of the analyte. The analytical methods employed were ICPMS or AAS for heavy-metal measurements and GC or HPLC for organic compounds. Mosses were used exclusively as indicators of heavy-metal pollution owing to the chelating properties of mosses. Sphagnum auriculatum was used to collect Pb in urban atmospheres with maximum exposure times of 1-2 months in high-exposure areas
(11).The analytical method associated with this approach was thoroughly examined with emphasis on optimized conditions, interferences, and precision with actual samples in Oporto, Portugal (12). Multielement assays using mosses was demonstrated in the urban area of Bremen, Germany, where Cd, Cu, Pb, and Zn were used to indicate heavy-metal pollution (13). In other studies, an expanded list of up to 33 elements was determined with ICPMS or ICP emission spectrometry (14, Z5). Moss can also be transplanted as test plants to industrial zones as demonstrated for an oil-fueled power plant in Hungary (16). Heavy metals in lichens (Pamelia caperata) in central northern Italy were shown to be comparable to pristine areas with the exceptions of Cu and Zn (17). Intercomparison of lichen species (Parmelia sulcata and Lecanora conizaeoides)was too variable to allow interspecies calibrations (18). However, a interlaboratory comparison for 17 elements suggested that methods based upon lichen sampling are feasible (19). Lichen were also sufiiciently selective to discern differences with heavy metals in ambient air in Mexico City (110). At a permanent sampling site in Maryland and Virginia, lichen (Flavopamelia baltimorensis) samples have been collected for over 100 years in one instance or since the 1970s elsewhere. Samples collected in 1988 and 1992 showed marked reductions in nine elements, but not Al (111). In contrast to the natural chelating sites in lichens and moss, trees offer hydrophobic phases on pine needles and leaves where organic compounds such as PCBs, pesticides, and PAHs can be preferentially enriched from the atmosphere. An HPLC method for PCBs in pine needle wax was described and results from western Germany showed 47 ng/g of wax (112). A GC/MS method was given for organochlorinecompounds in pine needles (Pinus radiata) and aromatic hydrocarbons from anthropogenic sources (113). Organochlorine compounds were used to measure pollution levels in six European countries, and regional differences were indicated by the relative composition of the pollutants (114). Plane tree (Platanus vulgaris) leaves served as sorbents for PCBs in France (115)and bark from the same tree allowed the detection of 19 PAHs (116). Evergreen oak leaves (Querm ilex) were found to be reliable indicators of pollution from vehicular traffk (117). A single reference to metal accumulation in tree leaves noted Cd fallout near a waste incineration plant (118). Exotic bioaccumulators included bird feathers for Pb, Cd, and Hg (119), kale for PAHs ( B O ) , moths for metals (121). Herbicides were tracked using bean, lentil and pea (122). Bioassays. In bioassays, a classic approach is to collect a sample and prefractionate an extract into parts before testing individual parts. Biologically significant fractions can thus be identified and subjected to further chemical characterizationswhile other fractions can be assigned low relative priority for characterization. This was done with ambient air in Boise Idaho where wood burning led to formation of PAHs and some others (123). Mutagenicity of auto exhaust was examined after photooxidation (124). The mutagenicity of emission from combustors of municipal and hospital waste was determined Q5). Indoor air (I26) was also examined. Miscellaneous Air Analysis Applications. One class of air pollutant that does not match neatly any previous category but which could have significant ramification for human health is microorganisms. Modem analytical methods of analysis, often using GC or GUMS, are based upon chemical characterization of microbes. Consequently, the subject is introduced in this issue
in recognition of the importance of airborne biological pollution and the use of chromatographic, mass spectrometric, and other methods in such assays. In the articles collected for this section of the review, the principal concern was with collection of bioaerosols or airborne microorganisms. In one study, several samplers were compared in terms of sampling efficiencies V I ) , where most samplers undersampled the surrogate aerosol stream. In a second work, this same group used Bacillus subtilis or Escherichia Coli and results were compared in view of the special properties of bacteria V2). Bacteria were also collected from ambient air using the low technology of medical-grade doublesided tape, which was missing the potentially toxic effect from the rubber-based adhesive of industrial-grade tape v3). One report that explored new analytical technology for microorganisms was the discussion of lidar-based remote measurements V4). WATER ANALYSIS APPLICATIONS General Comments. Because of the increasing number of articles appearing in the literature describing the analysis of aqueous matrices, the scope of this section has been limited to the analysis of trace pollutants in 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 (K1)and in the Water Analysis review in this issue of Analytical Chemistry. Reviews and Articles of Broad Interest. Trends in the analysis of organic compounds were reviewed (K2, K3). The fate and transport of organic compounds in Cape Cod’s groundwater were reviewed with 141 references (K4). Toxicity data for many hazardous compounds (2203 lines of data) were compiled by the European Chemical Industry Ecology and Toxicology Center; selection criteria and the structure of this database and its uses were described (K5). Methods for the analysis of pesticides (K6), phenols (K7),and organotin compounds by GGAED and AA have been reviewed (K8). Several reviews dealt with sample preparation. The use of soluble filters for preconcentration of trace elements in water was reviewed in 42 references (K9).M i n i tion of contaminationin the analysis of trace metals was discussed (K10). Also reviewed were instrumentationand automation used in wastewater treatment (K11),pollutant monitoring and determination (KIZ), and disinfection of water and wastewater, including analytical methods for the determination of trace components (K13). Continuous precipitation techniques in flow injection analysis (K14)and filtration and ultrdtration for size fractionation of aquatic particles, colloids, and macromolecules (K15)were discussed. On-line versus off-line solid-phase extraction for the determination of organic compounds were compared with 58 references (K16).Analytical techniques, as applied to water analysis, were reviewed, including in situ voltammetric measurements with 154 references, (K17),fluorescence spectroscopy (K18),IR and Raman spectroscopy (K19),ICPMS (K20), membrane introduction MS (KZI),and capillary electrophoresis (KZ2). Surface Water, Rivers, and Lakes. Interest in surface waters has increased-this section contains more than double the references cited in our last review. Perhaps this trend reflects an increased awareness of the importance of lakes and rivers in the transport of pollutants. Inorganic analytes were studied most Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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often. Nearly threefourths of the papers reviewed for this section dealt with studies of inorganic analytes. Sampling and Extraction Techniquesfor Inorganics. An instrument system for remote measurements of physical and chemical parameters in shallow water was introduced (151). A comparison of surface-grab and cross-sectionally integrated sampling showed that, while dissolved components were the same concentration with both sampling methods, concentrations measured for particlebound Mn, P, and Fe differed (U).Difficulties associated with preserving the integrity of Cr in water samples were discussed (D, L4). Several works described the speciation of metals, including Al (U-L7), As (L8),Cr (L9,LIO), Cu (LII),Pu (LIZ), Se (LI3),and Zn (L7). Complexation with thenoyltrinuoroacetone was an easy method for isolating sub-ppb concentrations of Mn (LI4). Coprecipitation of trace metals with Zr(0H)r (L15)or with pyrrolikinedithiocarbamate (LI6)were useful extraction methods. Various resins were used for the isolation of inorganic compounds-for example: poly(dithi0carbamate)was used to isolate Cu, Fe, and Zn (LI7), cellulose with immobilized triethylenetetraminepentaacetic acid for many trace metals (LI8),manganese dioxide for U, Th, Pu, Am, and Ra (LI9),Prussian blue impregnated-ion-exchangeresin for Cs ( U O ), silica gel for U (UI) , and quinolin-8-01immobilized on glass for Al, Ga, and In (UZ). Determinations of Inorganics. Flow injection analysis was often cited and used to determine Br- and P (U3),C1- (U4,and organic and inorganic Hg (U5)in environmental waters. Ion chromatography was also used in several studies. Anions and divalent cations in Australian surface waters were simultaneously determined using this technique (U6). Ion chromatographywas also used to study anions and cations in peatlands (L27,U8). On-site anodic stripping voltammetry was used to monitor the effectiveness of a Cu-based algicide dosing of a reservoir (129). Solid-phase spectrophotometry was used to determine ppb concentrations of Sn in natural waters ( D O ) . Time-resolved laserinduced spectrofluorometrywas used to investigate interactions of trivalent elements, Cm and Dy, with humic acids (L31). Laserexcited atomic fluorescence was used to study the distribution of Pb (4-25 ppt) in the Great Lakes (E&?). Results of a study of a-activity of water within 30 km of the Chemobyl Nuclear Power Plant in 1986 and 1990 were reported (D3). Onehundred freshwater samples collected in the former USSR were analyzed for various trace metals (L34). Other studies analyzed surface waters for As (L35),Ba (1963,Cd (L33, Cr (L38), Hg (L39,UO), Pt and Rh (IAI), Sb, Se and As (U.2), Sb (U3),U and Th (U4, U0z2+(IA5),V ( U 6 ,U7), and various trace metals (L48-130). Analysis of Organic Compounds (OCs). The collection of large sample volumes remains crucial for the detection of compounds of low solubility. The Goulden extractor was used to sample 80800 L of water and to determine PCB recoveries at different flow rates ( G I ) . This extractor type was also used to determine pesticides in river water (UZ).A filtration/adsorption unit for differentiating dissolved and particle-bound OCs was developed and used to determine PCB (U3)and PCDD and PCDF (U4) in river water. A semipermeable membrane was compared to the freshwater clam for PCB, pesticides, PCDD, and PCDF sampling in the Sacramento River (L55). Passive samplers, intended to mimic uptake of OCs from fish, were used to locate PCB sources along the Black River (US). Volatile OCs were monitored by membrane inlet mass spectrometry (L57)and were also used as tracers for the distribution and movements of effluent currents 230R
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in a bay (U8). Other studies described the separation and determination of dissolved and particulate humic substances (fig), the determination of carbonyl sulfde and hydrogen sulfide species (L6O),and the analysis and speciation of organotins (L61). Interest in polar OCs has increased. On-line dialysis-liquid chromatography was used to determine phenylurea pesticides (L62);an on-line method for concentrating OCs with porous graphitic carbon prior to HPLC separation was used to determine aminophenols and chloroanilines (L63);on-line extraction followed by LC was also used to determine N-methylcarbamate pesticides (L64);on-line solid-phase extraction followed by LC/thermospray MS was used to determine pesticides (L65).Novel analytical methods included the use of ion-pair LC coupled with thermospray MS to identify chlorinated phenoxy acids in the Rhine River (L66), micellar electrokinetic capillary chromatography to determine chlortriazine herbicides in river water and micellarenhanced flow injection fluorometry to determine carbendazim (L68). Groundwater, Wells, Reservoirs, and Springs. Several reviews (MI, MZ),including a book on groundwater contamination (M3),were published. The determination and fate of unstable contaminants (02, CH4, HzS, Fe(II), and organic carbon) in groundwater were reviewed (M4). The monitoring program at Savannah River (Ma, the quality control program at Hanford (Ma,and an overview of statistical methods for groundwater monitoring (M7)were described. Monitoring data from 500 waste disposal sites showed that volatile organic compounds are the most abundant class of organic contaminants in groundwater; thus, the presence of these pollutants can be used to establish the need for more extensive chemical analysis at a site (M8).Early-time transient electromagnetic (TEM) sounding and dc-resistivity sounding were used to monitor changes in a groundwater pollution plume; however, much improvement is needed in the operation and interpretation of TEM soundings (M9).Several articles discussed monitoring wells and sampling and are summarized in Table 9. Specific analytes investigated are listed in Table 10. DrinkingWater. During the review period, many methods for the analysis of drinking water appeared. Most methods represented incremental improvements in established methods-for example, the use of new resins for solid-phase extraction or tricks for improving detection limits. US.EPA regulations for maximum contaminant levels in drinking water were reviewed (NI). The U S . EPA also published health advisory reports for TI (N2) and Ag (N3) in drinking water. Inorganic Compounds. One field test, for the determination of Pb, was reported (N4). Laboratory methods for the analysis of inorganic analytes are summarized in Table 11. Organic Compounds. The OCs of most interest were chlorination byproducts, pesticides, and petroleum hydrocarbons. US. EPA methods remain the standard for the analysis of organic compounds in drinking waters; microextraction (NZO)and solidphase extraction (SPE) followed by supercritical fluid extraction can be used to make EPA methods environmentally friendly (NZI). SPE was used to extract chlorinated phenoxy acid herbicides (NZZ) and chlorinated acids and phenols (N23). Graphitized carbon black was used to extract phenols from water (N24). There is a trend toward increasing automation-a fully automated procedure for the analysis of pesticides by membrane disk extraction coupled to on-line GC was described (NZ5).
(fin,
Table 9. Groundwater Monitoring Wells and Sampling Information notes
ref
Sampler Design guidelines for the use of PTFE, PVC, and stainless steel in samplers reviewed with 50 references design and construction of PVC, 6.4 cm diameter, well casings detection, confirmation, and prevention of leaks in the casings of monitoring wells dual-walled screen made of wire-wrapped screens and filter packs was an effective well design for fine sand aquifers method for in-field design of monitoring wells in heterogeneous fine-grained formations Sampling Location piezometric cone penetration testing and penetrometer groundwater sampling for volatile organic contaminant plume location aids in placement of monitoring wells combined applications of cone penetrometer, Hydropunch sampling, and bore hole geophysics were used for site assessment to determine placement of groundwater wells Sampling monitoring with low-flow, dedicated pumping devices for purging and sampling of wells: dissolved 0 2 and specific conductance were used to decide when to sample for volatile organic compounds collection of mobile colloids described; slow pumping of groundwater samples yielded most representative in situ colloid populations sampling procedures for the determination of aqueous inorganic contaminants and assessment of their transport by colloidal mobility evaluated differences in water chemistry between the casing and screened interval volumes of four wells were studied; tracer experiments were used to study the differences in natural flushing between the casing and screened interval volumes multiport sampler with seven screened intervals was used to study vertical variations in water chemistry hypothetical numerical experiments and chemical analyses illustrate the impact of physical and chemical heterogeneity in an aquifer on samples drawn from wells nitrate and atrazine measured in imgation wells: in transmissive formations, samples may be taken after 15 min of pumping
M10 M11 M12 MI3 M14 M15 M16 M17 MI8 M19 M20 M2 1 M22 M23
Table 10. Analytes Monitored in Groundwater analyte actinides (Am, Pu,Np) As(III), As(V) B Cd, Pb, Cu, Zn 36c1
Cr Cr, Ni, Cu, Pb cu rare earths 99Tc dioxins, PCB ethylenethiourea organic compounds volatile organic compounds volatile organic compounds
notes Inorganics dependence of actinide solubility and speciation on carbonate concentration and ionic strength studied at pH 6 , 7, and 8.5 ion-exclusion chromatography and continuous hydride atomic absorption spectrometry used to study As speciation in geothermal water: As measured from 0.01 to 10 ppm application of B isotopes for identifying fly ash leachate in groundwater determined by differential pulse stripping voltammetry used as tracer to study the invasion of a uranium ore body by groundwater and the isolation of groundwater in the uranium deposit area adsorptive catalytic stripping voltammetry used to determine total Cr in a groundwater sample; detection limit 1 ppt synchrotron X-ray fluorescence spectroscopy and energy-dispersive X-ray analysis used to identify metals on colloids: the colloid’s nature, rather than the total amount present, controlled colloid-facilitated transport of contaminants Cu complexed with 4,7-diphenyl-2,9-dimethyl1,lO-phenanthrolinedisulfonate,concentrated on an ion exchanger packed in a flow-through cell, and detected by spectrophotometry; detection limit 80 ppt determined by ICPMS without treatment or preconcentration of samples: detection limit 50.5 ppt resin extraction followed by scintillation counting was an easy screening technique Organics a GC-cryogenic trapping FT-IR spectrometer was used to determine 200-800 pg quantities of PCB, chlorinated dibenzodioxins, and norflurazon: isomers could easily be identified several hundred samples of groundwater and river waters analyzed by GC-alkali flame ionization detection; detection limits 0.1 ppb fate in groundwater and soil at site in Ville Mercier, Canada, and identification and quantitation discussed purgeable organic chloride analysis was a complementary monitoring technique to purge and trap G C N S a passive sampler was constructed of a sorbent tube that fits inside a sampling chamber equipped with a diffusional membrane that is permeable to organic vapors: after exposure, the analytes are desorbed from the sorbent and determined by G C N S
Another system combined SPE with HPLC for the measurement of pesticides (NZS),and a robotic system was designed to screen trace pollutants at subppb concentrationsby SPE followed by GC (N27). Petroleum hydrocarbon contamination in drinking water was determined using a m o d ~ e dUS. EPA method 625 (N28). Ethylene thiourea was determined by GC-NPD in a collaborative study (N29). It was reported that method 5710B from Standard Methods may not always be adequate for predicting trihalomethane concentrations (iV30).New instrumental methods applied to the analysis of organic compounds in drinking water included thermospray mass spectrometry for the analysis of phenylurea herbicides (N31), membrane permeate and trap GC/MS for the detection of polar, volatile compounds (N32), and capillary electrophoresisfor the detection of metsulfuron and chlorsulfuron (N33).
ref M24 M25 M26 M27 M28 M29 M30 M3 1 M32 M33 M34 M35 M36 M37 M38
Seawater and Coastal Waters. Great interest has been shown in the analysis of seawater; many new methods for the determination of inorganic species have been reported. The determination of trace metals by ICPMS (OI),trace metal speciation (02), and flow injection analysis (03) for seawater analysis have been reviewed. Shipboard Methods. Several papers describing shipboard methods have been published, including sampling of dissolved and particulate trace elements (04, physical, biological, and chemical sampling (05),determination of Cr(I1I) and total Cr by derivatization with trifluoroacetylacetone followed by GC-ECD (OS), and rapid extraction and determination of Th, Pb, and Ra from large volumes of seawater (07). Znorganics. Newer methods for inorganic analysis that were used in studies of seawater are summarized in Table 12. Analytical Chemistty, Vol. 67, No. 12, June 15, 1995
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Table II.Inorganic Analytes Determined in Drinking Water analyte A1 A1 A1 A1 As Ba Be
Co, Mo, V Cu, Pb disinfection byproducts (C102-) Ge
Pb Pb trace metals U, Th, Po, Ra a
notes'
ref
flow injection spectrofluorometric method used salicylaldehyde carbohydrazone in presence of Triton X-100; dl = 2 ppb speciation studied in England neutron activation analysis: A1 in drinking waters was 80-170 ppb pyrocatechol violet, eriochrome cyanine R, and aluminon methods and AAS compared; pyrocatechol violet method was less susceptible to interferences arsenous, arsenic, monomethylarsonic, and dimethylarsinic acids separated using didodecyldimethylammoniumbromide vesicles for LC coupled to ICP-AES; dl = sub-ng Ba2+detected in well water from 89 sites in Italy at 10-925 ppb graphite furnace AAS: ammonium phosphomolybdate and ascorbic acid used as matrix modifiers eliminated common interferences: dl = 30 ppt determined in mineral water by ICP-AES following preconcentration by ion exchange portable potentiometric stripping analyzer; 0.4 mL sample required: Cu(I1) at 0.10-5 ppm and Pb(I1) at 1-50 ppb detected ion chromatography used for detection: agents evaluated for stabilization of disinfection byproducts preconcentration in a graphite furnace using a flow injection hydride generation technique; dl = 4 ppt with 5 mL sample reacted with 5,10,15,20-tetrakis([4-N-(sulfoethyl)pyridinium]porphyrinand detected by spectrophotometry: dl = 15 ppb Pb isotope ratios used to determine sources of Pb in tap water Cd, Cu, Fe, Mn, Ni, Zn preconcentrated as 8-quinolinol complexes; Ag, Cd, Cu, Zn preconcentrated as bismuthiol I1 complexes, and Cd, Cu, Zn preconcentrated as 8-quinolinol-5-sulfonic acid complexes on poly(chlorotrifluoroethy1ene)resin determined in mineral water by a-spectroscopy and liquid scintillation counting: dl = 0.1-2 mBq/L
N5 N6 N7 N8 N9 N10 N11 N12 N13 N14 N15 N16 N17 N18 N19
dl, detection limits.
Organics. PCBs and organochlorine pesticides were detected, in aqueous and particle phases, at ppt concentrations in large (28 L) volumes of seawater (042). Halogenated hydrocarbons, byproducts in chlorinated seawater used for drinking water, were identilied ( 0 4 3 ) . Phenol, cresols, and catechols were present at low-ppb concentrations in San Diego Bay (044). Alkyltin species remain compounds of interest (045, 0 4 6 ) . Municipal and Industrial Wastewaters. Two reviews described the use of ion chromatography (PI) and energydispersive X-ray fluorescence (P2) in wastewater analysis. The analysis of pulp and paper, nuclear power plant, and municipal wastes was the focus of most analytical research. Sewage and Municipal Wastewaters. Inorganic species of concern included Pb and Cd (P3) and free available chlorine and total residual chlorine (P4). Organic compounds monitored were aromatic surfactants (PS) and secondary alkane sulfonates ( P a . N-Chloroaldimines were identified in municipal wastewaters (P7). Hf was used as a radiotracer to iden* particulate deposits and biological effects of urban discharges from sewage outfalls (P8). Pulp and Paper Mill Discharges. Chlorinated organic compounds generated the most interest in discharges from pulp mills. Chlorinated benzaldehydes (P9),toxaphene (PI@,polychlorinated diphenyl sultides (P11), chlorinated furanones and hydroxyfuranones (P12), and aromatic coeluatents of polychlorinated dibenzcp-dioxins and dibenzofurans (P13) were determined in pulp mill wastes. Resin acids were determined by HPLC analysis of their 7-methoxycoumarin-4-yl and 7-acetoxycoumarin-4-ylmethyl ester derivatives (P14). Nuclear Power Plants. A radiochemistry procedure for the separation and measurement of @Co(II)and @Co(III)in authorized discharges from a heavy-water reactor was reported (PIS). 90Sr (P16) in solutions from a nuclear fuel reprocessing plant and lZ91 (P17) in water from a nuclear power reactor were determined. Miscellaneous Discharges. Potentiometry was used to determine Hg(I1) in chloralkali effluents (PI&'), cold-vapor AAS was used to determine Hg in wastewaters from research laboratories (P19), and flow injection ICP-AES was used to determine Au in metal refinery wastewaters (P20). HPLC and GC were used to 232R
Analytical Chemisfry, Vol. 67, No. 12, June 15, 1995
analyze nitrosulfonic acids in wastewater from TNT production (P22). Electroplating wastewater was analyzed for trace metals by formation of EDTA complexes and by performing reversedphase ion-pair chromatography (P22). Fifty-eight organic compounds resulting from the ozonation of wastewater from dicofol and tetradifon manufacturing were identilied (P23). Sulfonated polyphenols were determined by ion-pair liquid chromatography in tannery wastewaters (P24). Analytes and Techniques of Interest. Volatile organic compounds were monitored at ppb and low ppm concentrations by sparging and FT-IR (PZS). Nonionic surfactants (0.1-50 ppm) were also detected with FT-IR (P26). Ca and C1 were monitored by flow injection analysis coupled to a double membrane dialyzer (P27). Cr speciation has been studied by reversed-phase HPLC and W detection (P28). Several methods for the determination of CN- were compared (P29). Hg continues to be an analyte of concern and was analyzed by atmospheric pressure argon microwave-induced plasma AES (P30) and by cold-vapor AAS (P31). Landfill Leachates, Sludges, Waste Sites, and Runoff. Analytical methods for leachate characterization, for both inorganic and organic compounds, were reviewed (91). Problems encountered in metal analyses of landtill leachates and their solutions were described (92). The leachability of C1-, NO2-, NO3-, and Sod2- from samples collected at different locations in a land611 were studied by ion chromatography (93). Cu, Zn, Pb, and Mn speciation studies were performed on sewage sludges using sulfurous acid solution spiked with 35S(94). 201Tl, 99Tcm,and l3II, used in nuclear medicine, were detected at 1-250 Bq/kg in sludge samples from a sewage treatment plant in France by low-energy photon spectrometry; 134Csand 13'Cs associated with Chemobyl fallout were also detected (95). Polyhalogenated dioxins, furans, and diphenyl ethers were found in municipal wastewater sludge (96). Using steam distillation coupled with HPLC fractionation and GC-FID, a method for the determination of n-alkanes, linear alkylbenzenes, polynuclear aromatic hydrocarbons, and Cnonylphenol in digested sewage sludges was developed; this method was used to study contaminant concentrations over several months
Table 12. Inorganic Analytes Determined in Seawater analyte
Pu,Th, U Pu Th, Ra, Pb UWI) U misc heavy metals trace metals Cd. Cu. Mn. Ni. Pb. Zn Cd, Co, Cu, Hg, Mn, Th, U, V, Zn Cd, Cu Cr, Cu, Mn Cr(II1) Cu, Ni, Cd Cu, Ni, Cd Cu, Ni
Fe Hg Mo, V Mn 99Tc V V, Ni, As Zn
As As As Be Bi Ga, Ti, In H202 Pb Pb Sb Sb, As, Hg a
detectiono
preconcentration
Actinides and Lanthanides speciation in organic suspended matter studied coprecipitation of Pu with FeSO4 from 200 L of water, followed by acid digestion and adsorption to an anionic resin pump operating at 35 L/min filters seawater; y-counting dissolved species collected on cartridges flow determination by square wave adsorptive stripping voltammetry; dl = 0.1 pmol/L liquidlliquid extraction, with N-phenylspectrophotometric; dl = 1 ppm 3-styrylacrylohydroxamicacid Transition Metals total-reflection X-ray fluorescence energy-dispersive X-ray fluorescence; dl = precipitation with APDC 1 ppb (500 mL sample) Chelamine, chelating resin; recoveries '90% coprecipitation with 1-(2-thiazolylazo)-2-naphthol, neutron activation analysis; dl = ppb range pyrrolidinedithiocarbamate and N-nitrosophenylhydroxylamine graphite fumace AAS; dl = 4-24 ppt (0.5 mL CIScolumn loaded with sodium diethyldithiocarbamate sample) AAS Chelex-100 and Lewatit TP 207 resins voltammetry; dl = 1 pmol/L adsorption on silica and reoxidation to Cr(V1) ICP-AES; dl = 16-70 PPt 8-quinolinol immobilized on silica metal-dithiocarbamate complexes separated on C2 column coated with an ammonium pyrrolidin- 1-yldithiofomate-cetyltrimethylcolumn by HPLC with UV detection; dl = 0.5 ppb (10 mL sample) ammonium bromide ion pair speciation determined by competitive ligand equilibration-cathodic stripping voltammetry, differential pulse anodic stripping voltammetry, and graphite fumace AAS chemiluminescence detection;dl = 50 pmol/L chelating resin (8-quinolinol) (18 mL sample) anodic stripping voltammetry with glassy carbon electrode spin coated with 4,7,13,16,21,42hexaoxa- l,lO-diazabicycl0[8.8.S]hexacosane cellulose phosphate column ICP-AES graphite fumace AAS; dl = 50 ppt (80 pL sample) dl = 3 mBq/m3 anion exchange adsorptive stripping voltammetry; dl = 70 pM flow injection, cryogenic desolvation ICP/MS; dl = 10-20 000 ppt fluorescence; dl = 0.1 nM (4.4 mL sample) cation exchange and complexation with p-tosyl-8-aminoquinoline Other Inorganics cathodic stripping voltametry; dl = 3 nmol As(II1) and As(V) separated by APCDT/CHCl3 neutron activation analysis hydride trapping prior to AAS graphite fumace AAS; dl = 0.6 ppt adsorption on activated carbon as acetylacetone complex electrothermal AAS; dl = 0.3 ppt liquidlliquid extraction into xylene as dithiocarbamate complex ICPMS; dl = 0.01-0.4 ppt 8-hydroxyquinoline chelating resin preconcentration review with 51 references covers cycling and analytical methods laser-excited atomic fluorescence none spectrometry; dl = lppt ICP-AES; dl = 6 PPt Chelex-100 resin y-spectroscopy; dl = 0.4 mBq/L; allows absorption on MnO2 use of Iz5Sbto trace movements of water masses in English Channel ICPMS; dl 0.5-7 ppt flow injection 7
ref 08 09 010 0 11 012 013 014 015 016 017 018 019 020 0 21 022
023 024 025 026 027 028 029 030 0 31 032 033 034 035 036 037 038 039 040 0 41
dl, detection limits.
(97).Methods for the analysis of polychlorinated biphenyls by microextraction (98), cationic surfactants by SFE and HPLC (Q9), and 3(2-hydroxypropy1)-5methyl-2+xmlidinone(910) in sludges were reported. Biomonitors, Bioassays, Biological Sensors,and Chemical Sensors. Biomonitors. Plants and animals were important monitors for water contamination. Biomonitoring of trace elements was reviewed with 124 references (R1).Guidelines for evaluating Se data from aquatic monitoring studies that deter-
mined Se concentrationsat different points in the food chain were suggested (RZ).Species used as biomonitors for specitic pollutants are listed in Table 13;recent emphasis has been placed on the determination of pollutants in species that occupy the beginning of the food chain. When direct historical data were not available, algal microfossilswere used to assess deterioration and recovery in aquatic systems (R15). Bioassays and Biological Sensors. Biological sensors are important for the development of rapid and field-portableassays. Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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Table 13. Species Used as Biomonitors for Water Contamination biomonitor aquatic insects aquatic mosses aquatic plants (Ceratophyllum demersum, Ipomoea aquatica, Eichhornia crassipes, Spirodela polyrrhiza, Trapa natans, Chara corallina) benthic diatoms Ceriodaphnia
Cladophora glomerata fish bile foraminifera, corals mussel Mytilus galloprovincialis polychaetes pond slider (Trachemys scripta) and snapping turtle (Chelydra serpentina) river passerine eggs
notes monitored Cu, Cd, Pb, Zn, and As in rivers used to study accidental discharges of Cd, Zn, Hg, pentachlorophenol, and lindane; analytes detected up to 13 days after discharge biomonitoring of Cr, Mn, Fe, Cu, Cd, and Pb are discussed
R3 R4
y-spectra determined for 421 samples from the Baltic Sea from 1983 to 1989; short-lived radionuclides from Chemobyl were below detection limits after 1 yr, but Cs isotopes still present after 3 yr method sensitive for 17 pesticides at ppt to ppm concentrations; a method for estimating persistence of pesticides in waters was developed monitored heavy metals in the Danube River; metal concentrations differed according to developmental stage and changes in the dry weight of the Cladophora polynuclear aromatic hydrocarbonsmonitored by synchronous scanning fluorescence analysis of 1-hydroxypyrene indicated carbonate-bound Ba indicated Pb in N. Tyrrhenian Sea environmental monitoring reviewed, 55 references %, I3’Cs, 6oCo,Hg monitored; single-strand breaks in liver DNA also determined
R6
eggs indicated spatial pattems in organochlorine pesticides and PCBs, but only detected pronounced and sustained temporal trends
R14
While many biosensors and bioassays are available to assess overall water quality, only assays and sensors that are analytespecific will be considered here. Immunochemical analysis, as applied to water, was reviewed (RIG. Bioluminescent bacteria immobilized onto an optical light guide detected bioavailable naphthalene and salicylate in solutions saturated with jet fuel and in the leachate from a gas plant soil (RI7). Bioluminescence was also used to determine bioavailable Hg(II) in spiked freshwater, rain, and estuarine samples (RI8) and Fe(I1I) at a detection limit of 10 ppb (RI9). A fiber-optic sensor, based on the inhibition of the enzyme acetylcholinesterase, was developed for the early detection of pesticides in water (R2O). Many reports appeared describing the use of bioassays for the detection of triazine herbicides. Flow injection immunoassay yielded detection limits for atrazine of 30 ppt, without sample pretreatment (R21);solidphase extraction followed by magnetic particle-based enzymelinked immunosorbent assay (ELISA) provided detection limits for atrizine and alachlor of 5 ppt (R2Z).Magnetic particle-based ELISA also detected 35 ppt cyanazine (R23) and ppb carbaryl in water (R24). Photolithographically patterned enzyme membranes, based on enzyme inhibition, were developed for the detection of dichlorovos and Cu (II) at ppm concentrations (R25).A H4IIE rat hepatoma bioassay was used to measure 2,3,7,&tetrachlorodibenzo-$-dioxin toxic equivalents in the livers of white sucker collected downstream from eight pulp mills (R2G. Chemical Sensors. Chemical sensors have developed in response to the need for field-portable and on-line measurements. The use of chemical sensors and biosensors in water protection control (R27)and the use of fiber-optic chemical sensors (R28) have been discussed. A field sensor for the determination of Fe(II) was made by doping a sol-gel silica powder with 0phenanthroline; as water containing Fe(ID was passed through a capillary filled with this material, complexation of Fe(II) with o-phenanthrolineresulted in a visible color change (R29). A TI+selective, chalogenide glass sensor was used to determine TI in water samples in North Kazakhstan (R3O). A mid-IR fiber-optic sensor was evaluated for analysis of tri- and tetrachloroethylene 234R
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R5
R7 R8 R9 R10 R11 R12
R13
in wastewater and found to be unaffected by other pollutants (R31). A polymer-based, reflectometric interferencespectroscopy technique was coupled to flow injection sampling and evaluated for the detection of chlorohydrocarbonsin water (R32). Polymercoated, silver halide fibers were coupled with evanescent wave spectroscopy for the detection of chlorinated hydrocarbons in seawater (R33). A fiber-optic reflectance sensor, based on the use of eriochrome cyanine R immobilized on XAD-2 resin, was developed for the determination of Al(I1I) (R34). Methods for Water Analysis. Analysis of Inorganic Compounds. Many methods for the analysis of inorganic compounds were presented. Methods discussed in this section give a survey of available techniques but are not a comprehensive list. All methods listed in this section have, at the least, been tested, if not used for monitoring studies, on environmentalwaters. Extraction of Inorganics. Liquid/liquid extraction was combined with on-line monitoring for Pb ( S I ) . Iodide was concentrated by transport extraction based on solvent sublimation (SZ). Crown ethers were used to extract Th and La (S3) and Y and Sr (S4) from aqueous solutions. New thiohydrazone chelating reagents were described (Sa. Erythrosine B was used to complex Cu in mixtures containing other trace metals (SQ. Alkylene bisdithiocarbamates were used as complexing agents for trace metals (S7). Poly(amido-amine) (SS), TBP-plasticized dibenzoylmethaneloaded polyurethane foams (S9), and sulfonated styrenedivinylbenzene (SIO)served as sorbents for trace metals. The most novel concentration media for metals were silica-immobilized algae cells ( S I I ) and silica-immobilized lichen and seaweed biomass (SIZ). A poly(viny1 chloride) membrane containing bathophenanthroline was used to extract Fe ( S I 3 ) , and a liquid membrane containing tri-N-octylaminewas used to separate Pd (SI4)from water. A Donnan dialysis preconcentration method provided rapid extraction and ppt detection limits for cations (S15). Investigations of Metal Speciation. The speciation of organotins in water was reviewed with 56 references ( S I Q . The speciation of As (SI 7, SB),Cr ( S I 9 ) ,Sb (SZO),and trace metals (SZI)was discussed. In situ speciation of trace components in water was measured using thin-film gels to separate the aqueous solution
Table 14. Novel Techniaues for Detection of Inorganic Compounds In Water separatioddetection technique CE CE CE CE (isotachophoresis)
atomic absorption spectroscopy atomic absorption spectroscopy atomic absorption spectroscopy chemiluminescence fluorescence HPLC ICPMS ICPMS photodiode voltammetry infrared spectroscopy laser-induced atomic fluorescence spectroscopy X-ray fluorescence, energy dispersive X-ray fluorescence, total reflection desorption chemical ionization MS ion chromatography ion chromatography reversed-phase ion-pair LC thermal lens spectrometry voltammetry a
notes Capillary Electrophoresis (CE) compared to gravimetric and ion chromatographic methods for analysis of inorganic anions; dl = sub ppm demonstrated separation of anions; data correlated well with ion chromatography M alkaline-earth metal ions studied; dl = various solid-phase adsorbents studied for analytes in environmental and biological matrices optimization of injection technique discussed; low-ppb detection for trace anions On-Line Methods coupled to HPLC, Cr(II1) and Cr(V1) separated; dl = 30 ppb preconcentration on microcolumn packed with specially treated silica gel; dl = 10 ppb Pb modified XAD-2 resin for preconcentration; dl = 0.1 ppb for Ni(I1) dl = 0.01 ppb for Cr(II1) ppb Cr(II1) determined by reduction to Cr(I1) in flow-through cell method linear from 2 to 200 ppb with RSD 2-5 metal ions complexed with butane-2,3-dionebis(N-pyridinoacetyl hydrazone) and retained on XAD resin; dl = low ppt metals at dl < 0.5 ppb AI and Fe complexed with pyrocatechol violet; dl = 10 ppb UV digestion used to free trace metals from organic complexes Spectroscopic Techniques application to CN- speciation; dl = 10-100 ppm 16 elements had dl < 1 ppb Pb detected at sub-ppm concentrations new optical system improved heavy-metal detection Miscellaneous Techniques advantages for characterizing As compounds discussed; 100 ng of As detected simultaneous detection of anions and cations; conductivity detector and flame emission spectrometer used determination of inorganic and organic anions in one run with column switching and conductometric detection metal ions determined at ppb concentrations results presented for analysis of hydrous ferric oxide colloids; perhaps a useful technique to study metal speciation moss-modified carbon paste electrode used; dl = 2 ppb Pb
ref S23 S24 S25 S26 s27 S28 S29 S30 S31 S32 s33 s34 s35 S36 S31 S38 s39 S40
S41 S42 s43 s44 s45
S46 S41
dl, detection limits.
from an ion-exchange resin (S22). Determinations of Inorganic Compounds. Many methods for the analysis of inorganic compounds have appeared in the literature. Many of these articles described on-line techniquessample preparation has been combined with many different detectors. Some newer techniques, such as capillary electrophoresis, are maturing and finding a place in environmental analysis. Several newer instrumental techniques used in the analysis of inorganic compounds are listed in Table 14. Table 15 contains a listing of inorganic analytes and approximate detection limits for techniques that represent incremental improvements to established methods. Analysis of Organic Compounds. Recent developments in the analysis of OCs include the increased use of on-line techniques and methods, such as SPE and SFE, which minimize solvent waste. LC/MS is now being applied to many environmental problems. Sampling and Extraction of Organic Compounds. Solid-phase extraction has become a solidly entrenched technology. Various pesticides showed greater stability when stored on frozen SPE disks then when stored in water at 4 "C (S92). On-line SPE coupled to HPLC was used to detect 30 pesticides, including atrazine, simazine, alachlor, and molinate at 0.01-0.5 ppb (S93). On-line SPE was coupled to GC/MS to detect triazine herbicides at ppt concentrations (S94). Optimization of a SPE method for the extraction of metribuzin, atrazine, metolachlor, and esfenval-
erate was performed using a 25factorial experimental design and considering pH, elution solvent strength, and organic modAers (S95). The effectiveness of different SPE materials for the extraction of OCs has been studied; polymeric P W - S in combination with C18 was the best material for the enrichment of polar OCs (S96). CN-bonded SPE cartridges efficiently extracted chlorinated pesticides at ppb concentrations (S97). XAD-8 resin was used to extract chlorolignosulfonic acids and lignosulfonic acids for pulp mill effluents (S98). SFE of SPE materials was used to determine PCBs at 10 ppb (S99), PAHs, PCBs, organochlorine pesticides, and phthalate esters (S100),nonionic surfactants (S101),and explosives (S102). In addition, SFE was used to directly extract organochlorine pesticides from water (S103). The problem of using SPE for water samples with high particle concentrations was addressed by using glass beads to inhibit plugging of the SPE disk (S104). Unique methods of extracting OCs from water included the use of solid-phase microextraction with a polymeric phase immobilized onto a fused-silica fiber for the determination of PAH at 1-20 ppt (S105) and extraction of trichloroethene at 1ppb with a hollow fiber membrane directly interfaced to a GC (S106). A semipermeablemembrane, consisting of a thin film of neutral lipid, was developed for passive, in situ monitoring of OCs (S107). A hollow fiber membrane interface made of silicone rubber continuously purged with He could be used to detect subppb volatile OCs in drinking water (S108). Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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Table 15. Listing of Methods for the Determination of Inorganic Compounds Organized by Analyte analyte AI Al, Ga As, Se B Be Be Cd Cd Cf CI (free) CN.
cs Cu, Co, Ni, Fe, Hg, Pb cu Fe Hg Hg Hg Hg Hg Hg Hg Hg Hg In, Br Li Mg Mn Mn
os Pb Pb
Pb 210Pb Pb Po 226Ra 222Rn Sb Sb
Se Se Tb, Dy, Eu
23Ol-h Zn a
technique and detection limito
ref
solid-phase spectrofluorometry: 20 ppt fluorescence; 10 ppb fluorescence; 50-100 ppt Azomethine H method; 20 ppt photothermal spectrometry: 0.1 ppm fluorescence; sub-ppb fluorescence neutron activation analysis y-ray spectrometry on-wafer fabricated sensor; 1 ppb atomic absorption spectrometry; sub-ppb flame emission spectrometry energy-dispersive X-ray fluorescence; ppb
S48 s49
ion-selective electrode; 5 ppb HPLC: 10 ppb photochromism-induced photoacoustic spectrometry ICPMS, isotope dilution; 6 ppt ICP-AES: 2 ppb AAS, automated amalgamation: 2 ppt indirect spectrophotometry; 0.4 ppb microwave induced plasma emission: 0.05-0.15 ppt atomic absorption, graphite tube; 30 pg atomic fluorescence, 3 pg: atomic absorption, 0.9 pg; atomic emission, 2 pg fluorescence: gold amalgamation: 2 ppt neutron activation analysis neutron activation analysis; 3ppm amperometry; 6 ppm fluorescence:l8 ppt galvanostatic stripping kinetic spectrophotometry: 5ppt anodic stripping voltammetry potentiometric stripping with gold-coated screen-printed electrodes voltammetry with microelectrodes @-counting; < 1 pCi/L atomic absorption; 0.2 ppb a-spectrometry on membrane filter impregnated with Ag: 1 mBq/L Cerenkov counting: 53 mBq/L neutron activation analysis; ppt electrothermal atomic absorption spectrometry preceded by concentration on glass-immobilized fructose-6-phosphate kinase gas chromatography-electron capture detector spectrophotometric: 0.08 ppm fluorescence; sub ppb a-spectrometry fluorescence; 5 ppb
S61 S62 S63
S50 S5 1
S52
s53 s54 s55 S56 s57 S58
s59 S60
S64 S65 S66 S67 S68
S69 S70 S7 1 S72 s73 s74 s75 S76 s77 S78 s79
s80 S81 S82 S83 S84 S85 S86
S87 S88 S89 S90 S9 1
Numbers given indicate approximate detection limits.
Determination of Organic Compounds. Headspace analysis techniques remain important for the determination of volatile OCs. A dynamic headspace method was developed to measure OCs in a flow cell with a constant headspace which was sampled automatically and analyzed with a portable GC (S109). Conditions required to optimize sensitivity and precision of headspace GC were explored (S110). Many polar, volatile OCs were evaluated for possible inclusion in U S . EPA method 524 (S111) and, in general, could be detected at concentrations below 1 ppb. GC remains the most useful separation technique for OCs and has been used with novel introduction techniques or detectors. GC/ AAS and AES was used for the determination of organotin species in water (S112). Carbamate pesticides, at 25-50 ppt, were separated by GC after on-line flash-heater methylation (S113). 236R
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Chlorinated benzenes were determined by purging directly to a capillary column (S114). Methods that allowed direct injection of water into a GC were developed for pesticides and nitroaromatics (S115) and PAHs (S116). A LC/GC/MS method for online analysis of 1-10 mL water samples was developed and demonstrated using river water spiked with 168 pollutants (SI17). A semiautomatic HPLC method was developed to determine desethylatrazine, simazine, atrazine, and terbethylazine at 15-32 ppb in drinking water-100 mL of sample was concentrated on Tenax TA and introduced onto an analytical column (S118). Another on-line HPLC method was introduced for the detection of 27 polar pesticides in water at 1 ppb or less (S119). Micellar extraction followed by LC and fluorescence detection yielded low ppt detection limits for PAHs (S120, S121); micelles were also used in the extraction of aniline derivatives (S122). HPLC was used for solute focusing prior to supercritical fluid chromatography/MS and used to analyze process waste streams (S123). Capillary electrophoresis was used to analyze linuron, metolachlor, atrazine, and metsulfuron (S124), and capillary electrophoresis with on-line isotachophoretic sample preconcentration yielded detection limits of mol/L, with a 90 p L injection, for paraquat and diquat (S125). Other detection methods for OCs, including fluorescence and mass spectrometry, are summarized in Table 16. W Q C and Related Issues. QA/QC issues continue to increase in importance. Interlaboratory exercises and the production of reference materials by the Community Bureau of Reference of the Commission of the European Communities was reviewed with 33 references ( T I ) . The design of a quality assurance program incorporating sampling, chemical analysis, and data evaluation was described for the Marine Environmental Monitoring Programs of the European Community; this project coordinated a network of 80 laboratories (T2). A protocol was developed for performance of routine analyses of groundwater for EPA's list of Appendiv M compounds (T3). Quality control samples to assess 38 parameters were described (T4). Aqueous, certified reference materials were developed for the analysis of Cr and As (T', metals by total-reflection X-ray fluorescence (T6),and for NH4+, Cd, H30+,Mg, NO3-, K, Na, and S042- in rainwater (T7). A sewage sludge reference material containing Cd, Co, Cu, Pb, Mn, Hg, Ni, and Zn was described (TS). Results of several interlaboratory studies, including comparisons of analytical methods for analyses of halogenated hydrocarbons in drinking water (m), chlorinated dioxins by US. EPA method 1613 (no), chlorinated acids by GC-ECD (Til), dissolved, hexavalent Cr by ion chromatography (T12), and 20 trace elements by ICPMS (T13), were reported. Al, Cd, Cu, Fe Pb, Mn, and Zn were determined in water samples having wide ranges of suspended solids. EPA total and total recoverable methods underestimated the maximum metal concentrations in water samples with high particle loads (T14). A 22 laboratory study determined a practical quantitation limit (4 ppb) for As in drinking water (TI$. Measurements of eight water quality parameters taken by three different shipboard laboratories were compared (776). Eight laboratories participated in a round-robin study which measured metals in water by ICP-AES and ICPMS (TI7). SOIL AND SEDIMENT ANALYSIS APPLICATIONS
Sampling. Reviews on the problems associated with techniques and strategies of soil sampling (VI) and of the collection
Table 16. Techniques for Detection of Organic Compounds in Water method electrochemiluminescent sensing evanescent wave spectroscopy (FT-IR) fiber-optic evanescent wave spectroscopy (near-IR) fluorescence, with fiber-optic sensor synchronous solid-phase spectrofluorometry time-resolved laser-induced fluorescence spectroscopy atmospheric pressure ionization direct insertion membrane electrospray MS electrospray ion trap MS electrospray ion mobility spectrometry fast atom bombardment fast atom bombardment GCMS membrane introduction particle beam MS particle beam MS thermospray MS thermospray MS thermospray MS
notes“
ref
Spectroscopic Techniques selective detection of aromatic hydrocarbons in the presence of OH-containing species; dl = ppb with polymer-coated, silver halide fibers; simultaneous analysis of different chlorinated hydrocarbons; dl = low ppm sensing element is quartz glass fiber with silicone cladding which enriches nonpolar OCs; acceptable spectral distinction and semiquantitative analysis of chlorinated hydrocarbon solvents allows on-line and in situ detection of PAH at ppt concentrations dl = low ppb for PAH
S129 S130
dl = 0.5 ppm for PAH in water
S131
Mass Spectrometric Techniques 17 pesticides (triazines, phenylureas, carbamates, and organophosphates) studied; dl = 0.8-10 ng full scan and 0.01-1 ng selected-ion monitoring; API-MS is affected less than other LC/MS techniques by differences in analyte structure probebenzene, chlorobenzene, and dichloroethene studied at < 1 ppb MS/MS used to identify chlorodinitrophenol isomers MSMS used to study pesticides and dyes; dl = low ppb dl = 5 fmoUs for amines identification of surfactants by MS and MSMS discussed method for determination of ppt atrazine novel spray and trap technique for introduction into the MS used to confirm existence of NHBrCl and N-bromo-N-chloromethylamine used to identify unknowns in water; dl = 30-50 ppt for phenylurea pesticides; methane chemical ionization in positive and negative ion modes confiied identifications microliter flow rate interface used to determine 32 acid and basicheutral pesticides; improved response for high water content mobile phases reported C18 disks used to isolate captan, captafol, carbendazim, chlorothalonil, ethirimol, folpet, metalaxyl, and vinclozolin from water before MS analysis; dl = 0.5-2 ppb sensitivity and selectivity determined for 128 pesticides quantitative determination of linear primary alcohol ethoxylate surfactants
S 126 S127 S 128
S132 S133 S134 S135 S136 S137 S138 S139 S 140 S141 S 142 S 143 S 144
S145
dl, detection limits.
and preparation of soil samples for the Federal Soil Survey Laboratory Program (U2)have appeared. Factors affecting the realism of the collected sample were discussed by Burton (U3). Various sampling schemes for soils have been described (U4US). Different sampling designs are needed, depending upon whether the soil contamination is expected to be “spread over the whole area or exists in localized “hot spots” (U4). A decisionsupport system for the sampling of aquatic sediments in lakes was described by Wehrens and was applied to a real environmental problem (U5). Lame showed that the Fundamental sampling error for soils only affects the analytical variance when sample sizes are less than 10 g (Us).For larger samples, the variance is determined by the Segregation error. A sampling board method for estimation of the Segregation error was described. Skalski showed that a two-way compositing strategy could be used to attribute detected contamination in composited samples directly to constituent samples without further analyses (U7). Evaluations of various soil and sediment samplers have been reported (U8, US).The sediment shovel proved highly practical, but was limited because small particles tend to be lost when the shovel is l i e d (US). A cryogenic sediment sampler was less convenient to use, but allowed the collection of nearly undisturbed samples. Houba described a different device for the automatic subsampling of soil, sediment, and plant material for proficiency testing (US). In another study, Thoms showed that freezesampling collects representativesediment samples,whereas grab sampling introduces a bias in the textural composition of the 120 mesh fraction, due to washout and elutriation of the h e r fractions (U10).Contamination of soils with PCBs from laboratory air was demonstrated by Alcock and co-workers (U11).The calculated
average net dry deposition from laboratory air to soil samples was calculated to be five ,ug total PCB/m2-day. Inorganic Analytes. Sample Preparation. The risks of sample contamination using inappropriate materials, containers, and tools, as well as possible analyte loss during sample handling, were discussed by Rubio (VI). The influence of grinding procedures was discussed in another study, which found the availability of some analytes was significantly influenced by the degree of grinding in some soils (V2). Significant interest still exists in microwave extraction methods (V3-V6). In one investigation, the microwave extraction of cadmium in a soil reference material gave results comparable to those found after using conventional extraction procedures (V3). In another study, microwave versus conventional dissolution was compared for soils, sludges, sediments, and oils (V4). By microwave digestion of dust samples with a nitric acid/hydrofluoric acid mixture, over 90% of Pb and Cd were recovered within 30 min (V5). Microwave digestion procedures for the analysis of metal-contaminated soils were reviewed by Reynolds (Vs). Other extraction procedures for metals in soils and sediments were studied. An EDTA extraction procedure was evaluated in a collaborative study between six laboratories (V7). All laboratories produced some extreme outlying results, but most results were in good agreement once the outliers were removed. Acceptable accuracy and precision were obtained for metals in soil by using an ultrasonic bath digestion procedure (V8). An interlaboratory comparison study was reported involving 160 accredited hazardous materials laboratories (V9). In this study, each laboratory performed a mineral acid digestion on five soils spiked with As, Cd, Mo, Se, and Tl. Instrumental detection methods were ICPAnalytical Chemistry, Vol. 67, No. 12,June 15, 7995
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AES, ICPMS, flame AAS, electrothermal AAS, and hydride generation h4S. At most concentrations, ICP-AES exhibited higher precision and accuracy than the other techniques, but also the highest rate of false positives and negatives. Much work was reported for the evaluation of sequential extraction procedures. The three-stage sequential extraction procedure for speciation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR), was found to be repeatable and reproducible with some modifications (Vl0). In another study, the reproducibility of the BCR method (without modification), when applied to real sediments, was questioned (Vll). Lopez-Sanchez found that sign%candy different results can be obtained when different sequential extraction procedures are used (VlZ). Shan reported that various proportions of metals released from exchangeable, carbonatebound, iron and manganese oxide-bound, and organic-bound fractions were readsorbed onto the other solid geochemical phases during sequential extraction (Vl3). A sequential extraction study of Cr from contaminated aquifer sediments found that 65%of the Cr was extractable (Vl4j. Of this amount, 25%was exchangeable, 11%was bound to organic matter, and 30%was bound to iron and manganese oxide surfaces. Thomas also investigated use of the BCR sequential extraction procedure for river sediments and found the method to work well (Vl5). Improving sequential extractions by optimizing microwave heating was studied by Real (Vl6). Salin showed that direct analysis of solid samples is possible, by using furnace vaporization with Freon modification and ICP-AES (Vl7). The relative standard deviation of several metals in marine reference sediments varied from 3 to 15%. Determination of Mercury. Distillation was compared to alkaline digestion for the determination of Hg in sediments by isothermal GC-cold vapor atomic fluorescence (Vl8). The distillation approach produced results similar to those from conventional digestion procedures, but with fewer matrix effects. In another method for Hg in sediments, organomercury compounds were separated by HPLC, converted to Hg(0) in a continuousflow system, and detected by using atomic fluorescence (V29). One study showed that the use of H z 0 ~as oxidizing agent for organics in the sample during the extraction of Hg compounds can result in loss of Hg, because HzOz can act as reducing agent for Hg compounds (VZO). New procedures for Hg by using neutron activation analysis (NAA) (VZI), and by spectrophotcmetric determination after formation of a Hg-triphenyltetrazolium chloride complex (VZZ), were also reported. Determination of Organotins. A combination of supercritical fluid extraction and GC/atomic emission spectroscopy was used for the speciation of 13 organotin compounds (VZ3, VZ4). After extraction, the organotin compounds were treated with pentylmagnesium bromide to convert ionic organotin compounds into their neutral derivatives. Other methods include the in situ derivatization of organotins by using sodium tetraethylborate (VZ5),and this derivatization procedure was followed by extraction with methanol containing 0.5 M HCI (V269. Another investigation concluded that the speciation of some tributyltin compounds in sediment depends on the nature of the sediment (VZ7). The use of GC/MS and GC-AED was compared for the determination of organotins in environmental samples (VZ8). OtherMetals. Methods for Pb (VZ9-V32), As (V33, V34, Se (V35-V38), Sb (V39),and TI (V40) have also been reported. A method for Pb by EDXRF spectrometry, with arsenic present in 238R
Analytical Chemistry, Vol. 67,No. 12,June 15, 7995
the sample, was developed (V29). Correction for the interference is based on use of an arsenic-free reference sample. Ma and coworkers used a flow injection on-line sorbent extraction system for Cd, Cu, and Pb in river sediments (V30). Detection limits were 10 times greater for Pb, compared to Cd and Cu. Lead was also determined by using the method of standard additions and XRF measurement (V3l). By using known masses of a sediment matrix made from all of the samples, there was no need for standard additions to each separate sample. Lead was also determined by using a slurry sampling technique, with lead nitrate and magnesium nitrate as a chemical modifer (V32). Results were in good agreement with known concentrations of a standard reference material. Speciation of As(I1I) and A s 0 in marine sediments was accomplished at different pH conditions by hydride generation AAS (V33),and in soils by cathodic stripping voltammetry (V34). New methods for selenium in soils and sediments include the direct determination by using PKE (V35),hydride generation ICPMS (V36), and square-wave cathodic stripping voltammetry (V37). Haygarth compared the use of fluorometry, hydride generation AAS, hydride generation ICP-AES, hydride generation ICPMS, and radiochemical neutron activation for selenium in sediments (V38). For low-concentration samples, hydride generation ICPMS and the neutron activation methods exhibited better performance. Other methods were developed for the speciation of antimony (V39) and for the determination of thallium in soils (V40). Other developments in the determination of heavy metals in soils and sediments were reported (V4l-V44). A review of the suitability of the ammonium acetate extraction method to predict heavy-metal availability was prepared by Del Castilho (V4l). Other papers examined the speciation of heavy metals. In a BCR study, it was established that diverse procedures could be harmonized into agreed methods (V42). Metal speciation was also performed by using total-reflection XRF spectrometry (V43). In another investigation, the determination of heavy metals in sediments by using neutron activation and P E E were compared (V4'44). Radiochemical Species. Several studies examined methods for the determination of radiochemical species in soils and sediments (V45-V49). In one investigation, a formula was obtained and experimentally veritied for evaluating the a-radioactivity of soils by using track detectors (V45). In another study, results from field analyses of uranium in soil by in situ laser ablation-ICP/ AES technique were generally in good agreement with results from laboratory determinations (V469. Wu found that various conditions were needed for the determination of medium-lived radionuclides in soil by neutron activation methods (47). D'Silva compared the use of HC1gas for the remote dissolution of uranium in soil with microwave digestion (V48),and Tagami reported a simple method for the determination of 99Tc in soil by using ICPMS (V49). Miscellaneous Methods. Duckworth analyzed soils by using glow discharge mass spectrometry (V50). The method produced variable results for some metals but was generally suitable for rapid-screening applications. Sample preparation only required grinding, drying, and mixing the sample with a conducting host material prior to electrode formation. Wisbrun has been develop ing new methods for heavy metals in soil based on laser plasma spectrometry (V5l). For the application of time-resolved optical emission spectrometry from laser-induced plasma to the deter-
mination of metals in solid samples, detection limits in the 10pg/g range were obtained. A rapid, on-site method for screening hazardous metallic wastes was reported, based on the use of a field-portable XRF analyzer (V52). Ivanova reported on the application of the extraction system ammonium tetramethylenecarbodithioate/isobutyl methyl ketone to elements in soil digests (V53). Good results were obtained for the simultaneous preconcentration of As,Cd, and 1, followed by determination by AAS. Organic Analytes. Petroleum Hydrocarbons. The detection of total petroleum hydrocarbons (TF'Hs) and BTEX (benzene, toluene, ethylbenzene, and xylenes) continues to receive much attention. Supercritical fluid extraction was employed in some studies (Wl, W2). In one investigation, 14 laboratories participated in a round-robin study of proposed EPA methods 3560 and 8440, which involve SFE followed by IR spectrometry analysis (Wl). Mean recoveries of petroleum hydrocarbons were good, and the overall method accuracy for a wide range of concentrations was 82.9%. In another study, TPH results by using SFE were comparable or better than results using conventional extraction methods, but with SFE the use of Freon-113solvent was reduced by more than a factor of 10 (W2). The use of Freon solvent for TPH determinations can also be eliminated by using GGFID measurements (W3). GC combined with flame ionization and photoionization detectors can also be used on-site by adopting a jar headspace procedure (W4).Reported on-site TPH methods include the use of portable IR instrumentation (W5) and a rapid immunoassay system (W6). One paper warned of the possible false positive detection of BTEX compounds with EPA method 8020 (W7). For on-site applications, it was recommended that the use of method 8020 be supplemented with EPA method 8240. Various aspects of the sampling and analysis of soils for TPH and BTEX were discussed in other contributions (W8-Wll). Polycyclic Aromatic Hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs) received a great deal of interest since the previous review of this series. A number of researchers evaluated the use of SFE to extract the PAHs from soil and sediment samples (Wl2-Wl6). While C02 is less efficient for the heavier PAHs than other extractants such as NzO and Freon-22, its deficiency was remedied by using a mixture of water, MeOH, and CHzCl2 as modifiers and by adjusting other experimental conditions (Wl2). By optimizing SFE extraction parameters, followed by HPLC detection, a precision of about 10%RSD was achieved for 15 PAHs (Wl3). SFE methods can give recoveries comparable to Soxhlet extraction methods, even for soils with a high carbon content (Wl4). By using dichloromethane as a static modifier, 20-30 min SFE extractionsgave results comparable to those from conventional 4 h sample preparation methods (Wl5). In one study, better recoveries of PAH after SFE were obtained by using liquid/solid traps rather than analyte trapping in pure organic solvents (Wl6). A new, efficient method of extraction for PAHs in soil included an organic solvent extraction and a methanolic hydrolysis (saponification) of the soil (W17).Significantly higher quantities of organics were recovered compared to the use of only an organic solvent extraction. In a separate study, Soxhlet extraction plus saponification (and silica gel cleanup) also provided the best recoveries in sewage sludge-amended soils (Wl8). An ELISAbased rapid field screening procedure for PAH was reported (W19).Detection limits were 1 ppm PAH in soil, and the test detected the 3- and 4ring PAH, and most of the 5 and &ringed
PAH, with minimal matrix effects. Improvements in the removal of interferences for PAH determinations were also reported in another investigation, where an LC cleanup based on complexation between PAHs and silica with chemically bonded 2,4dinitroaniline was used, followed by G U M S detection (WZO)). An HPLC/ fluorescence system for rapid screening of petroleumrelated aromatics was found to give results comparable to those from GC/ MS analysis (W21).By application to sediments impacted by the Exton Valdez oil spill, differences in the HPLC chromatographic patterns among sediments suggested different sources of contamination (i.e., crude oil or diesel fuel). A new method of PAH analysis from contaminated soils involved use of laser desorption, laser photoionization time-of-flight mass spectrometry (LWFMS) (W23.Because this method can be applied directly to soils without extensive extraction and cleanup procedures, it has great potential as an on-site screening tool. Other contributions described PAH determinations by using luminescence spectroscopy (W23) and by adsorption and reversed-phase thin-layer chromatography (W24). Organochlorines (PCBs,Dioxins/Furans). In a series of papers that examined the sources of errors in the determination of PCBs in soil, better results were obtained by more polar extraction solvents and Florisil cleanup (W25).In this interlaboratory study, many laboratories submitted results that were strongly biased by improper calibration procedures (W26).Rapid field determinations of PCBs were made by using thermal desorption GC/MS, and the results were statistically equivalent to results by using laboratory-based EPA standard procedures (W27).Methods for rapid, interferencefree determinationsof PCBs in sulfurcontaining sediments were described (W28). The SFEbased method did not involve any manual cleanup or sample pretreatment. The optimization of SFE for PCBs in sediments was presented in another study (W29). Simple, rapid, and efficient isolation of nono-Chloro-substituted PCBs by using porous graphitic carbon columns was also reported (W30). Several other methods for the rapid determination of PCBs were based on application of immunoassay methods (W3l-W33). For the rapid, on-site determination of 2,3,7,&TCDD for cleanup operations, rapid alumina chromatography followed by bench-top GC/MS gave detection limits of about 3-5 ng/kg on a time scale of 2-4 h (W34). No significant differences were found for the determination of dioxins/furans in sediments between Soxhlet extractions using toluene or methylene chloride/acetone solvents (W35).An improved cleanup procedure for dioxins/furans in sediments and sewage sludge samples was based on a GPC/carbon system (W36). Other Organic Analytes. Other methods for organics in soil included SFE of aromatic amines (W37),pyridine (W38),organic acids and ketones (W39),phenols and cresols (W40),trialkyl and triaryl' phosphates using microwave extraction (W41), VOCs (W42),and entoviruses by using PCR (W43). Herbicides in soil were determined by application of solid-phase extraction techniques (W44),supercritical fluid extraction (W45), and by enzyme immunoassay (W46). Miscellaneous Papen. Soil type affects SFE extraction efficiency; a detailed study of soil parameters affecting the recovery of moderately polar analytes was presented (W47). In a study of sampling strategies, it was found that field sampling variance generally dominated the overall variance, so that improvement in the long-term analytical variance below 20-30% is of little benefit Analytical Chemistry, Vol. 67,No. 12, June 15, 1995
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(W48). Microwave-assisted extraction of organics from soils/ sediments is a viable alternative to Soxhlet extraction and requires smaller solvent volumes; extractions can be performed on the order of 10 min (W49).Effective extractions can also be performed by using s u b and supercritical water as extractant (W50).Toxicity testing of soils and sediments was reported by using the Mutatox (W5I) and Microtox (W52) assays. BIOLOGICAL SAMPLE ANALYSIS APPLICATIONS
Inorganic and Organometallic Analytes. Mercury and Organomercury. Four of the most commonly used wet digestion methods for Hg in fish were evaluated, and the one based on use of the HN03/H2S04 mixture was found to be the best (XI). Subnanogram determination of organic and inorganic Hg was performed by helium microwave-induced plasma-AES (X2). Detection limits were around 10 pg, and organic Hg was determined as the difference between total and inorganic Hg. The simultaneous determination of monomethyl Hg, inorganic Hg, and total Hg by using a procedure based on ethylation, room-temperature precollection, GC separation, and detection by cold vapor atomic fluorescencewas reported (X3). Absolute detection limits for each analyte were on the order of 1pg. Speciation of organomercury compounds was also performed by application of capillary electrophoresis (X4). A rapid method for methylmercury in fish involved sample dissolution in methanolic KOH, aqueous-phase ethylation, cryogenic trapping on a packed GC column, and GC/ AAS detection 0. Improvements to digestion procedures for inorganic Hg and methyl mercury in fish were reported by Gutierrez W6). Other methods for mercury speciation include the extraction of methlymercury as bromide from fish samples by chloroform (X7) and by an improved HPLC procedure (X8). Arsenic and Organotin. Arsenic species in fish were determined by direct coupling of HPLC to ICPMS (X9). A similar approach was taken by Le and cc-workers, who noted that changes in arsenic speciation occurred in sample extracts stored at 4 "C for 9 months @IO). Organotins were determined in biological samples by SFE, followed by LCACPMS detection W I ) . Reproducible extractions were completed within about 15 min, although recoveries were only 44% for tributyltin and 23% for triphenyltin. In another approach, butyltin compounds were converted into volatile hydrides by sodium tetrahydroborate, followed by cryogenic trapping, and then selective volatilization and on-line quartz furnace AAS ( X I Z ) . Miscellaneous. Multiple analytes in biological reference materials were determined by radiochemical neutron activation analysis (X13). High accuracy was achieved at subnanogram per gram concentrations. Accurate multielement determinations can also be made by using isotope dilution ICPMS 034). Trace elements in biological tissue samples were completely released after only 20 min of digestion with nitric acid at 105 "C ( X I @ . Rapid acid digestions were also obtained by using microwave oven heating (XIS>.
Organic Analytes. OrganochlorineAnalytes (PCBs,Dioxins, Toxaphene, Other). Many studies of the determination of PCBs in fish and other biological samples were reported (Xl7-X22). A vacuum drying procedure was developed that compares favorably with sodium sulfate drying but is more automated and less labor intensive (Xl7). A novel microextraction technique that uses 100 pL total extraction volume was developed for marine benthic Copepods WI8). Quantitation of PCBs could be per240R
Analytical Chemistry, Vol. 67,No. 72, June 15, 1995
formed for sample sizes in the order of 25 pg dry tissue weight. Rapid screening of PCBs in fish was also accomplished by using a matrix solid-phaseextraction procedure with GC-ECD detection (XI9). Isomer-specific determination of selected PCBs was described in several other reports (XZO-DZ). King reported a rapid screening method for dioxins/furans in fish, based on saponification,hexane extraction, GPC and sulfuric acid cleanup, and detection by high-resolution GC/low-resolution MS (323). At concentrations above the detection limit, results were comparable to those from high-resolution MS. In another method for dioxins/furans, fish samples were blended with anhydrous sodium sulfate, packed in a glass column, and the lipid fraction was eluted with methylene chloride 0 . Lipids were removed from the extracts by size exclusion chromatography, followed by acid/base silica chromatography and HPLC on basic alumina and activated carbon. The analytical methods used for a US. EPA national survey of dioxins/furans in fish were described by Marquis 0 . Other papers on the determination of the polychlorinated terpheand toxaphene (X27-X29) were also presented. nyls MiscellaneousApplications. Laser-excited Shpol'skii spectroscopy was used to determine benzo[a] pyrene metabolites in fish bile (X30). Detection limits were 0.005 ng/mL. By using synchronous fluorescence spectrometry, a screening method for the biomonitoring of PAH exposure was developed, in which a completed analysis could be performed within only 3 min (X31). Ariese reviewed the application of fluorescence spectroscopy techniques to the determination of PAH and PAH metabolites in marine samples (X32). In another review, Wells discussed the application of SFE to the determination of organics in aquatic sediments and biota (X33). Supercritical fluid chromatography was shown to be an excellent technique for the analysis of fish oils (X34).The SFC method did not require prior treatment of the fish oil, unlike GC- or HPLC-based methods. Other contributions included a method for the determination of methylsulfonylPCBs (X35), the determination of plant volatiles by thermal desorption (X36),and the large-scale dialysis of sample lipids by using a semipermeable membrane device (X37). QUALITY CONTROL, STANDARDS, AND DATA ANALYSIS
Quality Control and General Discussion. A recent book (Y1)and several reviews (YZ-Y6) discuss the current status and future trends in quality control for environmental analysis. The uncertainty of results is a simple and efficient means of quanti@ng quality (YZ). One review discussed quality and the need for information, total quality management, quality systems, and interlaboratory studies (Y3). Quality control issues specific to trace elements in biological samples were discussed in another review (Y4). Prasad reviewed quality issues related to environmental contamination assessments (Ys), while Quevauviller discussed the requirements toward accreditation (YQ. Work toward an International Guide for Laboratory Accreditation was reported (YQ,and the aims and organization of proficiency testing schemes in the UK were discussed (Y8). Other reports described the European Community measurement and testing program (Y9), the misuse of screening tests (YlO),historical data comparability when methods are changed (YII),and the relation between LIMS and quality systems (Y12). The extensive quality assessment procedures for serum dioxin/furan measurements in several highprofile investigations were also reviewed (Y13).
Reference Materials. Several reviews of the use of and need for environmental reference materials have appeared (Y14-YI8). Maier covered the use of CRMs, including the requirements for CRMs, suppliers of CRMs, and types of CRMs (Y14). The SRMs issued by the National Institute for Standards and Technology for the determination of organic analytes in environmental samples were described in another review (Y15). The role of CRMs (Y16) and their use in resolving different results between laboratories (Y17)were also reviewed. The tasks and organization of the CII (a group of 30 laboratories), which includes the preparation of reference materials, were reviewed by Daniel (Y18). The theory for intralaboratory accuracy validation of a technique, with the use of reference materials, was presented by Kuselman (Y19). Special problems in achieving adequate quality assurance are faced by developing countries (YZU). Problems with the stability of reference materials were discussed by Faure (Y21). The adequacy of reference materials and associated measurement errors was examined in another study (Y22). Other papers concerning reference materials have discussed the issues of global harmonization (Y23), the international database of reference materials, C O W (YZf),and experiences of the BCR in CRM preparation (Y25). Specimen banking is growing in importance, and recent activities in the United States (Y26), Sweden (Y27), Germany (Y28),and France (Y29) have been discussed. The preparation methods for biological samples in the German specimen bank were described in another paper (Y30). The preparation of new reference materials for trace elements in biological matrices (Y31), benzene/toluene/m-xylene (Y32), neutron activation analysis (Y33),dioxins/furans (Y34),PAHs (Y35),and PCBs (Y36)have been reported. Projects of the BCR for the improvement of the quality of environmental measurements, including preparation of new reference materials, have been reviewed (Y37). Environmental Data Analysis. The ellipse was used for the graphical comparison of interlaboratory quality control duplicate data (Y38). Cera reviewed the various modalities of multicomponent analysis, including multilinear regression, nonlinear optimization, and factor analysis (Y39). Automated data interpretation was demonstrated for EPA method 8080 (Y40). An approach was described for the determination of the optimal frequency of quality control analyses, with the view of minimizing the expected cost of measurement (Y41). An overview of the quality control requirements for several EPA organic analyte methods was presented (Y42). A new Bayesian slippage test for the detection of outlying subsamples has been developed (Y43). The treatment of the detection limit and data below the detection limit continues to receive considerable attention. For the correlation of dioxins/ furans with potential precursor compounds, values below the detection limit were replaced by a number smaller than the minimum of detected concentrations (Y44). In another investigation, regression methods were chosen that could accommodate left-censored data (Y45). Haas recommended the use of maximum likelihood estimation to replace nondetects in regression models (Y46). Determination of the method detection limit by using the US. EPA method was examined by 160 laboratories for metals in soil (Y47). It was found that the method produced accurate and precise results only in interference-free conditions. In a separate study where PCBs were tested, about two-thiids of the reported MDLs produced significant errors. Lindstedt discussed various definitions related to the detection limit with
respect to three major agencies (Y48). Fingerprintingpollution sources by use of statisticaltechniques is an important area of study. Rappe reviewed the various dioxin/ furan patterns observed in the environment, with respect to the patterns found in different industrial sources (Y49). Statistical techniques for fingerprinting sources of PCBs were discussed by Hwang (Y50). Pattern recognition for the analysis of complex mixtures was accomplished in another study by using a multiple reference peak identifkation method and outlier statistics (Y51). Principal component analysis of environmental data showed that the majority of dioxidfuran contamination from a polluted area is the result of contamination from several industries (Y52). Pattern recognition methods were also used to sourcetype jet fuels (Y53). Other reports included a method for accounting for method changes during long-term monitoring projects, which otherwise may preclude trend analysis for the entire data set (Y54). A nonstatistically based scoring system was described to evaluate interlaboratoryperformance for dioxins/furans in fish tissue (Y55). The use of fuzzy clustering analysis in environmental impact assessment was discussed (Y56). A new approach for evaluating analytical data, based on gnostical theory, was described (Y57). Whitfield discussed the need for quality assurance for electronic data acquisition (Y58). The quality assurance required includes sensor validations in the field, time controls for data loggers, and determination of the precision and accuracy of sensors over time. TOXICITY TESTING, BIOMONITORING,AND BlOlNDlCATORS
Many studies have been reported in which some feature of a plant or animal species was used to indicate environmental pollutants. In the previous reviews of this series, we have attempted to present a representative selection of these. However, it seems as though almost any species in a specified area can be used for this purpose, by measuring the concentration of a pollutant or some change in the plant or animal (i.e., enzyme induction). Therefore, this year our coverage is much more selective, as we concentrate on reviews, development of tests with general applicability, and associated papers that discuss the state and future directions of this aspect of environmental analysis. Although studies in this area are of increasing importance, this form of environmental analysis will not reach maturity until the use of results from toxicity tests become widely used as the basis for regulatory action. Major reviews have appeared in which the topics of monitoring environmental genotoxicants (ZI), use of biomarkers in quantitative risk assessment (E!), biomonitoring @3),and selection of bioindicators for marine pollution monitoring programs (24) are extensively covered. Specific reviews on the monitoring of heavy metals in soils by higher fungi (25),the use of mammals as indicators of human exposure (26),the detection of genotoxicity in air and water by using Tradescantia plants (29,and the use of invertebrate organisms as biological indicators of heavy-metal pollution (28) have also been presented. The role of plants as biomonitors was discussed by Gregson (29). A framework for the use of indicator species in the Environmental Monitoring and Assessment Program of the United States, including the linkage between indicator selection and successful assessment, was presented by Hunsaker (210). The reliability of quantitative toxicity test results was examined in another study (211). Analytical Chemistfy, Vol. 67,No. 12,June 15, 7995
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Table 17. Technology Cross=ReferenceTable technology/method supercritical fluid extraction (SFE) solid-phase extraction (SPE) liquid chromatography, HPLC ion chromatography mass spectrometry methods atomic absorption spectroscopy (AAS) infrared spectroscopy (IR, GC/IR, FT-IR, etc.) inductively coupled plasma (ICPMS) fielaremote methods sampling immunochemical methods
papers in review with reference to technology/method A5, A6-A8, C34, N21, Q9, V23-V24, W2, W12-Wl6, W28, W29, W37-W40, W45, W47, W48, X11, X33, X34, BB7, BB8 A4, A5, K16, L65, N21-N23, N25-N27, R22, S92-S99, S103, S104, S143 A l l , A16, A32, A33, B6, E112-El15, H9, H16,112, L63, L64, N26, N9, P14, P28, Q9, S28, S33, S62, Sll8,S119,S123,V19, W21,X9,XlO,BB15, BB16 L26-L28, N14, P1, S43, S44, S45 A12, A34-A39, B20, C1, C2, C31, C32, C41, D13, E14, E120-E123,113, K21, L65,N31, N32, S42, S117, S132-Sl45, V28, W22, BBP, BB18 A40, A41, C50,E136, H7, H10, N8, N11, N 1 5 , 0 1 7 , 0 1 8 , 0 2 6 , 0 3 3 - 0 3 5 , P18, P31, S28-S30, S58, S66, S69, S86, V18, V33, X12 AP.Cl0. Cll.El26. K19. P26.R31. S38. W5.BB4 A40, A43, F5,H8,14,15, K20,01, N9, N12, 025, 036,039, P20, P30, S34, S35, S64, S65, S68, T17, V36, V38, X9, X10, X14, BBlO A2, A17, A29, A37, B23-25, E126, F2, F3,54, L1,04-07, R29, V52, W5, W7, W19, W34, BB1, BB2 A3, E28-E69, C25, C27, E8, E l l , E127, E149, E150, G4, H1, H2, J1, L2-L4, L51, L55,L56, M10-M23, M38, Ul-U11 A10, A52, R16, R21, R22. R24, W6, W19, W31-W33
Table 18. Analyte Cross-Reference Table analyte mercury. organomercury lead, organolead tin. organotin arsenic chlorinated dibenzo-p-dioxins (dioxins)/ dibenzofurans (furans) polychlorinated biphenyls (PCBs) polycyclic aromatic hydrocarbons (PAHs) volatile organic compounds (VOCs) radionuclides
papers in review with reference to analyte C22,C23,C46-C49,H2,L25,024,041,P18,P19,P30, P31,R18, S63-S71,
V18-V22, Xl-X8 D18,D23, E19-E21, E78,E79,E81,E141,E142, L32,N4, N13,N15-16,038,039, S40, S78-S80, S82, V29-V32, BB12 K8,L61,045,046, SlS,V23-V28,Xll, X12 A27, M25, N9,031-033,041, S17, S18, S42, V33, V34, X9, X10, BB15- BB17 A20, A21, C25-C35, E9, E17, E106, H16, L54, L55, M34,Q6, T10, W34, W36, X23-X25 A22, E9, E69, E158-E161, H16,112,115, L53, L55, L56, M34,042, 48, S99, S100, W25-W28, W30, X17-X22, BB2, BB3, BBlO, BB18 A16-Al9, B11, C1, C17-Cl9, C36-C40, C43, D10, D24, E2, E6, E9, E99-E102, E107-E109, E112-E116, E156, E157, H15,116,120,47. S100, S105, S120, S121, S129-Sl31. W12-Wl6. W17. W20 W22 C2, C16, E3, E16, E71,E95’E98, E122, E126-El28, E130, E148, E153, F2, F3, L57, M37, M38, P25, X36 A26, B7, B8, C14, C55,C56, E22, E82-E84, Gl-G3, H13, L33, M33, N19,08- 012, P15-P17,05, S84, S90, V40, V45-V49, AA1-AA19. BB14
Consideration of statistical aspects of toxicity testing should receive more attention within the framework of standardization. The use of a multitiered framework has been proposed, in which indicators are selected as diagnostics to screen sites with increasing specificity (212). The basic strategy presented is applicable to a wide range of environmental monitoring programs. In a comparison of GC/MS determination of dioxin toxicity equivalents with results from an Ah receptor assay of trout and fly ash, lower results were found by the GC/MS method @I3). Correlation of toxicity tests with results of direct chemical analyses is an area where much additional work is required. Eklund described a 7-day reproduction test with the marine red alga Ceramium strictum (214). Advantages of this short-term test are that it is sensitive, the time needed to perform the test is short, and the test parameter is easily recognizable. In another investigation, tree ring analysis was found to be suitable for the retrospective evaluation of tritium fallout (215).Harkey studied the bioavailability of representative neutral hydrophobic contaminants in whole sediments and in aqueous extracts of whole sediment (elutriate and pore water) (21s). It was concluded that the bioavailabilityof the contaminants they tested cannot be accurately predicted in bioassays that expose organisms to aqueous representations of whole sediment. RADIONUCLIDES
Papers that describe the determination of radionuclides are included in earlier sections, depending on the matrix being tested (Le., air, water, or soil). Here we include contributions in which radiochemical methods are used for “general environmental 242R
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determinations” and for other matrices. Two reviews were published that cover this area in significantly more detail than is presented here (AA1, AA2). In another review, nonradiometric analytical techniques for the determination of long-lived radionuclides were described (AA3). An expert system for the quality control of environmental radioactivity measurements was described 0. Implementation of a quality assurance scheme in preparation for the accreditation of a radiochemical laboratory was discussed in detail by Pang (AA5).In a recent intercomparison exercise involving about 100 laboratories, most achieved satisfactory results (AA6). The reference materials available for the determination of radionuclides were reviewed by Strachnov W7),and the advantages of using neutron activation methods for the standardization and study of reference materials were described (AA8). A number of contributions described the methods needed to study the environment in and around nuclear plants or as a result of accidents (AA9-AA13). For environmental measurements after accidents, detection limits are not an issue (AA9). The speed and selectivity of analysis are more important considerations. The determination of plutonium-239 and -240 around a nuclear plant, and assay procedures for uranium in crude diuranate cakes produced at a natural uranium conversion plant (AAII),have been described. Methods for environmental analysis associated with the decommissioning of a nuclear power plant were discussed by Testa (AA12). Carbo1 described methods used for the speciation of y-emitting radionuclides observed in soil and water samples contaminated by the Chemobyl fallout (AA13).
In miscellaneous applications, a low-cost a-particle sensor system for Rn and Rn daughter monitoring and dosimetry was presented (AA14). McMahon described the use of various analytical methods based on X-ray spectroscopy for the determination of low levels of radionuclides W15).X-ray methods are relatively insensitive compared with mass spectrometric techniques but are suitable for the determination of long-livednuclides such as 23zrhand 238U. A new method for the rapid isolation of strontium radionuclides from environmental samples was described by Kremlyakova, based on the selective extraction of strontium with a solution of dicyclohexyl-l&rown-6 in tetrachloroethane from nitric acid solution (AAI6). Plutonium was isolated from environmental samples by a procedure that included an electrodepositionstep (AAI7). Harvey reported on an investigation to establish the lowest practical level at which aemitting plutonium and americium nuclides may be quantified based on a-spectrometry (AAI8). Amounts as low as 10 pBq can be determined,if counting times as long as 10 weeks can be tolerated. An alternative to radiometric methods for technetium-99, based on ICPMS, had the advantage of freedom from interferences caused by ionizing emissions from other radionuclides present in environmental samples (AA19).In addition, the ICPMS method could acquire data on the order of 1 min (after sample preparation), compared to several hours for radiometric determinations. MISCELLANEOUS APPLICATIONS
A fully self-supported mobile screening unit for site and waste characterization was described (BBI). Rapid, on-site screening for PCBs in environmental samples was based on room-temperature phosphorescence (BBZ). In another study, a screening technique for PCBs in waste oils involved extracting the PCBs from the oil samples, initiating a dechlorination reaction, and then using an amperometric detector to measure C1- (BB3). M a characterized the organic compounds in industrial composts by GUMS and IR (BB4). Static headspace GC was used to analyze dissolved gases and furan-related compounds in power transformer oils (BB5). The determination of organic solvents from industrial sludges was discussed by Ceccon (BBS). Supercritical fluid extraction was applied to diesel fuel (BB7) and for the extraction of PAHs from heterogeneous samples (BB8). In the latter study, it was stated that spike recovery studies are not valid for developing quantitative extraction methods for heterogeneous environmental samples. Other miscellaneous applications include a study of isotope dilution glow discharge mass spectrometry for lead in waste oil samples (BB9), the use of electrothermal vaporization ICPMS for PCBs in waste oil (BBIO), and a study of the multivariate analyses of trace element patterns for environmental tracking (BBII). Miscellaneous Speciation Studies. Reviews of speciation methods include the speciation of organolead compounds by GC with atomic spectrometric detection (BBIZ), the use of GC with element-specilk detectors for speciation studies (BB13), and a large review of speciation of radionuclides in the environment (BBI4). Speciation methods for arsenic based on liquid chromatography (BBI5),HPLC (BBI6) and by coprecipitation with zirconium hydroxide (BBI7) have been reported. Speciation of PCB congeners was performed by using multidimensional GCNCI/mass spectrometry (BBI8) and by using active coal columns (BB19).
TECHNOLOGY AND ANALYTE CROSSREFERENCE
Tables 17 and 18 list key technologies and analytes, respectively, and the associated citations in this review where these were central to the reported study. These tables are included to allow readers to quickly access information concerning these technologies and analytes, regardless of the environmental application. Most of the major papers are included in these tables, but they are not comprehensive. Gas chromatography was not included as a heading in Table 17, because so many of the reported environmental analysis applications employed GC techniques. R a E. Clement is Senior Research Scientist with the Ontario Ministy
of &vtronment and Enera, Luborato Services Branch. He graduated with his Ph.D. from the University of $terloo in 1981. He has published over 100papers and reports concerning the determination of toxic organics in the environment, most related to the GC/MS determination of ultratrace concentrations of the chlorinated diozins/furans, and he is currently working.on h+ fifth book. He h+s tau ht undergraduate and graduate cources in environmental analysts a n k s Adjunct Professor at the Universi of Western Ontario and Carleton University. Dr. Clement is active in tre Environmental and Analytical Divisions of the.Canadian Society for Chemisty, and ako serves on the Board of the Azr & Waste Management Association- Ontario Section.
G a A. Eiceman is a professor in the Department o Chemist and Bioxemisty at New Mexico State University in Las Jruces, Ni$ He received his Ph.D. in 1978 at the University of Colorado, Boulder, CO and was a postdoctoral fellow at the University of Waterloo, Ontario, Canada, from 1978 to 1980. In 1987-88, he was a Senior Research Fellow at the (now) Edgewood Research, Develo ment and Engineering Center, E ewood, MD, where he was a NationaIResearch Councilfellow in 1992. %e ISalso an invited lecturer at the Universidad Autonoma de Chihuahua. He has authored or coauthored over 100 research articles, reviews, or chapters and a book, Ion Mobility Spec!romety (CRC Pres$. He teachesfrom freshman through graduate level an chemlsty, quantitative analysis, separations, and electronics. Carolyn J. Koester is a research chemist with the Anal ical Sciences Division of Lawrence Livermore National Laboratoy. S$ received her Ph.D. from Indiana University in 1991, where she studied the atmospheric fate a.nd deppsition of chlorinated dioxins andfurans under the direction of Dtstingulshed Professor Ronald A. Hates. Dunng a ostdoctoral appointment with Trent University and Ontario .Ministy of kvironment and Energy, she studied environmental appl?cations of particle beam LC/ MS and ion traps. Dr. Koester's current interests include the study of extraction and mass spectrometric techniques for the determination of polar organic compounds in water, the identajkation of refigerant decomposition roducts, ap ltcations of capillay electrophorests, and the development olchemisty Amonstrations for public schools. LITERATURE CITED GENERAL REVIEWS
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Marin, S.R.; Olave, S.G.; Andonie, 0. E.; Arle i, 0. G. Int. bEnviron. Anal. Chem. 1993,52(1-4), 127-$! alyschew, A; Schmidt, H.J.; Weil, IC G.; Hoffmkn, P. Atmos, Environ. 1994, 28(9), 1575-81. Abbas, M. Z. M.; Bruns, R. E.; Scarminio, I. S.; Ferreira, J. R. Envzron. Pollut. 1993, 1992, 79(3), 225-33. Hoffman, F. 0.; Thiessen, IC M.; Frank, M. L.; Blaylock, B. G. Health Ph s 1992, 62(5), 439-42. Vong, R. J. Jnal. Chim. Acta 1993, 277(2), 389-404. Hewett, C. N.; Gardner, B. Sci. Total Environ. 1993, 135(13). 55-66. --(H16) Bushb , B.; Femandes, A; Wallace, D.; Kibblewhite, M. Sci. Total $nuiron. 1993, 135(1-3), 81-94. (H17) Clarke, J. F.; Ed erton, E.; Boksleitner, R P. Goo. Rep. Announce. Index (ES.) 1992, 92(5), Abstr. 211,066. (HlS) Brown, M. A; Petreas, M. X.; Okamoto, H. S.; Mischke, T. M.; Stephens, R D. Envzron. Scz. Technol. 1993,27(2), 388- I , - -
a7
(H19) Wklin on, T. J.; Sehested, J.; Dearth, M. A.; Hurley, M. D. J. Photocfka. Photobiol., A 1993, 70(1), 5-8. (H20) Heikes, B. G. J. Geophys. Res. IAtmos.1 1992,97@16), 1800113. (H21) Smith, D. F.; Meindienst, T. E.; Hudgens, E. E.; Bufalini, J. J. Int. Envwon. Anal. Chem. 1994, 54(4), 265-81. (H22) Hark , R A.; Cass, G. R. Environ. Sci. Technol. 1994,28(1), 88-9g. (H23) Ciccioli, P.; Cecinato, A; Cabella, R.; Brancaleoni, E. Atmos. Eviron., PartA 1993, 27A(8), 1261-70. BiomonitoringIBioassays
:elos, M. T.; Tavares, H. M. NATO ASI Seru., Ser. A
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G. IARC Sci. Publ. 1993, No. 109(12 , 353-76. S.; Louis, J. B.; Rosen, J. D. J. A 0 C Int. 1993, 76(5), 1121-6. (E160) Balfanz, E.; Fuchs, J.; Kieper, H. Chemosphere 1993,26(5), 871-8n
(E161) Yamashita, T.; Haraguchi, IC; Kido, A; Matushiita, H. J. Chromato r 1993, 657(2), 405-11. (E162) Kawata, F!;'Minagawa, M.; Fu'ieda, Y.; Yasuhara, A J. Chromatogr. 1993, 653(2), 369-74. Air Emissions from Waste and Waste Sites
(Fl) U S . EPA, US.Environ. Prot. enc OffAir Qual. Plann. Stand., [Tech. Rep.] EPA 19935P2451iR-03408. (F2) Minnich. T. R: Scotto. R L.: Leo. M. R.: Solinski. P. 1. Sambling Anal. Airborne Pollut: 1993, 247-55,' (F3) Berkle , R. E.; Miller, M.; Chan ,J. C.; Oliver, IC;Fortune, C. Gov. Jeb. Announce. Index . . 1993. 93(14). . . . Abstr. 341,052.(F4) Kitsa,V.; Lioy, P. J.; Chow, J. C.; Watson, J. G.; Shu ack S.; Howell, T.; Sanders, P.Aeroso1 Scz. Technol. 1 9 9 2 , 1 7 & ) ,2i3~I
I
_
I
"
(8,s.)
29
(F5) $mer, A. V.; Feldmann, J.; Go el, R.; Rapsomanikis, S.; Fischer, R.; Andreae, M. 0. ApppOrganomet. Chem. 1994, 8(1), 65-9. (F6) Pauley, B. J.; Maxwell, D. R Proc., Annu. Meet.-Air Waste Manage. Assoc. 85th 1992, (2B), Paper 92/75.18. Accidents and Emergencies
(Gl) Lyul, A Yu.; Kolesov, G. M.; Cherkezyan, V. 0.2%.Anal. Khim. 1993, 48(10), 1683-9. (G2) Vapirev, E. I.; Hristova, A V.J. Environ. Radioact. 1993,20(1),
Bruening, F.; Kreeb, IC H. Plants Biomonit. 1993, 295-401. Steinnes, E.; Johansen, 0: Roe set, 0.;Oedegaard, M. Environ. Monit. Assess. 1993,25(2), ST-97. Pilegaard, K. Environ. Monit. Assess. 1993, 27(3), 221-32. Tuba, Z.; Csintalan, 2. Plants Biomonit. 1993, 403-11. Loppi, S.; Chiti, F.; Corsini, A.; Bernardi, L. Environ. Monit. Assess. 1994, 29(1), 17-27. Sloof, J. E.; Wolterbeek, B. Th. Environ. Monit. Assess. 1993, 25(2), 149-57. Quevauviller, P.; Van Renterghem, D.; Muntau, H.; Griepink, G. Int. J. Environ. Anal. Chem. 1993, 53(3), 233-42. Gonzalez, M.; Carmen, M.; Tenorio, T.; Antonio, M. Proc. APIEInt. Soc. Opt. Eng. 1993, 1716, 188-98. Lawrey, J. D. Byologzst 1993, 96(3), 339-41. K lin, H.; Grimvall, E.; Oestman, C. Environ. Sci. Technol. 1694,28(7), 1320-4 Franich, R. A; Jakobsson, E.; Jensen, S.; Kroese, H. W.; Kylin, H. Fresenius'J. Anal. Chem. 1993, 347(8-9), 337-43. Calamari, D.; Tremolada, P.; Di Guardo, A.; Vighi, M. Environ. Sci. Technol. 1994,.28(3), 429-34. Granier, L.; Chevreuil, M. Water,Air, Soil Pollut. 1992, 64(34), 575-84. Sturaro, A; Parvoli, G.; Doretti L. J. Chromatogr. 1993,643(12)., 435-8. -, -_- -. Capannesi, G.; Cecchi, A; Ciavola, C.; Sedda, A. F. J. Radioanal. Nucl. Chem. 1993, 167(2), 309-20. Robin, D.; Martin, M.; Haerdi, W.Arch. Sci. 1991,44(2), 25364.
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(121) Pollanen. R Environ. Monit. Assess. 1993. 28(3). 239-54. (G5) Jankovic, J.; Jones, W.; Castranova, V.; Dalal, N. App. Accup. Envzron. Hyg. 1993, 8(7), 650-4. Atmospheric Chemistry, Transport, and Deposition (H1) DeBoer, J. L. M.; Fortezza, F. Water, Air, Soil Pollut. 1992, 64(3-4), 467-74. (H2) Vermette, S.J.; Peden, M. E.; Willou hb , T. C.; Lindberg, S. E.; Weiss, A D. Proc.,Annu. Meet.-% &mte Manage. Assoc. 85th 1992, (2A), Paper 92/69.06. (H3) Baechmann, IC; Haa , I . Roeder, A Atmos. Environ., Part A 1993,27A(13), 195f-8:
321-35. 024) Meindienst, T. E.; Smith, D. F.;,Hudgens. E. E.: Snow. R. F.: Perry, E.; Cl+on, L. D.; Bufalini. J. J.: Bkkk, F. 'M.; Cupitt, L: T. Atmos. Envwon., Part A 11f92,-26A(16), 3039-53. 025) Wants, R R; Lemieux, P. M.; Grote, R. A; Lowans, R W.; Wilhams, R W.; Brooks, L. R; Warren, S. H.; DeMarini, D. M.; Bell, D. A,; Lewtas, J. Envrion. Health Penbeet. 1992, 98, 227-34. AnalyticalChemistry, Vol. 67, No. 12, June 15, 1995
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026) Tepper, J. S.; Costa, D. L. Indoor Enuiron. 1992, 1(6), 36772. Miscellaneous Air Analysis Applications
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I
WATER ANALYSIS APPLICATIONS Reviews and Articles of Broad Interest
(Kl) MacCarthy, P.; Klusman, R. W.; Cowling, S. W.; Rice, J. A. Anal. Chem. 1993, 65(12), 244R-92R. (K2) Noi’ T. H. M.; Schulting, F. L. Water Su ly 1993 11 (1 European Specialized Conference o n g c e n t l y Identified Pollutants in Water Resources: Dnnking Water Treatment in the Nineties, 1992), 59-77. (K3) Jensen, J. N.: Dietrich, A. M. WaterEnuiron.Res. 1994,66(4), 774--91 ”*.
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Barber, L. B., I1 Environ. Sci. Pollut. Control Ser. 1 9 9 2 , 4 (Groundwater Contamination and Analysis at Hazardous Waste Sites), 73-120. Solbe, J. F. de L. G.; Buyle B.; Guhl, W.; Hutchinson, T.; Laen e, R.; Mark, U.; Munk, k.; Scholz, N. Sci. Total Environ. 1998, (Suppl., Pt. l), 47-61. Barcelo, D. J. Chromatogr. 1993,643(1-2), 117-43. Marko-Varga, G. A. Tech. Instrum. Anal. Chem. 1993, 13 (Environmental Analysis), 225-71. D i r k , W. M. R.; Lobinski, R.; Adams, F. C. Anal. Chim. Acta 1994,286(3), 309-18. Goto, K.; Taguchi, S. Anal. Sci. 1993,9(1), 1-7. Nriagu, J. 0.;Lawson, G; Wong, H. K. T.; Azcue, J. M. J. Great Lakes Res. 1 9 9 3 , 19(1), 175-82. Sweeny, M. W. Water Environ. Res. 1993,65(4), 374-7. Goo, R. Water Environ. Res. 1 9 9 4 , 66(4), 298-301. Blatchley, E. R., 111 Water Enuzron. Res. 1 9 9 3 , 65(4), 35360.
(314) Kuban, V. Fresenius’J. Anal. Chem. 1993,346(10-ll), 87381. (K15) Buffle, J.; Perret, D.; Newman, M. Environ. Part. 1992, 1, 171 * . * -71n -””.
Liska, I. Chromatogr. 1 9 9 3 , 655(2), 163-76. Tercier, L.; Buffle, J. Electroanalysis 1 9 9 3 , 5(3),187-300. Goldberg, M. C.; Weiner, E. R. Fluoresc. S ectrosc. [Lect. Conk “Methods Appl. Fluoresc. Spect?osc.’’l 1 9 8 1 , 213-41. Davies, J. E. D. Scz. Total Enuzron. 1993,135(1-3), 145-52. Brenner, I. B.; Taylor, H. E. Crit. Reu. Anal. Chem. 1992, 23(5), 355-67. Cooks, R. G.; Kotiaho, T. ACS Sym Ser‘ 1992, No. 508 (Pollut. Prev. Ind. Processes), 126-&. Nielen, M. W. F. Tech. Instrum. Anal. Chem. 1993, 13 (Environmental Analysis), 607-33.
h.
Surface Water, Rivers, and Lakes
(Ll) Luettich, R A., Jr.; Kirby-Smith, W. W.; Hunnings, W. Estuaries 1993,16(2), 190-7. (L2) Martin, G. R.; Smoot, J. L.; White, K. D. Water Enuiron. Res. 1992, 64(7), 866-76. (L3) Archundia, C.; Bonato, P. S.; Rivera, J. F. L.; Mascioli, L. C.; Collins, K. E.; Collins, C. H. Sci. Total Environ. 1993, 1301 3 1 . 231-6. (L4) Cox, A.G.-McLeod, C. W. Mikrochim Acta 1992, 109(1-4), 161-4. Alvarez, E.; Perez, A.; Calvo, R. Sci. Total Environ. 1993, 133(1-2), 17-37. Fairman, B.; Sam-Medel,A; Gallego, M.; Quintela, M. J.; Jones, P.; Benson, R. Anal. Chim. Acta 1 9 9 4 , 286(3), 401-9. Lu Y.; Chakrabarti, C. L.; Back, M. H.; Gregoire, D. C.; Schroeder, W. H. Anal. Chim. Acta 1994,293(1-2), 95-108. Hasegawa, H.; Sohnn, Y.; Matsui, M.; Hojo, M.; Kawashima, M. Anal. Chem. 1 9 9 4 , 66(19), 3247-52. Vidal, J. C.; Sanz, J. M.; Castillo, J. R. Fresenius’].Anal. Chem. 1992, 344(6), 234-41. Nusko, R.; Heumann, K. G. Anal. Chim. Acta 1994,286(3), 283-90. Parthasarathy, N.; Buffle, J. Anal. Chim. Acta 1993,284(3), 6A4-5-9 V _ ”
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(LE) Suutarinen, R.; Jaakkola, T.; Paatero, J. Sci. Total Enuiron. 1993, 130-1, 65-72. (L13) ?Ftosa, S. J.; Sato, J.; Tanaka, S. Anal. Sci. 1993,9(5), 657OL
.
(L14) Billah, M.; Honjo, T.; Terada, K. Anal. Sci. 1993,9(2), 2514. (L15) Nakamura, T.; Oka, H.; Ishii, M.; Sato, J. Analyst 1994,119(6), 1397-4ni - - - . - - -.
(L16) Beazley, P. I.; Rao, R. R.; Chatt, A. J. Radioanal. Nucl. Chem. 1 9 9 4 , 179(2), 267-76. (L17) Yebra-Biurrun, M. C.; Bermejo-Barrera, A; Bermejo-Barrera, P. Mikrochim. Acta 1992, 109(5-6), 243-51. 248R
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(L18) Burba, P.; Rocha, J. C.; Schulte, A. Fresenius’J. Anal. Chem. 1993,346(4), 414-9. (L19) Cres 0 , M. T.; Gascon J. L.; Acena, M. L. Sci. Total Enuiron. 1998, 130-131, 383-L91 WO) Godoy, J. M.; Guimaraes,’J. R. D.; Carvalho, Z. L. J. Environ. Radtoact. 1 9 9 3 , 20(3), 213-9. W1) Favel, J.; Vrchlabsky, M.; Kohn, Z. Talanta 1992,39(7), 795J.
Mohammad, B.; Ure, A. M.; Littlejohn, D. J. Anal. At. Spectrom. 1 9 9 3 , 8(2), 325-31. Freeman, P. R.; Hart, B. T.; McKelvie, I. D. Anal. Chim. Acta 1 9 9 3 , 282(2), 379-88. Sagara, F.; Tsu’i, T.; Yoshida, I.; Ishii, D.; Ueno, K. Anal. Chim. Acta 1992,2$0(1), 217-21 Sarzanini, C.; Sacchero, G.; Aceto, M.; Abollino, 0.;Mentasti, E. Chromato r. 1 9 9 2 , 626(1), 151-7. I e k a s , C. A. Analyst 1 9 9 3 , 118(8), 1035-41. Shotyk, W. J. Chromatogr. 1 9 9 3 , 640(1-2), 309-16. Shotyk, W. J. Chromato r. 1 9 9 3 , 640(1-2), 316-22. Chow, C. W. IC;Davey, . E.; Mulcahy, D. E. Anal. Lett. 1994, 27(1), 113-30. Valencia, M. C.; Gimeno, D.; Capitan-Vallvey,L. F. Anal. Lett. 1993,26(6), 1211-26. Moulin, V.; Tits, J.; Moulin, C.; Decambox, P.; Mauchien, P.; De Ruty, 0. Radiochim. Acta 1.992,58-59(Pt. l), 121-8. Cheam, V.; Lechner, J.; Desrosiers, R.; Sekerka, I.; Nna , J.; Lawson, G. I n q Environ. Anal. Chem. 1993 53(1), l v 2 7 Gromov, A ., Kopchenov, V. E.; Krivokhatskiy, A. S.; Nikolaev, V. A; Stolyarov, S. V.; Tokarevski , V. V.; Pautov, V. P. Nucl. Tracks Radiat. Meas. 1993,21(31, 377-82. 034) Shiraishi, K; Nakajima, T.; Takaku, Y.; Tsumura, A.; Yamasaki, S.; Los, I. P.; Kamarikov, I. Y.; Bizinny, M. G.; Zelensky, A. V. J. Radaoanal, Nucl. Chem. 1 9 9 3 , 173(2), 313-21. Hwang, C.; Jian , S. Anal. Chzm. Acta 1994,289(2),205-13. Yamagaki, K.; foshii, M.; Yamada, K. Anal. Sci. 1993,9(3),
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O%a,k.; Naka’ima, N.; Inui, S.; Winefordner, J. D.; Mizuno, T. Talanta 1 9 9 2 , 39(12), 1643-5. Fung, W. S.; Sham, W. C. Analyst 1994, 119(5), 1029-32. Janjic, J.; Kiurski J. Water Res. 1994,28(1), 233-5. Jian, W.; McLeod, C. W. Talanta 1 9 9 2 , 39(11), 1537-42. Colodner, D. C.; Boyle, E. A.; Edmond, J. M. Anal. Chem. 1 9 9 3 , 65(10), 1419-25. Haraldsson, C.; Pollak, M.; Oehman, P. J. Anal. At. Spectrom. 1 9 9 2 , 7(8), 1183-6. Brondi, M.; Gragnani, R.; Pros en, M. Ap 1. Zeeman Gra hite Furn. At. Absorpt. Spectrom. Ciem. Lab. #oxicol. 1992, !43A4
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(L44) Mktinezirre, A.; Garcia-Leon, M.; Ivanovich, M. Nucl. Instrum. ethods Phys. Res., Sect. A 1994, 339(1-2), 287a?
(L45) Kolezel, P.; Kahle, V.; Krejci, M. Fresenius’ J. Anal. Chem. 1 9 9 3 , 345(12), 762-6. L46 Farias P. A. M . Takase I. Electroanal is 1992,4(8), 823-8. ha71 Kawdubo, S.; h a n g , B.; Iwatsuki, Fukasawa, T. Analyst 1 9 9 4 , 119(6), 1391-5. (L48) Paukert, T.: Sirotek, Z. Chem. Geol. 1 9 9 3 , 107(1-2), 133-
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(L49) Pikine, M.; La Noce, T.; Liberatori, A. Ap 1. Zeeman Gra hite [urn. At. Absorpt. Spectrom. Chem. Lab. #oxicol. 1 9 9 2 , !65I I.
Ihnat, M.; Gamble, D. S.; Gilchrist, G. F. R Int. J. Environ. Anal. Chem. 1993,53(1), 63-78. Pearson, R. F.; Kin P. A; Holmes, M. W.; Eisenreich, S. J.; Swackhamer, D. L. %atL Meet.-Am. Chem. Soc., Diu. Environ. Chem. 1993,33(1), 441-4. Foster, G. D.; Gates, P. M.; Foreman, W. T.; McKenzie, S. T.; Rinella, F. A. Enuiron. Sci. Technol. 1993,27(9), 1911-7. Goetz, R.; En e, P ; Friesel, P.; Roch, K.; Schillin B.; Hartmann, B.; b u n s c h , H. Fresenius’ J. Anal. Chem. f 9 9 4 , 348(10), 694-5. Goetz, R.; En e, P.; Friesel, P.; Roch, K.. Kjeller, L. 0.;Kulp, S. E.; Rappe, Chemos here 1 9 9 4 , 28(1), 63-74. M.; Bums, S. A.; Weismuller, T.; Prest, H. F.; Jarman, TvJrtin, M.; Huckins, J. N. Chemosphere 1992,26(12), 1811-
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@&3) &kenon, J.; de la Guardia, M. Anal. Chim. Acta 1994,287(12), 49-57. Groundwater, Wells, Reservoirs, and Springs
(M1) Mayer, A S.; Rabideau, A J.; Mitchell, R J.; Imhoff, P. T.; M. I.; Miller, C. T. Water Environ. Res. 1993,65(4),
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(M2) Barcelona, M. J.; Helfrich J. A ASTMS ec. Tech. Publ. 1992, STP 1118 (Curr. Pract. Ground Water eadose Zone Invest.),
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