Anal. Chem. 2001, 73, 2761-2790
Environmental Analysis Ray E. Clement* and Paul W. Yang
Laboratory Services Branch, Ontario Ministry of the Environment, 125 Resources Road, Etobicoke, Ontario, Canada M9P 3V6 Carolyn J. Koester
Analytical Sciences Division, Lawrence Livermore National Laboratory, Livermore, California 94551 Review Contents General Trends Review Articles Solid-Phase Microextraction Applications Characterization of Organic Compounds Water Analyses Soil, Sediments, and Pore Waters Air Monitoring Inorganic/Organometallic Compounds Air Monitoring and Analysis Applications General Comments Sampling Volatile Organic Compounds Semivolatile Organic Compounds Inorganic Compounds Chemometrics and Real-Time Monitoring Automated Analysis Deposition and Atmospheric Transport Incineration and Miscellaneous Water Analysis Applications Sample Collection Extraction and Sample Preparation Integrated Extraction and Detection Separation and Detection Analytes of Interest Solid Sample Types Analysis Applications Soils and Sediments: Metals Soils and Sediments: Organics Sewage Sludge: Metals Sewage Sludge: Organics Organometallic Analytes Biota Analysis Applications Radionuclides Quality Assurance, Reference Materials, and Related Topics Biomonitoring and Biomarkers Literature Cited
2761 2766 2766 2767 2767 2767 2767 2767 2767 2767 2768 2769 2769 2771 2772 2772 2773 2773 2774 2774 2774 2775 2775 2777 2777 2777 2779 2780 2780 2780 2780 2781 2781 2782 2782
This review covers developments in applied environmental analytical chemistry from November 1998 to the end of October 2000, as found in the Chemical Abstracts Service CA Selects for gas chromatography, mass spectrometry, inorganic analytical chemistry, pollution monitoring, and environmental pollution. We have coordinated our efforts with Susan Richardson, who prepared the review on Water Analysis for this issue, and therefore have greatly reduced our coverage in areas she has reviewed in detail. As in the previous review in this series (A1), we have not 10.1021/ac0103930 CCC: $20.00 Published on Web 05/01/2001
© 2001 American Chemical Society
attempted to cover industrial hygiene, greenhouse gases, guidelines and regulations, risk assessment, human levels, modeling, commercial products, and food. We emphasize the determination of trace organics, trace metals, and organometallics in real environmental samples. In an ongoing attempt to control the size of this review, we changed our strategy somewhat this year, by focusing on overall trends in environmental analysis, rather on the number of citations in a given area. The citations we use are therefore representative of the current state of the art and should be used by the reader as a starting point for further investigation. However, for readers who wish much more detail, an extensive annotated list of review articles published by others over the past two years is presented in Table 1. In preparing this review, we have noticed that more citations now appear in published conference proceedings than was the case for the first review in this series. Also, some of the key studies reported in proceedings may not appear in published journals at all. We attribute this, at least in part, to our observation that a proportion of environmental publications are generated from industrial and government researcherssfor whom journal publication is often less important than for academic researchers. We also note that although the Internet is not yet a significant source of published papers in the environmental analysis field, it is likely that more information will be disseminated in this manner in the near future. Therefore, the authors believe that those who wish to keep up to date in the environmental analysis field will have to consider all of these sources of information, not just printed journals. In the previous review in this series (A1), we included a table of Internet URLs we believe are of significant value to environmental analytical researchers. Some of these URLs refer to science societies or conference sites where some of the conference proceedings cited here may be obtained. The only addition we wish to make this year is the web site of the International Society for Optical Engineering (SPIE). Many significant advances in chemometrics, sensor technology, and remote and automated environmental monitoring are presented at various SPIE meetings. Published proceedings for many of these meetings can be found through their web site (www.spie.org). GENERAL TRENDS The first review in this series was published in 1991 (A2). Ultratrace methods were considered those that could achieve Analytical Chemistry, Vol. 73, No. 12, June 15, 2001 2761
Table 1. Environmental Analysis Review Articles, 1998-2000 review topic/analyte
no. papers cited or pages published
general
240 pp
general air monitoring remediation
249 pp 160 pp 420 pp
air air
many 16
air air air
45 58 31
air air
106 57
air
17
air air
57 many
air air
22 10
air air
204 165
air
27 pp
air
26
air automobile air solid wastes and leachates
58 25 60 13
water groundwater
672 90
wastewater river water marine water
16 21 27
metals
30
metals
47
supercritical fluid extraction liquid chromatography stripping voltammetry
25 141 117
HPLC-ICPMS
11
atomic spectroscopy capillary electrophoresis ICPMS
many 179 118
SPME metals microwave-induced plasmas phosphorus organometallics
40 199 131
Hg
80
Hg
322
Hg
80
Hg, As, Se
34
93 17
review title and comments 1. Conference Proceedings EnviroAnalysis: Proceedings of the Third Biennial International Conference on Monitoring and Measurement of the Environment Proceedings of the 2nd Euroconference on Environmental Analytical Chemistry Air Monitoring and Detection of Chemical and Biological Agents Environmental Monitoring and Remediation Technologies 2. Matrix-Specific Analysis of organic compounds in air Measurements of concentrations of air pollutants; covers methods, deployment, site selection, networks Modern methods of the measurement of atmospheric trace gases X-ray fluorescence analysis of ambient air samples The physicochemical characterization of urban air particulate matter; diesel exhaust particles and carbon black are emphasized Trace element determination of airborne particles by neutron activation analysis Trace element analysis of airborne particles by atomic absorption spectroscopy, and inductively coupled plasma mass spectrometry Composition of air pollution particles; includes definitions of airborne particle types and sources of PM10 Sampling and analysis of individual particles by aerosol mass spectrometry Organic atmospheric aerosols: review and state of the science; main objective is to present a basis for defining what data are needed in this area Accelerator based ion beam techniques for trace element aerosol analysis Health-related monitoring and assessment of airborne particulate matter: an overview of recent IAEA (International At. Energy Agency) programs Mass spectrometry of aerosols; off-line MS techniques discussed New concepts for sampling, measurement, and analysis of atmospheric anthropogenic aerosols Real-time single particle mass spectrometry: a historical review of a quarter century of the chemical analysis of aerosols Correlations of personal exposure to particles with outdoor air measurements: a review of of recent studies Aerosol time-of-flight mass spectrometry Gas detection for automotive pollution control; emphasis on chemical sensors Reactive sorption concentration in air pollution Multielemental analysis of solid wastes and leachates; NAA, XRF, ICP-AES methods are covered Water analysis; extensive review of developments in water analysis Field methods for site assessment and remediation of contaminated ground waters Trends in monitoring of waste water systems; focus on use of sensors Use of flow injection analysis for continuous monitoring of river water quality Introduction - environmental analytical chemistry as a tool for studying chemical processes in marine environments
3. Metals and Organometallics Speciation The role of speciation in analytical chemistry; coverage includes use of sequential extraction Speciation in the environmental field. Trends in analytical chemistry; special attention to need for speciation analysis in biota Supercritical fluid extraction in speciation studies Liquid chromatography: a tool for the analysis of metal species Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters High-performance liquid chromatography-isotope dilution inductively coupled plasma mass spectrometry for speciation studies: an overview Speciation studies by atomic spectroscopy Element speciation analysis by capillary electrophoresis New approaches for elemental speciation using plasma mass spectrometry Metal speciation by SPME-CGC-ICPMS Chemical speciation of trace metals Microwave-induced plasma-optical emission spectrometryfundamental aspects and applications in metal speciation analysis Phosphorus speciation in water and sediments Improving the reliability of speciation analysis of organometallic compounds Analytical methods for mercury speciation in environmental and biological samples - an overview The determination of mercury species in environmental and biological samples The speciation of mercury and organomercury compounds by using high-performance liquid chromatography Speciation and analysis of mercury, arsenic, and selenium by atomic fluorescence spectrometry
2762 Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
ref A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31
A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49
Table 1. (Continued) review topic/analyte
no. papers cited or pages published
As, Se
152
Sn Cr
129 224
POPs endocrine disruptors endocrine disruptors endocrine disruptors endocrine disruptors estrogens toxaphene PCBs
many 14 21 12 pp many 7 pp 257 302
pharmaceuticals PAH PAH
154 many 11
nitro-PAH
9 pp
VOCs
157
drinking water herbicides phenols
67 50 108
aldehydes
16 pp
isocyanates petroleum hydrocarbons petroleum hydrocarbons algal analysis microorganisms
138 61 82 89 107
heavy metals in water metals trace elements
57 many 90
Hg Hg
52 85
Sb tributyltin
117 24
organometallics phosphate lanthanides
69 29 484
sulfide As marine waters
125 many many
marine biological samples seawater
99 60
marine waters
27
radiochemistry radiochemistry NAA radionuclides long-lived radioisotopes radiochemistry radiochemistry proficiency testing
many many many 181 27 many 7 32
accelerator MS
many
Ra
132
review title and comments
ref
3. Metals and Organometallics Speciation Speciation of arsenic and selenium compounds by HPLC hyphenated to specific detectors: A50 a review of the main separation techniques; covers papers published since 1980 Determination of tin species in environmental samples A51 Chromium occurrence in the environment and methods of its speciation A52 4. Organic Analytes Persistent Organic Pollutants (POPs): state of the science Monitoring endocrine-disrupting chemicals Endocrine-disrupting chemicals in a source water; drinking water source reservoirs Identifying endocrine disruptors by high-resolution mass spectrometry Endocrine disruptine chemicals in the aquatic environment Mass spectrometry applied to the analysis of estrogens in the environment Toxaphene. Analysis and environmental fate of congeners Methods for the determination and evaluation of chlorinated biphenyls in environmental matrices Pharmaceuticals and personal care products in the environment: agents of subtle change? The analysis of polycyclic aromatic hydrocarbons in marine samples Application of stable carbon isotopic analysis to source polycyclic aromatic hydrocarbons in the environment Chromatographic methods for carcinogenic/mutagenic nitropolycyclic aromatic hydrocarbons Anthropogenic volatile organic compounds in ambient air and natural waters: a review on recent developments of analytical methodology, performance and interpretation of field measurements Analysis of organic micropollutants in drinking water Determination of herbicides in water using HPLC-MS techniques Liquid chromatographic and biorecognition techniques for the determination of phenols and their substituted derivatives in water samples A user’s guide to aldehyde analysis using PFBHA derivatization and GC/ECD detection: avoiding the pitfalls Determination of isocyanates in air Environmental monitoring of petroleum products Oil and greases and petroleum hydrocarbon analysis Algal analysis-organisms and toxins Bacteriological analysis 5. Inorganic Analytes Heavy Metals; review covers the biosensor monitoring of heavy metals in water Metals and air pollution particles; includes discussion of lung injury from exposure Plasma source isotope dilution mass spectrometry: an optimum combination for high-precision analysis of trace elements Sampling and determination of particulate mercury in ambient air: a review Sample preparation procedures for total mercury determination in materials of natural origin Methodologies for determination of antimony in terrestrial environmental samples Collaborative evaluation of methods for tributyltin determinations in sediment and mussel tissue Separation of metal chelates and organometallic compounds by SFC and SFE/GC Phosphate; review covers multi-enzyme-based biosensors for phosphate in water Trace determination of;anthanides in metallurgical, environmental, and geological samples; covers literature since 1980 Analytical strategies for the detection of sulfide: a review Arsenic compounds in terrestrial biota Automated techniques for real-time shipboard determination of dissolved trace metals in marine surface waters Trace metal status in marine biological samples: a review Flow injection with chemiluminescence detection for the shipboard monitoring of trace metals Electrochemical monitor for near real-time determination of dissolved trace metals in marine waters 6. Radionuclides Environmental radiochemistry and radioactivity. A current bibliography Radiochemistry and radiochemical separations. A current bibliography Analysis by nuclear reactions and activation. A current bibliography Determination of radionuclides in environmental samples Ultratrace determination of long-lived radioactive isotopes Radiochemistry: inconvenient but indispensable Chemical yield tracers for radiochemical analysis ISO recommended reference radiations for the calibration and proficiency testing of dosimeters and dose rate meters used in radiation protection Accelerator mass spectrometry analyses of environmental radionuclides: sensitivity, precision and standardization Radon in the environment: a current bibliography
Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90
A91 A92 A93 A94 A95 A96 A97 A98 A99 A100 2763
Table 1. (Continued) review topic/analyte
no. papers cited or pages published
U
many
Pu
8
actinides
10
general review
84
general environmental general review monitoring ICPMS flow injection general review
859 319 54 101 255 676
XRF remote sensing acid interferences
many 32 161
portable MS portable MS membrane MS
22 22 37 pp
environmental MS
532
LC/MS LC/MS
241 159
LC/ICPMS
21
INAA and ICPMS
8 pp
GC-AED IC IC IC and CE
59 211 131 119
CE
43
biosensors sensors sensors sensors
421 pp 393 pp 30 76
biosensors biosensors biosensors sensors electrodes biosensors sensors
32 76 5 pp 71 many 122 20
sensors sensors microelectrode arrays
48 95 53
sensors biosensors gas sensors microbial sensors sensor arrays
171 205 15 36 10 pp
stripping voltammetry electrochemical detection
230 110
SPME
44
2764
review title and comments 6. Radionuclides Analytical methods for the determination of uranium in geological and environmental materials Determination of Pu isotopes at trace levels in environmental samples: radioisotopes and stable elements evolution during the radiochemical method. Comparison of three radiochemical protocols. Separation of mono-, di-, tri-, tetravalent and actinide cations on a cation exchange chromatography column with ICPMS detection 7. Atomic Spectroscopy Analytical atomic spectroscopy going into the next millennium: photons or ions, atoms or molecules? Environmental analysis; extensive review of field Atomic mass spectrometry Atomic spectroscopy in environmental monitoring and process control Environmental applications of plasma spectrometry Applications in environmental analysis Advances in atomic emission, absorption and fluorescence spectrometry, and related techniques X-ray fluorescence spectrometry New spectroscopic methods for environmental measurement and monitoring Acid interferences in atomic spectrometry: analyte signal effects and subsequent reduction 8. Mass Spectrometry and Chromatography Advances in field-portable GC/MS instrumentation Advances in field-portable GC/MS instrumentation Membrane introduction mass spectrometry; review of MIMS techniques and applications, including environmental Environmental Mass Spectrometry; comprehensive coverage of mass spectrometry as applied to environmental analysis, covers 1998-1999 LC/MS interfacing systems in environmental analysis: application to polar pesticides Applications of liquid chromatography-mass spectrometry in environmental chemistry: characterization and determination of surfactants and their metabolites in water samples by modern mass spectrometric techniques Speciation of metal-containing compounds found in the environment by micellar liquid chromatography interfaced to inductively coupled plasma mass spectrometry Comparative use of INAA and ICP-MS methods for environmental studies; review includes an element-by-element assessment Environmental applications of gas chromatography-atomic emission detection Advances in the determination of inorganic anions by ion chromatography Ion chromatography in elemental analysis of airborne particles Developments in sample preparation and separation techniques for the determination of inorganic ions by ion chromatography and capillary electrophoresis Recent developments in the separation of inorganic and small organicions by capillary electrophoresis 9. Sensors and Electrochemical Biosensors for environmental monitoring Proceedings of the seventh international meeting on chemical sensors Chemical and biological sensors: meeting the challenges of environmental monitoring Other types of sensors for organic pollutants; focus on immunosensors for organics in water Update on environmental biosensors Other organic pollutants: enzymatic biosensors Enzyme sensors for environmental analysis Fiber optic sensors in environmental monitoring Electrodes; extensive review on signal transduction by electrochemical techniques Gas-phase enzyme electrodes In situ electrochemical monitoring: from remote sensors to submersible microlaboratories Affinity sensor systems Microelectrode sensors for biomedical and environmental applications Microfabricated ultramicroelectrode arrays: developments, advances, and applications in environmental analysis Advances in the microfabrication of electrochemical sensors and systems Molecular probes and biosensors in bioremediation and site assessment Next-generation diode laser gas sensors for environmental and industrial monitoring Biochemical oxygen demand Electronic tongues for environmental monitoring based on sensor arrays and pattern recognition: a review Stripping voltammetry in environmental and food analysis Metalloporphyrin, metallophthalocyanine and related macrocycle complex-based film modified electrodes: review of selected significant designs and applications to the electrochemical detection of pollutants New developments in SPME
Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
ref A101 A102 A103
A104 A105 A106 A107 A108 A109 A110 A111 A112 A113
A114 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125
A126 A127 A128 A129 A130 A131 A132 A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147
Table 1. (Continued) review topic/analyte
no. papers cited or pages published
SPME SPME
40 12 pp
SPME SPME
40 16
SPME
41
SPE SFE
9 pp 29
sample preparation microwave extraction microwave extraction microwave extraction pressurized liquid extraction membrane extraction membrane and SPE extraction cellulose sorbent preconcentration organic analytes in water
36 pp 73 33 61 40
water removal from samples SFE POPs
55 14 pp 174
sample handling
1138 pp
water sampling sediment sampling soil water sampling vocs in air passive dosimetry monitoring programs
20 pp many 33 190 14 pp 10
diffusive sampling
147
quality assurance long-term monitoring airborne particles
many 69 10
airborne particles
38
QA and QC reference materials
34 54
reference materials
56
reference materials uncertainty
16 75
uncertainty statistics chemometrics
15 95 142 pp
chemometrics TMS derivatization blank optimization analyte stability
60 65 25 86
freshwater biomonitoring fish as biomonitors
43 144
vegetation as biomonitors marine biotests
154 84
great lakes fish
64
mussel biomonitors
many
24 43 42 167
review title and comments
10. SPE, SPME, and Sample Extraction Analysis of industrial pollutants in environmental samples Solid-phase microextraction: a promising technique for sample preparation in environmental analysis Metal speciation by SPME-CGC-ICPMS Organometallic speciation by combining aqueous phase derivatization with SPME-GC-FPD-MS The application of SPME-LC-MS to the determination of contaminants in complex environmental matrices Advances in solid-phase extraction disks for environmental chemistry On-line detection for supercritical-fluid extraction 11. Sample Handling and Extraction Sample preparation for environmental analysis; state-of-the-art review Microwave assisted extraction of organic compounds Application of microwave techniques in analytical chemistry Microwave-assisted solvent extraction of environmental samples Pressurized liquid extraction of persistent organic pollutants in environmental analysis Liquid membrane extraction in analytical sample preparation Ion separation in membrane and solid-phase extraction systems Functionalized cellulose sorbents for preconcentration of trace metals in environmental analysis Chemical analysis: sample handling and analysis of organic pollutants in water matrices Water vapour removal from gaseous samples used for analytical purposes Properties of supercritical fluids relevant to extraction and chromatography Separation, clean-up and recoveries of persistent trace organic contaminants from soils, sediment and biological matrices 12. Sampling, QA and QC, Chemometrics Sample handling and trace analysis of pollutants: techniques, applications and quality assurance Sampling methods in surface waters Sediment trap sampling in surface waters Collection of soil solution Sorbent trapping of volatile organic compounds Passive sampling for long-term monitoring of organic pollutants in water Designing monitoring programs to evaluate the performance of natural attenuation Monitoring the ambient environment with diffusive samplers: theory and practical considerations Quality assurance in environmental monitoring Ensuring quality in long-term environmental monitoring for chemical speciation Quality assurance, quality control, and data validation in environmental analysis of airborne particles Quality assurance and quality control in the elemental analysis of airborne particles Quality of residue data Certified reference materials for quality control of measurements in environmental monitoring Standard reference materials for the determination of trace organic constituents in environmental samples Proper use of reference materials for elemental speciation studies Sources of uncertainty in gas chromatography and high-performance liquid chromatography Evaluating uncertainty in routine analysis Some applications of statistics in analytical chemistry Pattern recognition, chemometrics, and imaging foroptical environmental monitoring Spectral pattern recognition: the methodology Artifacts in trimethylsilyl derivatization reactions and ways to avoid them Blank optimization for elemental analysis of laboratory water down to ppt levels Stability of chemical species in environmental matrices 13. Biomonitoring and Biomarkers Biomonitoring for the 21st century Biomonitoring and ecotoxicology: fish as indicators of pollution-induced stress in aquatic systems Biomonitoring using aquatic vegetation Choice of biotests and bioindicators for evaluation of the quality of the marine environment Neoplastic and inflammatory liver diseases of white suckers as environmental quality indicators The mussel watch approach and its applicability to global chemical contamination monitoring programs
Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
ref A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160 A161 A162 A163 A164 A165 A166
A167 A168 A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180 A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192 A193 A194 A195 A196
2765
Table 1. (Continued) review topic/analyte
no. papers cited or pages published
EROD induction dendroanalysis tree monitoring bivalve markers biomarkers bioremediation efficiency
60 22 172 many many 28
Watertox bioassays toxicity testing guideline
98 pp many
marine toxicity
many
endocrine disruptors aquatic plants whole effluent testing whole effluent testing
many many many many
monitoring trends asthma agents monitoring management humics dendrochemical monitoring
260 73 11 80 many
review title and comments
ref
13. Biomonitoring and Biomarkers EROD induction in fish: a tool to measure environmental exposure Dendroanalysis: a tool for biomonitoring environmental pollution? A decade of forest tree monitoring in Canada: evidence of air pollution effects Appraisal of prospective bivalve immunomarkers Biomarkers of exposure Biomarkers for monitoring efficacy of bioremediation by microbial inoculants
A197 A198 A199 A200 A201 A202
14. Toxicity Watertox Bioassays; comprehensive discussion of Assessment of the U. S. EPA methods for identification of hazards to developing organisms: the developmental toxicity testing guideline Characterizing and identifying toxicants in marine waters: a review of marine toxicity identification evaluations Assays for endocrine-disrupting chemicals: beyond environmental estrogens Aquatic plants for toxicity assessment Field assessments in conjunction with whole effluent toxicity testing Whole effluent toxicity testing: usefulness, level of protection, and risk assessment 15. Miscellaneous Review Topics Trends in environmental analytics and monitoring Environmental monitoring of chemical agents The proper place of analytical chemistry in environmental management Humic substances in water Monitoring historical changes in soil and atmospheric trace metal levels by dendrochemical analysis
parts-per-trillion (ppt) detection limits, and methods achieving these levels were mostly based on high-resolution mass spectrometers (HRMS). Capillary columns for trace organics determination were commonplace, but many packed column methods were still used. Many citations to methods for the chlorinated dibenzo-p-dioxins, dibenzofurans, and PCBs were found. Speciation methods for organometallics were beginning to achieve impressive results, with detection based mostly on atomic absorption (AA) techniques. Supercritical fluids for extractions and microwave ovens looked like huge new developments, and the promise of immunoassays for rapid screening appeared promising. Ten years later, the environmental analysis field has changed significantly. Few references to improved methods for dioxins/ furans/PCBs were found, as HRMS methods for these analytes have now matured. Impressive improvements in detection limits for such analytes are such that ppt detection is routine for many organic analytes, even by using benchtop quadrupole and ion trap mass spectrometers. Parts-per-quadrillion (ppq) detection is now becoming routine, and detection of a few hundred femtograms of some analytes is now possible, although such detection levels cannot yet be considered routine. Relatively new organic groups such as the nonylphenol ethoxylates, pharmaceuticals and steroids as environmental contaminants, and higher molecular weight polar compounds are being studied. Many seemingly different chemicals are now listed under the label of endocrine disruptors, the study of which will be an exceedingly difficult analytical challenge because of the low detection limits required and widely varying analytical properties of the many chemicals in this group. Such investigations have greatly expanded over the past few years because of the maturing field of liquid chromatography/mass spectrometry (LC/MS). Benchtop LC/MS models are now available for this work that make such studies available to a much greater range of researchers, much as the benchtop GC/MS did in the early 1980s. For metals and organometallics determination, 2766
Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
A203 A204 A205 A206 A207 A208 A209
A210 A211 A212 A213 A214
the field is rapidly becoming dominated by the inductively coupled plasma mass spectrometry (ICPMS) technology. Although AA is still widely used, most significant new developments in the environmental analysis field are ICPMS based. Other technologies that have been significantly advanced in the past two years are GC/time-of-flight mass spectrometry (GC/TOFMS), membrane introduction MS, pressurized liquid extraction, and real-time emissions monitoring. Microwave ovens for sample extraction are still being developed, but have not yet achieved the widespread use that seemed inevitable a few years ago, and supercritical fluid extraction (SFE) now seems to be a terrific technique for selected applicationssbut it now appears SFE will not reach the status of an essential, widely applicable technology. One relatively recent development that has exploded in the past two years is solid-phase microextraction (SPME). So many references to environmental analysis applications by using SPME were published, that we decided to highlight this technique in a special section immediately following the summary of review articles. REVIEW ARTICLES This section is the only one of this review where our intention was to be inclusive rather than exclusive. By summarizing other published review articles relating directly to environmental analysis, the authors hope to provide readers with a source of more detailed follow-up information. We have done this because it is impractical for a single article to be comprehensive in coverage for such an active and broad field as environmental analysis. These citations are presented in Table 1. SOLID-PHASE MICROEXTRACTION APPLICATIONS The use of SPME, in which a small, polymer-coated fiber is used to extract analytes from aqueous samples or air, has exploded since our last review. The first SPME device was described in 1990 (B1) and represented an innovative approach to sample
preparation. Analyte collection and concentration, from an aqueous sample, were accomplished simultaneously. Because thermal desorption was used to transfer the analytes from the SPME fiber to the GC/ECD, no harmful organic solvents were required for sample introduction into the detection system. Continued interest in SPME has been fueled by its commercialization by Supelco (Bellefonte, PA) in 1993 and by the choice of almost a dozen different fiber coatings, which allow the analyst to optimize the extraction of various compound classes. SPME can be considered a universal extraction method, as it can be used on gases, liquids, and solids (the headspace above the solid is typically sampled). SPME can be coupled easily with both GC and LC. Because SPME coupled with GC requires no solvent, it is an excellent sample preparation technique for field analyses and is particularly well suited to rapid response applications. Despite the fact that there have been many publications about this technique, some aspects of SPME, including the fundamentals of how analytes interact with the fiber coatings and the stabilities of analytes collected on a fiber, remain to be addressed. In addition, obtaining accurate quantitation with SPME can be challengingsfactors such as matrix composition, temperature, pH, and extraction times must be strictly controlled. The theory and application of SPME were summarized recently in several books (B2-B4). Because a comprehensive review of SPME is outside the scope of this paper, we will highlight articles that illustrate trends and recent SPME applications. Characterization of Organic Compounds. The largest use of SPME is for the characterization and quantitation of organic compounds. SPME/GC/MS was used to characterize landfill leachate; aliphatic and aromatic compounds with alcohol groups were detected (B5). SPME was used to sample the headspace above fish tissue extract; approximately 170 organic compounds were detected by GC/MS (B6). Automated SPME/GC/FID, which operated in a “stop-flow” mode, allowed on-line pH adjustment of samples, internal standard addition, and unattended field operation for 1 week, was used to monitor part-per-billion concentrations of organic compounds in industrial wastewater (B7). SPME/GC/FID and pattern recognition algorithms were used to characterize different types of jet fuels and to determine contamination sources (B8). Water Analyses. SPME/GC/MS was used for the determination of 55 volatile organic compounds; this technique had linearity comparable to and detection limits (50 ng/L for some analytes) better than purge-and-trap GC/MS (B9). Precise pH adjustment is critical for the extraction of organic acids and bases; small changes in pH change the concentrations of neutral species in water and, thus, affect their partitioning between water and the SPME fiber (B10). This can make quantitation challenging. SPME/GC/MS has been applied to the analysis of small, polar molecules, such as volatile amines (B11) and gasoline oxygenates (B12, B13). SPME/GC/MS yielded excellent detection limits, ∼10 ng/L, for the gasoline oxygenate methyl tert-butyl ether (B12, B13) and 15 µg/L for ethanol (B13). SPME/GC/MS, with derivatization, was used for analyses of haloacetic acids at concentrations as low as 10-500 ng/L (B14) and pharmaceuticals at concentrations of 0.2 and 50 µg/L (B15) in water. There continues to be interest in coupling SPME with LC/ MS. Linear alkylbenzenesulfonates, at detection limits of 0.5 µg/
L, were determined with SPME coupled with electrospray MS (B16). In-tube SPME, which uses a polymer-coated tube instead of a conventional fiber, coupled with LC/MS was used to determine trimethyl- and triethyllead, at 10 µg/L (B17). A homebuilt electrospray probe was developed, coupled to a SPME graphite fiber, and used to detect 10-9 M Triton-X (B18). Soil, Sediments, and Pore Waters. SPME was used to concentrate organic compounds in the headspace above sediments and soils. Polycyclic aromatic hydrocarbons, at an estimated detection limit of 1 µg/kg sample, were detected in sediments by SPME/GC/MS (B19). SPME/GC/MS was also used to determine polychlorinated biphenyls, at submicrogram per kilogram concentrations, in soils (B20). In an unusual application (called “matrix SPME”), poly(dimethylsiloxane)-coated glass fibers were used as samplers of polychlorinated biphenyls (PCB) in sediment pore water (B21). The results of this work might be considered controversial, as absorption partition coefficients are used to calculate PCB concentrations (B22). It has been asserted that surface adsorption is more important than absorption for controlling SPME collection of high molecular weight compounds, such as PCB (B23, B24); thus, PCB concentrations calculated on the basis of adsorption partition coefficients would not be accurate. Air Monitoring. Air monitoring is a relatively new application of SPME. A rapid, SPME-based method, with 1-min sampling and 15-min analysis times, was used to determine BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) in air; when coupled with GC/PID, detection limits were ∼1 ppb and results were comparable to those produced by a standard method of the National Institute of Occupational Safety and Health (B25). SPME/GC/AED was used to determine organic sulfur compounds at detection limits of 4-50 parts-per-trillion; however, low storage stability of the analytes, artifact formation, and the adverse effect of humidity on extraction efficiency limit SPME’s utility for quantitative, on-site analyses (B26). Bartelt and Zilkowski refined their model of the relationship between airflow rates and the absorption of analytes on a SPME fiber (the importance of sample temperature was also considered). Using their new model, they could measure a broad range of analytes, collected under different conditions, without prior calibration of the SPME fiber, and regardless of whether equilibrium conditions were established (B27). Temperature and humidity influence the partitioning of analytes between the air and SPME fiber, thus affecting method calibration and increasing the complexity of analyte quantitation (B28). While the previous studies focused on the determination of volatile organic compounds in the gas phase, the feasibility of using SPME (and also a needle trap device inspired by SPME) to sample aerosols and airborne particles was demonstrated for polycyclic aromatic hydrocarbons in diesel exhaust, triamcinolone in an asthma drug, and DEET in insect repellent (B29). Inorganic/Organometallic Compounds. The application of SPME to analyses of inorganic compounds is increasing. Several recent applications are described in Table 2. In these applications, headspace sampling of the resulting extract was most often used to minimize interferences. AIR MONITORING AND ANALYSIS APPLICATIONS General Comments. This review emphasizes the development of novel sampling and analytical methods and their applicaAnalytical Chemistry, Vol. 73, No. 12, June 15, 2001
2767
Table 2. SPME Applications to Environmental Analysisa analyte
method
matrix
D.L (ng/L)
ref
Hg, methylHg, methylPb, tetraethylPb, alkylSe Sn, Hg, Pb Sn, butyl- and phenylSn, butylSn, triphenyl-
water extraction, NaBEt4 derivatization, SPME/GC/MS SPME/thermal desorption/ICP/MS NaBEt4 derivatization, SPME/GC/MS NaBEt4 derivatization, SPME/GC/MS derivatization with 4,5-dichlor-1,2-phenyldiamine, SPME/GC/MS NaBEt4 derivatization, SPME/GC/ICP/MS NaBEt4 derivatization, SPME/GC/FPD
spiked soil water, reference tissue water water tap and river water surface water and sediment water, sediment, sewage sludge
200 400 100 6 0.1-4 0.006-0.6
B30 B31 B32 B33 B34 B35 B36
NaBEt4 derivatization, SPME/GC/FID TMAH or KOH-EtOH extraction, NaBEt4 derivatization, SPME/GC/ICP/MS
water, reference sediments water, potatoes, mussels
30 0.1
B37 B38
a Abbreviations: AAS, atomic absorption spectroscopy; DL, detection limit; EtOH, ethanol; FID, flame ionization detector; FPD, flame photometric detector; GC, gas chromatography; ICP, inductively coupled plasma; NaBEt4, sodium tetraethylborate; MS, mass spectrometry; SPME, solid-phase microextraction; TMAH, tetramethylammonium hydroxide.
tions in the characterization and analysis of toxic airborne pollutants. In addition, developments in areas of photochemical precursors are also included. Articles related to nonmetal gases, acid gases, and criteria gaseous pollutants are not covered here. The review is organized by analytes and applications with the intent to highlight new technologies and/or methodologies for the sampling and analysis of different types of toxic airborne pollutants. These include sampling (design, phase distribution, sector sampling, and specific sampling devices), volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), inorganic compounds, and spectroscopy/chemometrics (optical spectroscopy, mass spectrometry, postdata processing, and data interpretation algorithms). Papers on the subjects of automated analysis, especially its application to the monitoring of photochemical precursors and emissions from incineration, have been included. Finally, publications on the subjects of bacterial load, single aerosol particle analysis using particle-induced X-ray emission (PIXE), and applications of a quartz crystal microbalance sensor are reviewed. Several new trends were observed in air analysis since the 1999 review. As discussed earlier, SPME methods have been applied to the sampling and sample preparation of VOCs and SVOCs in environmental sample types such as water, soil, and air. SPME is a great screening tool but, due to a limited amount of adsorbent that can be coated on the surface of the SPME fiber, using SPME to achieve accurate quantitative analysis can be challenging. The development of an improved SPME method, the stir bar sorptive extraction (SBSE) approach where a glass stir bar coated with poly(dimethylsiloxanes) (PDMS), up to 500× of loading capacity of a typical SPME fiber, was successfully applied for the sampling and quantitative analysis of airborne VOCs and SVOCs (C10, E20). SBSE is a relatively new method, and we expect to see more applications in the future. Airborne polycyclic aromatic hydrocarbon (PAH) analysis continues to be a popular subject. In fact, more than 40% of the SVOC publications are the sampling, analytical method development, and characterization of airborne PAHs. Similar to PAHs are the endocrine disruptors that may be released from many sources but have yet to be characterized in a systematic manner. We expect to see more PAH and endocrine disruptor-related publications in the future. In the area of inorganic applications, we noted an increasing number of publications related to the use of chromatographic separation followed by 2768 Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
various detection techniques for the analysis and speciation of metals and organometallics. The instrumentation typically consists of GC/MS, ion chromatography (IC), LC/ICPMS, and LC-atomic emission spectroscopy (LC-AES). We expect to see more publications related to separation-enhanced speciation of inorganic compounds. Sampling. The collection of representative air samples for laboratory analysis remains the most challenging part in environmental air monitoring and analysis. Proper sampling and sample storage procedures are essential to ensure that laboratory data are representative of the sampling site and comply with applicable technologies and regulations. Romano described a method to determine and optimize the number of monitoring stations required in an air pollution network (C1). Using clean quartz and tobacco smoke particles as a model for mineral surface and aerosol organic matter, Pankow studied two mechanisms by which gas/ particle partitioning of SVOCs such as PAHs, PCBs, and organochlorines (OCs) can occur via adsorption to particle surface or organic aerosols (C2). Gas/particle phase distribution of PAHs, PCBs, and OCs was also studied by Bidleman using a high-volume air sampler which employs a filter and a sorbent trap to retain particulate and gaseous compounds (C3). Using a similar experimental setup, Sanusi studied the characteristics of gas/particle distribution of OCs and carbamate pesticides in urban, rural, and remote sites (C4). A study on the effect of meteorological parameters on the size distribution of particle-adsorbed PAHs was carried out by Schnelle-Kreis. Depending on wind direction, maximum PAH concentrations varied on particles depending on their geometric mean diameters, which varied from 75 to 920 nm (C5). The capability of a porous plastic foam and an air-to-liquid membrane for particle size-selective sampling and/or direct airborne particle sampling, respectively, was also evaluated (C6, C7). The use of a multisorbent-based cartridge for VOC sampling followed by thermal desorption-GC/MS (TD-GC/MS) analysis has been popular since the introduction of the USEPA method TO-17 in 1996. A study was carried out to evaluate the performance of Tenax GR and Carbosieve SIII as VOC sampling media followed by a short-path thermal desorption analysis of 77 VOCs (C8). The performance of a Carbograph 2 and Carbograph 5 multisorbent cartridge was also evaluated at various sample loadings and sample volumes ranging from 0.1 to 1000 mg/m3 (C9). Contrary to the
multisorbent-based VOC sampling is the SBSE-based approach, where equilibrium sorptive enrichment on PDMS instead of an adsorption process was used to concentrate VOCs in the air sample prior to analysis. This allows the use of a high-inertness sorption material such as PDMS and provides an analytical blank free from interference (C10). The use of new sampling media such as mesoporous carbons for airborne polar VOC sampling (C11) and a reversed-phase packing material (C18-Silica) for airborne VOC sampling (C12) followed by off-line extraction or elution and GC-flame ionization detector (GC-FID) or GC/MS analysis was evaluated against criteria such as compatibility with Tenax, reusability, and background interference in the GC analysis. The use of fullerene-extracted soot (a byproduct of fullerene production) in place of the Tenax GR (C13) was also evaluated using 17 VOCs. The applicability of two different types of Nafion membrane dryers and a poly(phenylene sulfide) wool-based O3 scrubber was evaluated for the adsorptive sampling of selected volatile organosulfur compounds and was demonstrated to provide an artifactfree analytical results (C14). Due to the potential health effect induced by the long-term exposure to ambient VOCs, continuous sampling periods of 4 weeks, 7 days, and 24 h were evaluated at 0.5, 2.0, and 14 mL/min sampling rates via a multisorbent sampling tube followed by GC/MS analysis (C15). It was found that, except for vinyl group-bearing compounds, concentrations of other TO-14 target compounds estimated by 4-week and 7-day sampling methods were approximately equal to the 24-h mean concentration. The feasibility of using Carbopack B 60/80 for diffusive sampling of VOCs was evaluated and found to have a superior uptake rate to Tenax TA 60/80 for the majority of VOCs analyzed (C16). The Carbopack 60/80 showed a stability of up to 28 days. Similarly, the performance of the 3M 3520 organic vapor monitor as a passive VOC sampler was evaluated for 24-h periods under various humidity and temperature conditions. It was found that, except for 1,3-butadiene, styrene, and methylene chloride, the 3520 device can be effectively used over the range of concentrations and conditions tested with a 24-h sampling period with an error of ( 25% (C17). In the bioaerosol sampling area, glycerol was tested as a collection substrate for passive sampling from three fungal species with results compared with a closed-face polycarbonate filter sampling method (C18). The glycerol was demonstrated to have good correlation with the closed-face sampler and to have a sample storage time of up to 7 days. Indoor air sampling methods for the assessment of environmental contamination were also investigated. A field comparison of the standard dust wipes method and the Lioy-WainmanWeisel (LLW) sampler was carried out to evaluate comparability of these two methods of indoor dust lead analysis. Correlation results within paired samples indicated that the LLW sampler has a significantly higher internal reproducibility for Pb loading than the dust wipe method (C19). Tedlar air sampling bags were used extensively for both indoor, ambient and abatement, sampling purposes. A study examining the adsorption and desorption behavior of six different organic compounds was carried out to evaluate the reusability of Tedlar air bags for air sample collection (C20). It was demonstrated that one should consider carefully before the start of any sampling program using Tedlar air bags.
On the other hand, it was also demonstrated that Tedlar air bags can be an effective and a convenient sampling tool collecting volatile metalloid compounds in ambient air (C21). The ability of Tenax or XAD or activated carbon-embedded solid-phase extraction (SPE) disks for SVOC sampling in diesel exhaust was validated and compared with a conventional polyurethane foam (PUF) sampling method (C22). The capability of a personal air sampler for 24-h collection of fine particles and SVOCs, especially PAHs, was critically evaluated (C23) for use in human exposure and biomarker studies. The suitability of using diffusive samplers for indoor air benzene, toluene, xylenes, and ethylbenzene sampling was evaluated using headspace SPME and GC-FID analysis (C24). Finally, a new personal aldehyde and ketone sampler was developed and validated using dansylhydrazine derivatization on solid sorbent with part-per-billion sensitivity (C25). Volatile Organic Compounds. VOC analysis requires the use and preparation of low-concentration standard gas mixtures with good consistency and high accuracy. This is usually prepared by using either a static dilution system or a dynamic dilution system with primary standards that can be traced back to a certified reference material (CRM). Combining a diffusion device with a dynamic dilution system, a new VOC standard preparation system was developed and validated at the part-per-trillion, v/v (pptv) to part-per-billion, v/v (ppbv) levels for various VOCs over 21 months. The system was demonstrated to be suitable for compounds with a wide range of boiling points from 305 (32 °C) to 418 K (145 °C) and a linear dynamic range of ∼104 (D1). A procedure using an active charcoal packed porous poly(tetrafluoroethylene) (PTFE)-based tube passive sampler followed by toluene extraction and GC-electron capture detection (GCECD) analysis of 18 indoor and ambient airborne organohalogen VOCs was developed and validated using real world samples (D2). Two direct sampling ion trap MS (ITMS) systems were evaluated for monitoring trace levels of halogenated VOCs in air. It was found that both direct sampling ITMS systems offer comparable analytical results with a detection limit at ∼50 ppbv in selection ion monitoring (SIM) and MS/MS operation modes (D3). The capability of multisorbent-based sampling followed by GC/MS analysis of a wide range of VOCs was investigated and demonstrated that by changing the sample volume and the amount of Carbotrap B and Carboxen 1000 in the sampling cartridge, one could analyze VOCs from dichlorofluoromethane (CFC12) to 1,2,3trichlorobenzene at method detection limits from 0.02 to 0.4 ppbv (D4). Analysis of odorous and/or polar VOCs remains a major challenge for analytical chemists. The capabilities of various sampling methods, sample preparation procedures, in situ or offline derivatization schemes, and analytical systems were evaluated with the goal to optimize the system performance to enhance data quality. Table 3 summarizes these activities according to the analytes, sampling methods, derivatizing schemes, and analytical systems used in the method (D5-D14). Semivolatile Organic Compounds. New procedures for the sample preparation and analysis of SVOCs including OCs, PAHs, and pesticides have been reported. These measurements have stringent quality control and quality assurance (QC and QA, respectively) protocols to support the usability of analytical data. Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
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Table 3. Polar/Odorous VOC Analytical Methods analytes
method/description/comments
refs
chlorine- and sulfur-containing biogases from sewage and landfill ambient sulfur-containing odorous VOCs
Summa canister followed by GC/MS or GC-atomic emission spectroscopy (GC-AES) analysis automated Tenax GR trap preconcentration, liquid N2 focusing, followed by GC and flameless sulfur chemiluminescence detection impinger sampling followed by solid-phase extraction (SPE) and GC/MS analysis sampling with in situ derivatization of formaldehyde on 3,5-bis(trifluoromethyl)phenylhydrazine-coated silica followed by GC-ECD and GC/MS analysis; results were validated with NIOSH method 3500 and 2,4-dinitrophenylhydrazine derivatization sampling with 200-mL glass bottle followed by the reaction with 200 ppmv nitrogen dioxide on the glass surface to form alkyl nitrites and then by GC-ECD analysis. direct MS identification of vapor-phase and particulate samples collected in heavy traffic area; five chemical classes of aromatic were found to exist in the samples. impinger sampling and in situ derivatization of carbonyl compounds with o-(2,3,4,5,6-pentafluorobenzyl)hydroxyamine hydrochloride; further reaction of hydroxy carbonyls with bis(trimethylsilyl)trifluoroacetaamine followed by GC/ITMS analysis multisorbent cartridge sampling followed by TD-GC using a new PLOT column capable of separating ketones and aldehydes from hydrocarbons in situ 2,4-dinitrophenylhydrazine sampling and derivatization followed by HPLC-APCI-MS analysis using stable isotopelabeled standards in situ 2,4-dinitrophenylhydrazine sampling and derivatization followed by micro-HPLC analysis and fiber-optic-based UV detector
D5
ambient polar VOCs such as carboxylic acids, alcohols, and phthalates airborne formaldehyde
atmospheric alcohols particulate matter-associated aromatic amines ambient carbonyls and hydroxy carbonyls
ambient aldehydes and ketones ambient formaldehyde and acetaldehyde ambient formaldehyde and acetaldehyde
D6 D7 D8
D9 D10 D11
D12 D13 D14
Table 4. Ambient PAH Analytical Methods analytes PAH azaarenes PAH PAH, DDT, BHC B[a]P diones B[a]P PAHs and nitro-PAHs PAHs nitro-PAHs PAHs PAHs and thiaarenes PAHs NIST 1649 PAH SRM
method description/comments
refs
sample preparation method for airborne particulate-associated PAHs using focused microwave extraction for GC/MS analysis with 3-h sample preparation time and superior recovery and precision airborne particulate-associated azaarenes analysis using normal-phase semipreparative LC fractionation followed by RP/LC-FL analysis of nine azaarenes critical evaluation of LC-UV, GC-FID, and GC/ITMS for the analysis of 19 airborne particulate-associated PAHs laser desorption-ITMS screening method of target compounds on a single airborne particle column chromatographic cleanup of soot aerosols followed by LC/atmospheric pressure chemical ionization/MS (LC/APCI-MS) analysis isotope dilution B[a]P analysis using a benchtop GC/MS direct screening of aerosol filter samples using laser desorption-time-of-flight-MS (LD-TOFMS) grease-coated Denuder sampling for the determination of phase-distributed PAHs extraction of particulate-associated nitro-PAHs, reduction of nitro-PAH to amino-PAH, and derivatization of the amino-PAH followed by GC/ECD analysis at the picogram level method was developed for LC/APCI-MS analysis of particulate-associated high molecular weight PAHs (MW >300) workplace air of an aluminum reduction plant was analyzed using GC-AED; running GC-AED in sulfur-selective mode allowed the analysis of thiaarenes without prior separation of PAH from thiaarenes PAHs in gasoline and diesel fuels and emissions from engine exhaust were characterized and quantitated at mg/L and µg/kg levels microscale sealed vessel (MSSV) thermal extraction-GC/MS and MSSV-pyrolysisGC/MS methods were evaluated using the SRM and found to be useful for the characterization of PM10 organics.
E2
In addition, the use of CRMs and standard reference materials (SRMs) improve precision and accuracy. For the determination of PAHs, the National Institute of Science and Technology (NIST) has recertified PAH urban dust SRM 1649 as SRM1649a using normal-phase liquid chromatography (NPLC) followed by reversedphase liquid chromatogrphy-fluorescence detection (RPLC-FL), i.e., NPLC/RPLC-FL for isomeric PAH analysis and GC/MS analysis using three different stationary phases (E1). Twelve new procedures were developed for PAH sample preparation and/or analysis using optical or MS-based detection methods (E2-E14). These applications are summarized in Table 4. 2770 Analytical Chemistry, Vol. 73, No. 12, June 15, 2001
E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14
In addition to PAH analysis, the long-term performance of a GC/negative ion chemical ionization MS (GC/NICI-MS) system for the continuous measurement of peroxyl acetyl nitrate (PAN) and its homologues was studied. Sensitivity and linearity of the GC/NICI-M system were demonstrated at the pptv level with significant sensitivity drift that can be corrected using an internal standard (E15). A method using GC/ITMS and GC/NICI-MS for atmospheric s-triazines and their metabolites, at detection limits from 0.8 to 15 pg/m3, was developed (E16). Identification of unknowns in multicomponent organic aerosols was demonstrated by a temperature-programmed thermal desorption particle beam
Table 5. Inorganic Applications and Methods analytes 206Pb, 207Pb, 208Pb
Pt, Pd, Rh 235U, 238U NiCl2, NiO, NiCO3 Mn, Fe, Co, Ni, Ag, Cd, Sn, Sb, Pb Zn, Co, Fe2+, Fe3+, Mn, Cd, Pb Zn, Cu, CO, Fe, Cd Be Ni(CO)4, Fe(CO)5, Mo(CO)6, W(CO)6 Sb(CH3)3, Sn(CH3)4, Sn(CH3)2(C2H5)2, Bi(CH3)3 butylated trimethyl-, dimethyl-, triethyl-, diethyllead arsenic Sb(CH3)3, Sb Ca, Cu, Fe, Mn, Ni, Pb, V, Zn silicon S, Ca, K, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb lead S, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Pb As, Ca, Co, Cd, Cr, Fe, Ga, Ni, Pb, Pt, V, Zn Hg Pb
methods/comments ICPMS-Based Methods Pb isotope ratio analysis of size-fractionated aerosols for source apportionment applications method performance for the analysis of airborne Pt, Pd, and Rh from vehicle’s catalytic converters using 235U/238U ratio obtained from tree bark for the discrimination of nuclear and nonnuclear emission sources method performance for the analysis soluble and insoluble Ni compounds in airborne particulate matter determination of size-fractionated particles from arctic air for trace metal monitoring
refs F3 F4 F5 F6 F7
Chromatography-Assisted Methods isocratic ion chromatography separation, postcolumn derivatization, UV detection at detection limits of 10-60 ppb capillary electrophoresis separation and direct UV detection at detection limits 0.5- 3 ppb micellar electrokinetic chromatography analysis of Be in airborne particulate at 1 ppm detection limit cryotrapping-GC/ICPMS analysis of sewer gas of analytes as a fermentation byproducts
F13 F14 F15
GC/ITMS an GC/ICPMS analysis of volatile organometals in land fill and fermentation gases
F16
GC/ICPMS analysis of organolead compounds using tetraethyllead as internalstandard with detection limits of 2-9 fg for a 1-mL injection
F17
speciation of arsenic in coarse and fine urban aerosols using sequential extraction and LC-atomic fluorescence detection with comparable results obtained from INAA analysis LC/ICPMS analysis of analytes in airborne particulate
F18
XRF-Based Methods XRF analysis of aerosol filters of 150-mm diameter with comparable quantitative results from AA and ICP-OES XRF analysis of silicon in airborne-particulate matter with quantitative results validated by LA-ICPMS performance of chemical speciation of analytes in airborne dust by sequential leaching and XRF was validated by NIST 1648 CRM performance evaluation of portable XRF instrument for analyzing dust wipe samples with results validated by AA XRF analysis of analytes in particulates of emissions from two disel fuels with different sulfur content
F12
F19 F20 F21 F22 F23 F24
comparison of sample preparation methods using oxygen-plasma ashing on sapphire carriers and acid digestion for XRF analysis of analytes
F25
silver-coated filter sampling followed by XRF analysis of mercury in flue gases evaluation of portable XRF for the determination of analyte in workplace air
F26 F27
Mercury Analysis analysis of ambient Hg2+ using KCl-coated denuders followed by TD and cold vapor atomic fluorescence analysis at detection limit of
