Sound environmental measurements are an essential part of the data needed to ensure the quality of the environment and the health of the public
At this year's conference half a dozen sessions were listed in the environmental papers. In Atlantic City, N.J., sessions were held on the topics of gas chromatographic analyses, industrial hygiene monitoring, and air and water pollution analyses. Gas chromatography The advent of commercially available, fused silica capillary columns (FSCC) has presented the environmental scientists with a new and valuable tool. Such columns are rapidly becoming the method of choice for a number of environmental analyses. J. R. Dahlgran of OH Materials Co. said that they have gained wide acceptance for priority pollutants analysis. T. R. Smith of Energy Resources Co., Inc., said that the acid and base neutral fractions of priority pollutants should be composited before introduction onto the FSCC. This procedure would minimize any interaction that may occur among the components in solution. M. P. Turner of HewlettPackard said that such columns are being used for high resolution and quantitative analysis of polynuclear aromatic hydrocarbons. The PAH mixture can now be injected on the column without discrimination. Nevertheless, applications remain where conventional techniques using packed columns are still the methods of choice. There are still some definite advantages to the use of conventional 276A
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packed columns in the field of environmental analyses. For example, J. F. Debrecht of Analytical Instrument Development reported that it was now possible to detect formaldehyde at the 3 ppm threshold limit value (TLV) established by the OSHA. This GC analysis has been made possible since the advent of photoionization detectors. For pesticide analysis, toxaphene residues in environmental samples were routinely analyzed by GC with electron capture detection, according to M. T. Zaranski of the University of South Carolina. Soot samples from a fire involving PCBs in a state office building in Binghamton, N.Y., were analyzed with a combined high resolution gas chromatographic/high resolution mass spectrometric ion monitoring system. D. R. Hilker of the New York Department of Health said that such analyses showed as many as 15 different tetrachlorofurans and dioxins, including the highly toxic 2,3,7,8TCDD and 2,3,7,8-TCDF. In some cases it is necessary to concentrate the environmental sample before placing the sample onto a GC column. There were two such devices to accomplish this task. R. G. Wes-' tendorf of Tekmar Co. said that closed-loop stripping analysis is a preconcentration technique that is useful for the analysis of semivolatile organic compounds in water at the ppt level by GC or GC/MS methods.
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© 1982 American Chemical Society
There is a Tekmar instrument that automatically performs the purge step; concentration is achieved by recirculating the headspace above a water sample to a trap, through a pump, and returned to purge the sample. A. G. Gargus of Chemical Data Systems told of a concentrator that is used for the analysis of trace organics in water. The concentrator accomplishes the task of multiple sample-handling in the purge-and-trap method, with excellent reproducibility. Gas chromatography with a flame ionization detector offers a good technique for the analysis of sulfur gases in process streams, natural gas, and atmospheric samples, according to M. Feeney of Hewlett-Packard. Equipped with a microprocessor, the instrument automatically measures sulfur compounds in gas samples. Industrial hygiene monitoring Recently, concerns for public health have evolved, such as industrial workplace hazards that require the development of sophisticated analytical methodologies. With the tools of analytical chemistry, progress is being made to develop the necessary information with which to assess the potential hazard to public health. Analyses are evolving for the measurement of materials in the workplace. For example, G. L. Swallow of the Manville Service Corp. said the best technique for asbestos analysis was with a membrane filter personal sampling method, with analysis of the filter by contrast light microscopy. This technique can be used for the routine evaluation of airborne concentration of asbestos fiber in the workplace. For monitoring airborne concentrations of asbestos dust at levels below those normally encountered in the workplace, the scanning and electron microscopes are useful. J. A. Small of the National Bureau of Standards said that the agency designed a program to develop standards and to evaluate measurement methods for airborne asbestos fibers. With the analytical electron microscope (AEM), each individual fiber is correlated by its relative position within the grid square. A second part of this program was designed to develop Standard Reference Materials with certified amounts of chrysotile asbestos at two loading densities. Passive monitors are those gas and vapor samplers that trap the sample without the aid of pumps. Such monitors have attracted the attention of industrial hygienists. Some 20 manufacturers produce 50 passive monitors. D. G. Taylor of NIOSH reported on
one sampler that had been evaluated for nitrous oxide. In a number of occupations, workers are exposed to polycyclic aromatic hydrocarbons (PAHs) in body fluids. The analytical procedure is based on the reduction of the metabolites in urine to the parent PAH compounds (reversed metabolism) and subsequent HPLC analysis. In other occupations, workers are exposed to aromatic and aliphatic diisocyanates. T. W. Dolzine of the U.S. Army Environmental Hygiene Agency reported on a gas chromatographic method for the determination of diisocyanates in air. Three commercially produced materials—TDI, MDI, and HDI—can be determined at levels well below the limits recommended by the NIOSH. The limit of the method is approximately 0.5 ppb of diisocyanate in a 40-L air sample. L. A. Currie of the NBS was interested in determining the sources of carbonaceous gases and particles in the
atmosphere. He found radiocarbon, l4 C, to be a unique tracer for this purpose; it clearly distinguished fossil from biogenic sources. Application of the counting of l4 C beta particles to environmental samples has been under way for the past few years; the newer technique of direct l4 C counting by accelerator mass spectrometry is in an early stage of development. In some industries workers are exposed to a variety of inorganic compounds. E. L. Johnson of Dionex Corp. said that ion chromatography was being used to study the presence of HF, HC1, H 2 S0 4 , azide, aliphatic amines, and formaldehyde. Organic vapors in workplaces can be analyzed with an instrument, a portable organic vapor meter, that uses the photoionization principle as the detector. J. O. Frohliger of Industrial Hygiene Associates, Inc., said this detector requires a high energy UV
lamp to ionize the sample that is drawn into the instrument. The ionized sample produces an ion current that is proportional to concentration and is measured with a pico ammeter. Formaldehyde, a known irritant and suspected carcinogen, is receiving attention as an indoor air pollutant. T. G. Matthews of the Oak Ridge National Laboratory spoke on recently developed voluntary emission standards for particleboard and plywood materials produced in the U.S. He said that the standards were based on a two-hour statistic desiccator-based methodology. Quinoline, another important carcinogen in the workplace, is found in tobacco smoke, urban particulate matter, automotive exhaust, synfuel plants, and industrial sources. T. VoDinh of the Oak Ridge National Laboratory said that a dosimeter has been developed for the detection and collection of quinoline in the vapor phase. Based on the principle of molecular diffusion, the collection process involves adsorption of quinoline vapor onto a paper substrate treated with heavy-atom salts such as lead acetate or thallium acetate. The quinoline species adsorbed on the paper substrate can then be directly detected using room temperature phosphorimetry. This simple method requires no extraction procedure and can detect 10 ppb of quinoline after only a fiveminute exposure period. There is a commercial instrument for monitoring a host of trace organic materials in the workplace. S. S. Cantor of Foxboro Analytical/IR center said that the MIRAN 80 instrument is a single beam infrared analyzer with a programmable microcomputer system. It is suited for the analysis of more than 300 OSHA-defined gases. A new analytical instrument was described for monitoring of hazardous vapors in the workplace environment. Charles Sadowski of Perkin-Elmer Corp. said the P-E Automatic Thermal Desorption System was designed to meet the requirements for automatic thermal desorption as specified by a group of industrial hygienists from petroleum and chemical companies. The system has a new sampling device, includes 50 adsorption tubes, and can be operated in the passive or pumped sample modes. R. C. Leveson, of Photovac, Inc., described a portable gas chromatograph useful for the monitoring of trace organic air contaminants. It is sensitive to a wide range of trace organic air pollutants in the workplace at sub part per billion sensitivities, withEnviron. Sci. Technol., Vol. 16. No. 5, 1982
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out any type of preconcentration. This system employs a photoionization de tector design that permits the use of air as carrier gas. A major benefit is that a number of data points can be col lected without recourse to the usual labor-intensive methods. In the past, ambient air has been sampled for PAHs using glass fiber filters. C. K. Dettmer of the University of South Carolina said that polyurethane foam (PUF) can be used to trap vapor phase PCBs and pesticides in ambient air. Total hydrocarbons were analyzed using G C - F I D and individ ual PAHs were determined using re versed phase HPLC with fluorescence detection. The porous polymer, Tenax, has been widely used for the collection and concentration of organic vapors in ambient air. Liam Horgan of the N.J. Institute of Technology found two other solid sorbents useful, namely Spherocarb and Ambersorb XE340. Another way to detect PAHs in ambient air was described by L. J. Jandris of the University of South Carolina. He looked at the minimum fluorescence detectability of several PAHs in the gas phase by laser in duced molecular fluorescence (LIMF). Results for anthracene showed that a plot of log Ρ vs. 1/T yields a curve that is linear over at least four orders of magnitude and exhibits a measured room temperature vapor pressure of 9.75 Χ 1 0 - 9 atm. Similar measured vapor pressures were ob tained with other PAHs. A spokesman for H.S.A. Reactors, Ltd., said electrochemical systems have been found useful to analyze trace toxic heavy metals—Cd, Pb, Cu, Zn, as well as Ag and Au. In the past, spectroscopic procedures were the most popular approach for this type of analysis. Now, electrochemical methods, particularly pulse and strip ping voltammetry, are becoming more widely used. Air pollution analyses Analysis of ambient air for individ ual hydrocarbon normally requires some method of preconcentration, gas chromatographic separation, and de tection. The only detector capable of species conformation is the mass spectrometer. An alternative approach was described by R. D. Cox of Radian Corp. His technique used photoion ization and flame ionization detection that added additional identification power to the capillary gas chromato graphic method for determining C2-C10 hydrocarbon species in air. Hydrocarbon species in ambient air are of interest since they are the pre 278A
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cursors to the formation of ozone, PAN, and other atmospheric pollu tants. M. A. McDevitt also of Radian Corp. described a method to provide C2-C10 hydrocarbon species identifi cation in ambient air on a single in strument. Data evaluation was ac complished with a Varian Vista 401 Chromatography Data System inter faced to an Apple II Plus microcom puter. More than 250 ambient samples were analyzed by this technique; hy drocarbons were always observed above the limit of detection—1 ppb by volume carbon. Analytical methods are also being applied to the characterization of inhalable particles. R. K. Stevens of the U.S. EpA and colleagues elsewhere reported on analysis techniques for ambient aerosols that assist in source apportionment studies. The determi nation of chemical compounds by
X-ray diffraction analysis in a mixed aerosol sample represents a novel ap proach for atmospheric particle source apportionment. They said that scan ning electron microscopy (SEM) coupled with an X-ray fluorescence analyzer for particle elemental analysis and the interfacing with a computer system for image analysis and electron beam control offer yet another method for source apportionment. The atmospheric pressure chemical ionization mass spectrometer has been used to evaluate air pollutants from landfill sites. Such sites emit air pol lutants other than methane and am monia. Ν . Η. Hijazi of Sciex said the instrument, the T A G A system (ES&T, Vol. 16, No. 1,1982, p. 38A) has been used to highlight different classes of compounds including oxy genated organics, nitrogen-containing species, aromatic and polyaromatic hydrocarbons, inorganic acids, reduced sulfur compounds, and phenols, carboxylic acids, aldehydes, and SO2. D. Karlesky of Texas A & M Uni versity worked out a procedural ana
lytical technique involving the three steps of collection, extraction and separation, and detection for the polynuclear aromatic compounds. A knowledge of the gas adsorption effi ciency of solid adsorbents is becoming important for air sampling devices. Y. Ueno of Texas A & M University said that the solid adsorbents tested in cluded Chromosorb LC-9 (100 mesh), Ci8 (20/40 mesh), Tenax GC (35/60 mesh), Amberlite XAD-2 (16/50 mesh), and activated charcoal. The apparatus was said to be able to esti mate the vapor pressure of various polynuclear aromatic hydrocarbons for air pollution studies. This scientist also described several methods of aerosol size distribution; the aerosols measured from 0.1 Mm up. Background levels of existing pol lution are still an order of business for environmental scientists. M. N . Khattak of the Saudi Arabian Uni versity of Petroleum and Minerals said that total suspended particulate mea surements in ambient air had been made over a period of two years at three cities along the Arabian Gulf in Saudi Arabia. The purpose of this study was to provide an adequate basis for the evaluation and regulation of industrial and urban activities cur rently existing in the Kingdom of Saudi Arabia. The measurements were analyzed for seasonal trends and epi sodic characteristics. In the area of ambient air analysis, a relatively inexpensive sulfide ion electrode was used to monitor the hy drogen sulfide content of coke oven gas, according to O. P. Bhargava of Stelco, Inc. R. A. Kagel of the University of Idaho described a promising new technique for the selective concentra tion of airborne gases containing sul fur. Current monitoring equipment lacks sufficient sensitivity to detect ultratrace concentrations of S-gases when the samples are not preconcentrated. This technique could have broader applications in the precon centration and for other trace envi ronmental pollutants, or in subsequent selection analysis, for example, of ni trogen oxides and acid halides. R. M. Vasta of Drexel University designed an instrument for measuring free ammonia in the atmosphere that is not complicated by the concentration of ammonium ion present in the aero sol. They designed a nondispersive photon counting instrument with rap idly pulsed, low-pressure mercury lamps as the source. One of the biggest application areas for ion chromatography is that of precipitation analysis. A. W. Fitchett
of Dionex Corp. said IC is being used in all the major deposition networks assessing the "acid r a i n " phe nomena. Water pollution analyses The analysis of priority pollutants in water is a continuing area of concern for analytical scientists. J. Fulford of Sciex said that the TAGA system, the triple quadrupole mass spectrometer, has been used to obtain preliminary results for the direct analysis of drinking water without any preconcentration. Detection limits were in the 1-50 ppb range. A main advantage of this system is that the entire analysis can be done on site, thus minimizing the possibility of contamination, deg radation, or transformation of the samples. Ion chromatography can also be used without sample preparation. A. W. Fitchett of Dionex Corp. said that the IC has the ability to determine both high (ng/L) and low ( μ / n g / L ) level concentrations on the same in strumentation. This allows the analyst to determine both macronutrients and micronutrients in ground, surface, and wastewater samples. He explained that a new type of analysis, which he called mobile phase ion chromatography, permits the analysis of a wide variety of hydrophobic and hydrophilic anions and cations such as aliphatic and aro matic sulfuric acid surfactants, alkanolamines, and quaternary amines. Water scientists are often concerned with the particles in water systems. Methylene blue adsorption has been used for many years to estimate sur face area. F. W. Page of the University of New Hampshire said that pyronine Y, similar in structure to methylene blue, can be used as an alternate sorbate for surface area measurements. Pyronine Y fluoresces in solution but does not when bound to particles. Adsorption data are necessary to. predict the fate and transport of or ganic pollutants in the environment. If an organic pollutant fluoresces, it is possible to get adsorption data without having to effect a separation. A. J. Lapen of the University of New Hampshire said that if the adsorption causes the fluorescence to be quenched, then the extent of adsorp tion can be determined directly from fluorescence intensities. Adsorption data can also be obtained by adding fluorophors to the sample; the fluo rescence from adsorbed fluorophors is more polarized than the fluorescence from free fluorophors. In some cases the analysis of toxic metals is important such as, for ex ample, in drinking water samples. D.
E. Shrader of Varian Instrument ex plained that furnace atomic absorption can be used to analyze for seven metals regulated in drinking water, and met als listed as hazardous wastes. The metals included As, Ba, Cd, Cr, Pb, Se, and Ag. Development of an oil shale industry presents a challenge to analytical chemists. Surface retorting of oil shale produces large volumes of solid waste. When the retorted oil shale contacts water, the aqueous solution rapidly develops a salt content often higher than 2% and the pH can approach 12. C. L. Grant of the University of New Hampshire discussed the extensive analytical data contained from a composite aqueous sample from a 50-year-old retorted shale pile gener ated by the Rulison project, an un derground nuclear explosion con ducted by the U.S. Department of In terior to generate oil or gas.
Nuclear and Chemical Dating Techniques Interpreting the Environmental Record
A C S S y m p o s i u m S e r i e s N o . 176 Lloyd A. C u r r i e ,
Editor
National
of
Bureau
Standards
Based on a symposium jointly sponsored by the Divisions of Nuclear Chemistry and Technology, Geochemistry, and His tory of Chemistry of the American Chem ical Society. Latest techniques for extracting in formation from archaeological and en vironmental samples This 24-chapter book reviews the latest developments and state of the art of physicochemical dating methods to gether with biogeochemical and ar chaeological applications.
Rainfall can leach hazardous waste materials from landfilled sites. C. M. White of the Pittsburgh Energy Technology Center of DOE said that analytical techniques are being devel oped for 20 target compounds in aqueous leachate. Obviously, soils differ in their abil ities to adsorb hazardous materials. J. D. Stuart of the University of Con necticut told how a series of eight soils had been used to contrast the removal of phenol and trichloroethylene from water. The uptake of these two chem icals was discussed in relationship to the total organic matter, clay content, and surface area. Humic and fulvic acids play a key role in the speciation, transport, and bioavailability of organic and inor ganic compounds in both surface water and groundwater. G. A. Baur of the University of New Hampshire dis cussed how time and mineral acid composition effect the removal of such materials from soil humic acids. —Stanton Miller
The fascinating volume begins with an historical perspective by the late W.F. Libby, the Nobelist who developed radiocarbon dating, in which he discusses topics ranging from cosmic ray physics to the history of modern man. The remaining chapters are grouped into three sections: cosmochemical and geochemical appli cations; natural archives; and chemical evolution, extinction, and archaeology. CONTENTS Historical Perspective of Nuclear Dating · Radioactive and Chemical Dating · ' Electrostatic Tandems · Mea surement of Natural l 0 B e and 14 C · Electrostatic Ac celerator Dating of Radiocarbon · Ion Probe Mg Isotopic Measurements · 8 1 Kr-Kr Dating by Mass Spectrometry • Laser Microprobe 39 Ar- 4 PAr Dating · Resonance Ioni zation Spectroscopy · Counters, Accelerators, and Chemistry · Dating Groundwater · Isotopic Records from Tree Rings · Fluctuation of Atmospheric Radio carbon · Historic Climate Indicators · Glaciochemical Dating Techniques · Dating Polar Ice by 1 4 C and 2 2 2 Rn · Dating Recent Events in Sediments by 2 l 0 P b · DeepSea Sedimentation · The Antiquity of Carbon · Cause of the Cretaceous-Tertiary Extinctions · IncenseBurner Trade in the Palenque Area * , 4 C Dating of an Iron Bloom · Problems in the Radiocarbon Dating of Bone · Travertines from Archaeological Sites
516 pages (1982) Clothbound US & Canada $48.95 Export $58.95 LC 81-20649 ISBN 0-8412-0669-4 Order f r o m : Distribution Dept. 21 American Chemical Society 1155 Sixteenth St., N.W. Washington, D.C. 20036 or CALL TOLL FREE 800-424-6747 and use your credit card.
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