Reprinted from Hydrocarbon Contaminated Soils, Volume II, 1992, Chapter 11, Pages 153-172.

ARTCL-1

CHAPTER

11

Review of Field Screening Methodology for Analysis of Soils

J. N. Driscoll, J. Hanby, and J. Panaro, HNU Systems, Inc., Newton, Massachusetts

INTRODU eTION The passage of the Resource, Conservation and Recovery Act (RCRA) in 1976 and the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA or Superfund) in 1980 led to an expansion of the list of hazardous chemical compounds under Environmental Protection Agency (EPA) regulation. This large number of contaminants or "priority pollutants" resulted in emphasis of analytical methods with multianalyte capabilities such as gas chromatography/ mass spectrometry (GC/MS) for organic analysis and inductively coupled plasmaatomic emission spectrometry (lCP) for analysis of inorganic species. The desire for legal defensibility of laboratory data resulted in complex analytical methods with heavy documentation and quality control requirements making quick turnaround of analytical data difficult, if not impossible. The assumption that all Superfund related data must be of litigation quality was challenged by the EPA and its regional Superfund contractors, e.g., Field Investigation Teams (FIT) and Technical Assistance Teams (TAT). I Under the EPA's Contract Laboratory Program (CLP) turnaround time from laboratories in the program was typically 30 days, but much to the dismay of the environmental professionals waiting to finish reports, 30 days was frequently exceeded. It soon became apparent that, for certain applications, there was a need
ISBN 0-87371-791-0 © 1992 by Lewis Publishers

153

156

HYDROCARBON

CONTAMINATED SOILS

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Figure 11.2.

Photo of P1101: Hanby Kit; GC311: SEFA P (XRF).

Another example of a tool for Level I (and sometimes Level II) screening is the HNU-Hanby Field Test Kit (see Figure 11.2) which is a procedure for analysis of water and soi I for aromatic pet roleum hyd rocarbons over a wide range 0 r concentrations. This procedure provides a colorimetric indication of the presence of aromatic compounds (BTEX, gnsol inc, d iesel , etc.) and is cu rrcntly bei ng used by investigators during tank removals to quantify contamination levels in order to assess the extent of contaminant plurnes.s'

154

HYDROCARBON CONTAMINATED SOILS

for faster, lower cost, field screening methods to supplement, and in some cases replace, the laboratory methods." A 30-day turnaround was not acceptable for many critical and timely decisions that had to be made. This led to the evolution of field screening and analysis methods in the 1980s by the EPA and the FIT and TAT teams. In order to support these new methods, portable versions of analytical laboratory instruments were needed to provide similar, if not identical, analytical capabilities in the field environment. The star performers of these methods were portable field instruments such as the total volatile organics analyzer, gas chromatographs, and X-ray fluorescence spectrometer (XRF). The instrumentation and methods for organics and inorganic species will be described briefly in this chapter and will be supplemented with data from a recent review of field collection and analytical methods for volatile hydrocarbons from leaking underground storage tanks which was compiled by the EPA.2 The integration of the sampling and analytical techniques will be discussed in detail.

SCREENING AND ANALYSIS LEVELS The framework of the EPA methodology involves five levels of investigative screening or analyses (Fig. 11.1). The first level (Level I) involves field screening with hand-held analyzers (EPA protocol specifies a photoionization detector like HNU Model PI or HWI01) shown in Figure 11.2 (b and c) and other site characterization equipment such as an oxygen meter, explosimeter, radiation survey equipment, and chemical testing tubes. Level I effort is designed to determine the real time total level of contaminants present (i.e., total volatile organics) which allows determination of the appropriate level of onsite respiratory protection and evaluation of air quality for existing or potential threats to surrounding populations." Additional benefits include more efficient and cost-effective sampling and analysis, and assistance in guiding quick and suitable cleanup efforts. The second level (Level II) involves field analysis with more sophisticated instrumentation (i.e., portable GC and XRF shown in Fig. 11.2d and 2e, respectively) to provide identification (as far as possible) of specific components present. The final three levels (Levels ID-V) use laboratories located offsite and frequently involve CLP analysis." We will not be concerned with these latter techniques in this chapter. Level I Screening The purpose of Level I field screening is to find total contaminant levels (i. e., total volatile organics). Using a screening/survey instrument, such as the HNU Model HWlOl (see Figure 11.2b and c), for example, it is possible to accomplish the following during Level I Screening:

FIELD SCREENING METHODOLOGY

155

methods in off-site lab

Level IV CLP Level III Off-site analytical lab EPA procedures without CLP documentation and validation Level II Field Analysis with more sophisticated portable analytical instruments. Tentative ID-GC/AAlXRF Level I Field Screening/Portable Instruments Total Organicllnorganic Vapor Detection
Figure 11.1. Summary of EPA screening levels.

..

• identification of contamination source, • monitoring soil vapor wells to determine the extent of the pollutant plume
(soii gas monitoring),

• measuring the total concentration profile in a borehole to determine contaminant migration on the groundwater or leaching down through the soil and thus contaminating the underlying groundwater, and • protecting the health of workers involved in the investigation and remedial work.

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157

Level II Screening Once a Level I screening identifies a contaminated area and delineates its extent, a Level II screening technique can establish the identity of the compound(s) and relative concentrations. Previously this was done predominantly by sending samples to a laboratory for detailed analysis. The intermediate Level II analysis was introduced by the EPA in order to reduce both the time required to start remedial actions and the high costs associated with laboratory analysis and keeping trained personnel in the field waiting for results." Field analytical equipment is currently used for onsite detection and identification of organic and inorganic contaminants in air, water, and soil. Portable GCs, i.e., HNU (Model 311, 321, see Figure 11.2) are used for characterization of volatile organic compounds, semivolatile organics, pesticides, and polychlorinated biphenyls (PCBs).

...

COMPARISON OF HYDROCARBON EXTRACTION AND MEASUREMENT TECHNIQUES Introduction Although headspace analyses? are common for volatile hydrocarbons, the most commonly used field analysis technique for site characterization is soil gas analysis" where the sample is collected by in situ pumping of a well. While the soil gas concentrations are useful in the trend of contamination levels, no direct relationship to the contamination levels in soil has been shown. Thus, it serves as a useful qualitative method for determination of the direction and source of plumes, as well as planning of remediation activity. With a GC311, the soil gas sample stream can be sampled directly. The advantage of the soil gas technique is that wells can be evaluated quickly (one hour running duplicate samples and standards) if the GC analysis time is kept to less than 10 minutes (this is still possible even for complex samples such as gasoline). Thus, 8 to 10 wells can be surveyed in one day. Several years ago, some underground tanks ruptured in Falmouth, Massachusetts, and spread the contents over a considerable area as a result of the sandy soil in the region. Initially, the site was investigated using a portable PID (HWlOJ) to rapidly survey a number of soil gas wells. 7 This type of Level I screening could also be used to determine the extent of contamination of the soil ("total" but not individual hydrocarbons) and groundwater which occurred (see following). Once this Level I survey is accomplished, a portable GC (GC311) could be used to characterize the wells. A typical set of chromatograms is shown

172

HYDROCARBON CONTAMINATED SOILS

Uncontrolled Hazardous Waste Sites. Hazardous Materials Control Research Institute, Silver Springs, MD, 1985, p. 97. 7. Duffy, M., and J. Hayhurst. "Field Investigation of Environmental Problems, The Role of Photo ionization (PID) Based Instruments," International LABMATE Vol. XIV, issue VII. 8. Driscoll, J., et. al. "Rapid Screening Techniques for Determination of Residual Organics in Foods, Polymers and Soils," Pittsburgh Conference, Paper 11603 (1981). 9. Robbins, G. Groundwater Monitoring Rev. (1989). 10. Robbins, G., and J. Stuart. University of Connecticut, private communication (1991). 11·. Field Screening Methods Catalogue (Users Guide, EPA/540/2/88/005), Hazardous Site Evaluation Division, U.S. Environmental Protection Agency, Office of Emergency and Remedial Response, Washington, DC, 1988. 12. Federal Register, 55(#145) July 27, 1990. 13. Driscoll, J. N., M. Whalen, C. D. Woods, M. Duffy, and C. A. Cihak. "Looking for Pesticides," Soils January/February 1992, pp. 12-15. 14. Driscoll, J. N., J. K. Marshall, C. Wood, and T. Spittler. Am. Lab. 23:25-26 (July 1991) .

15. Fribush, H., and J. Fisk. "Survey of U.S. E.P.A. Regional FieJd Analytical Needs,"
American Environmental Laboratory, October 1990, p. 29.

158

HYDROCARBON

CONTAMINATED

SOILS

in Figure 11.3, where the toluene concentration and distance from the source are also given. Site characterization can be done rapidly and in "real time," allowing a quicker assessment of the site. When multiple sources are present, this fingerprinting data could also be used to identify the source of contamination.

x1

x1
2

3
100

tt.

50 ft.
30 ppb GC analysis of soil gas vapor

x10 1 25 ft. 20 ppb

6 ppb

RANGE POINT # DISTANCE FROM MAIN PLUME APPROX. CONC. (Toluene)

Figure 11.3.

wells in Falmouth.

Volatile Hydrocarbon Methods Headspace
Headspace methods are easy to perform, and require a minimum of equipment. To obtain accurate results, the sample must be volatile and both the sample and standards must be at equilibrium. One typical procedure involves weighing (or measuring) 1 g of soil into a weighing boat which is placed in a container of about 100 cc volume, which can be sealed (a series of half-pint clean paint cans could suffice), placed in an oven at 600C for 15 minutes, and cooled to room temperature. 8 Standards bracketing the samples should be run at the same time and under exactly the same conditions. For total hydrocarbon measurement, the vessel top is removed or punctured and the reading (maximum) is.taken and recorded. (For a GC measurement, a gas tight syringe, 0.1 to 1 cc, is used to remove a sample for injection into the Gc.) The concentration can then be determined by comparison to a calibration curve generated from standards. With a portable PID, the gasoline range hydrocarbons can be detected with a 10.2 eV lamp, while the low molecular weight chloroalkanes can be detected with the 11.7 eV lamp. Robbins" described a headspace method using a polyethylene bag, where samples are collected in a modified (through the addition of a sealed connector and a ball valve to the bag) one-quart polyethylene bag. Twenty-five grams of soil are added to the bag and the bag is inflated with a hand pump until taut. The bag is manually agitated during the four-minute equilibration process; then the heads pace is ready to be measured. A calibration curve such as that shown in Figure 11.4 should be generated, then the readings on the portable PID can be

FIELD SCREENING METHODOLOGY

171

placement of monitoring levels during treatability firmatory analysis.">

wells; to optimize sampling grids; to establish cleanup studies; and to identify critical samples for CLP con-

CONCLUSIONS
As the EPA has become more experienced with field data, it was determined that when very little is known about a site or its contaminants, it is usually more cost-effective to use the CLP (or an equivalent, like a state certified lab) as a screen, rather than to conduct extensive field analyses designed for analyzing a limited number of target compounds. Field analytical methods were determined to be most useful when the contaminants of concern have already been identified, so that appropriate methods, dilutions, calibration ranges, etc., can be employed.15 It was also found that credibility could be lent to field data by using quality control techniques similar to laboratory methods (i.e., duplicates, standards run at regular intervals, etc.). Now that instrumentation is available to perform Level I and Level II field analyses, site crews can carry out their work faster, more easily and more reliably than in the past. More routine use of these technologies by those involved in environmental investigations, coupled with confirmatory laboratory analyses and adequate quality control, will firmly establish the role of these new methods. We have shown here that field methods and laboratory methods can yield similar results for volatile and nonvolatile hydrocarbons as well as heavy metals in soil as long as proper sampling techniques are used and proper quality control procedures are followed.

REFERENCES
I. Williams, L. R. "Guest Editorial," Amer. Environ. October 1990, p. 6. 2. Field Measurements; Dependable Data when You Need It, U.S. Environmental Protection Agency, EPA/530/UST -90-003, September 1990. 3. Clay, P. F., and Spittler, T. M. "The Use of Portable Instruments in Hazardous Waste Site Characterizations," Proceedings of the National Conference on Management of Uncontrolled Hazardous Waste Sites, Hazardous Materials Control Research Institute, Silver Spring, MD, November 29 (December 1, 1982), p. 40. 4. Data Quality Objectives for Remedial Response Activities, U.S. Environmental Protection Agency, Development Processes, PB 88-131370, March 1987. 5. Hanby, J. "A New Method for the Detection and Measurement of Aromatic Compounds in Water," Hydrocarbon Contaminated Soils and Groundwater, Volume I. P. T. Kostecki and E. J. Calabrese, Eds., (Chelsea, MI: Lewis Publishers, Inc., 1991). 6. Morin, J. O. "Development and Application of an Analytical Screening Program to Superfund Activities," Proceedings of the National Conference on Management of

FIELD SCREENING METHODOLOGY

159

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GASOLINE CONC. (mg/kg)
Figure 11.4. Calibration curve for gasoline in soil with PIO (Groundwater Monitoring).

converted into contaminant concentrations in the soil. Detection limits with a portable PID are in the low ppm range. 9 If the determination of individual hydrocarbons is required, then a portable GC is the instrument of choice. Here, the vessels could be modified to include a Swagelock connector that incorporates a septum. A gas-tight syringe is used to remove a sample (0.1 to 1 cc) and inject it into the GC. Static Headspace This method was developed by Robbins and Stuart'? at the University of Connecticut for the extraction of low levels of volatile organics from water. A 4-g soil sample was added to 25 mL of water in a 40-mL VOA vial (see Figure 11.8) and 100 J-tLof mercuric chloride (2.4 giL) was added as a preservative. Each vial was shaken for 10 seconds, inverted, and placed in a water bath for 30 minutes

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fluorescence analysis is an ideal analytical method since very little sample preparation is needed and the analysis is done onsite, which is a requirement of an EPA analytical Level II method.

REPORTING DATA
After developing and demonstrating the ability or field screening and analytical methods to supplement or replace laboratory analytical methods, the EPA and its contractors had the task of developing a policy or reporting and using the data. The resulting doctrine stipulated that data should be reported and used with care. Field analyses results were to be reported as a "tentative identification" rather than a definitive identification, as field analysis was not meant to replace laboratory analysis using greater sophistication and analytical controls (i .e., CLP analysis). A popular method of reporting data that resulted was one of ranges (i.e., low, medium, and high). It was determined that the purpose for obtaining field data should be clearly defined and it was important that such data not be extrapolated beyond the intended purpose. Fjeld analytical data seemed to best supplement laboratory methods when laboratory analysis had already identified the contaminants present at a site. Field analytical methods could be used to sct worker safety levels; to determine the extent of contamination and the

160

HYDROCARBON CONTAMINATED SOILS

at 25 +1- O.3°C to reach thermal equilibrium. A 50-ilL gas sample is injected into the Gc. A typical chromatogram using this method is shown in Figure 11.5. This method is also useful for the determination of volatiles in water.

17

20

6

ANALYTICAL RESULTS DATE
09/04/91

TIME
17:01 :51

PEAK#

COMPOUND NAME

6 17 20
Figure 11.5.

Toluene m-Xylene o-Xylene

CONCENTRATiON = 0.7 mg/kg = 6.3 mg/kg = 10.0 mg/kg

Chromatogram of soil analysis via static headspace. (Courtesy of G. Robbins, University of Connecticut.)

Solvent Extraction Volatile hydrocarbons can be extracted from soil using an appropriate solvent and analyzed by gas chromatography II or the Hanby method (described below).

FIELD SCREENING METHODOLOGY
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Figure 11.11. Comparison of AA vs XRF lor soil samples at wood treatment site.

HAZARDOUS WASTE SITE
ABANDONED WOOD PRESERVATIVE SITE

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3D plot of the arsenic concentration at the hazardous waste site.

FIELD SCREENING METHODOLOGY

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Nonvolatile Hydrocarbons Solvent Extraction-GC Semi volatile compounds cannot be detected via headspace or soil gas analysis and must be removed from the soil by solvent extraction. II These compounds have a low vapor pressure and include polychlorinated biphenyls (PCBs), pesticides, and polyaromatic hydrocarbons (PAHs). Solvent extraction can be used for these compounds in sailor water samples. The EPA has described a variety of field methods for sampling and analysis of semivolatile hydrocarbons in their field methods manual. II The method!' described above involves taking an SOO-mgsoil sample or 10-mL water sample, adding I cc ofa 1:4 water methanol mixture, adding 1 mL of hexane, shake for 30 seconds, then let stand for 30 seconds (if the mixture emulsifies, then centrifuge the sample) and inject the top layer (hexane) into the Gc. •. This method was originally developed for the analysis of PCBs; as a result, tests were performed on the extraction efficiency of DDT and some of its isomers to determine its viability. We ran our tests at the 1 to 10 ppm levels, since the action level for DDT is presently 2 pprn.P A typical GC-PID chromatogram of DDT is shown in Figure 11.6. Note that a portable GC with an oven capable of operating at temperatures of 150°C is essential. The method is described in more detail by Driscoll et al. 13 The efficiencies of extraction from soil spiked with DDT were 95% to 99%. Samples were analyzed onsite with the GC311, and grab samples collected for laboratory analysis were stored in glass jars and analyzed with in a few weeks of the time of collection. In Table 11. 1, the GC311 field results are compared with the lab GC results. Note the excellent agreement.
Table 11.1. Comparison of Fie1dvs Lab GC-ECD PPM DDT Field GC-PID 0.314 0.500 0.774 5.26 10.235 lab GC-ECD 0.170 0.400 0.410 5.560 6.000 12.150

The detection limit for DDT in soil by PID was 0.1 ppm, while the detection limit for the electron capture detector (ECD) is several orders of magnitude lower, as shown by the chromatogram in Figure 11.7. Note the difference between Figure 11.6 and Figure 11.7 where the isomers of DDT are readily identified in the latter

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of sample selection provided the best correlation between AA and XRF because it minimizes any sampling or stratification errors. A plot of the AA vs XRF results is shown in Figure 11.11. The agreement between these results is excellent (correlation coefficient = 0.99), considering that soil composition and particle size affect the results. At the wood treatment plant, surface soil samples were collected, bagged, coded, and brought to the SEF A P at the edge of the contaminated reduction zone for analysis. Several hundred samples were analyzed onsite during a four-day period. To characterize a hazardous waste site, typically, 300 to 400 samples are taken and at least 100 analyzed to characterize the level of contamination of the surface soil." The results obtained (ppm arsenic) can be analyzed, input into a spreadsheet program like Lotus 123 and presented in three-dimensional form, and plotted on grid using a Lotus add-in like 3D graphics. This produces a three-dimensional plot such as that in Figure 11.12 of the concentrationprofiles at the various sampling locations. Samples were generally taken between 0 and 12 from the surface, and at this site there was some stratification, as indicated in Figure 11.13. Contaminated soil samples may contain levels from low to many thousands of ppm, and X-ray
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DDT

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chromatogram at ppb levels. The correlation coefficient (r2) between the field and laboratory results was 0.99. The concentration found for DDT (11.99 ppm) was quite close to the PID results of 10.235 for the same results in the field. About 44 samples were collected and analyzed during a three-day period. Using this method and with the onsite analysis with the portable GC, the Corps of Engineers was finally able to clean up the area, while this had not been possible during the two previous visits, where only laboratory analysis was used. Hanby Method A field test kit for screening gasoline, kerosene, JP4, etc., was developed by Hanby" and is based on the Friedel-Crafts reaction by which a colored product is formed from the alky lation of aromatic compounds (in the fuel) in the presence of a catalyst. The color of the solution is compared to a chart to determine the concentration of the fuel. This technique has been recommended by the EPA for leaking underground storage tanks? and was used recently for assessment at the Exxon Valdez spill site. The technique is easy to use, rapid, and provides reliable onsite results. The method can be summarized as follows: weigh 5 g of soil into a 50-mL beaker, add 10 mL of solvent from the ampule supplied with the test kit, stir for three minutes, pour solvent from the beaker into the kit test tubes up to the mark, add contents of the catalyst vials to the test tube, shake vigorously for three minutes, and compare the developed color to the photograph supplied with the kit. This method is typically used for the detection of fuels- such as gasoline (orange to rust brown) or diesel (beige to green) at low ppm levels in soils, but low molecular weight chloroalkanes (yellow-green), PCBs (pink), and PAHs (violet to blue violet color) can also be detected with this method. A gray scale chart of different levels of unleaded gasoline in soil is shown in Figure 11.8. This is quite different from the visual colors actually observed, but it suffices to show color gradation to low ppm levels. Some typical reflectance spectra are shown in Figure 11.9. A number of soil samples were spiked with gasoline at levels of 50, 100, and 150 ppm and analyzed by both the Hanby method and extraction followed by gas chromatographic analysis using a PID (an average of three results at each concentration was used to determine the level). The results shown in Table 11.2 indicate that excellent agreement can be obtained between the Hanby method and laboratory techniques. The results of the Hanby method indicate a range of +/- 30 %, which is well within the +l-: 50% required by the EPA as a screening method for Levell. A comparison of the sampling and analytical techniques for volatile and non- (or semi-) volatile hydrocarbons are summarized in Table 11.3, while in Table 11.4, the detection limits are compared for the various extraction/analytical techniques.

INORGANIC ANALYSIS A portable XRF instrument (i.e., HNU Model SEFA P, see Figure 2e) is ideal for onsite screening of heavy metals and other harmful elements. This instrument

166

HYDROCARBON CONTAMINATED SOILS Sampling Techniques

Table 11.3.

For Volatile Hydrocarbons in Soil (Types of Hydrocarbons: Gasoline, Kerosene, Diesel Fuel, BTEX, Solvents) Type of Sample Handling Soil gas Description Direct measurement of vapor Syringe sample Headspace Weighed amount of soil placed in container of known or fixed volume and allowed to equilibrate Weighed amount of sample extracted with solvent Weighed amount of soil placed in VOA vial containing water and preservative and allowed to equilibrate For Nonvolatile Hydrocarbons in Soil (Types of Hydrocarbons: PCBs, Pesticides, PAHs) Type of Sample Handling Extraction Description Weighed amount of sample extracted with solvent Analysis Method Hanby, GC·PIO, GC-ECO Analysis Method PID, FlO, GC 311, Colorimetric table GC w/PIO or FlO

Extraction Static headspace

PIO, FlO, Colorimetric tube, GC-FIO, or GC-PIO Hanby, GC

GC-PIO

categories, depending on the use of the data. The SEF A can be used for analytical levels I and II. The EPA recommends the use of XRF during remedial response activities in its Report No. EPAIS40lG/87/004 "Data Quality Objectives for Remed ial Res po nse Acti v ities. ' '4 The instrument consists of a radioactive source, typically a gamma emitter, with sufficient energy to excite X-ray fluorescence (relaxation of inner shell electrons) of the various elements. These X-ray fluorescence spectra are characteristic of the elements and can be used for identification. The high resolution of the Si(Li) detector enables the type of spectra shown in Figure 11.10, where the peaks of clements neighboring lead (chrome, copper, and iron) arc sharply resolved. We have determined the detection limits for arsenic in various media including soil, and we found that although the detection limits in soil are the poorest of the three media (as a result of the scattering encountered with the soil samples compared to water or oil samples where there is less scattering), the detection limits are well within the range needed to comply with EPA regulations. Selected samples were sent to an outside laboratory for atomic absorption (A A) analysis. These samples were first analyzed by X-ray (nondestructive analysis), then the same samples were sent to the outside laboratory for analysis. This type

164

HYDROCARBON

CONTAMINATED

SOILS

Blank

0.5

5.0

20.0

... Figure

_._-----

.-.-----.~-------,-------------'

Super Unleaded Gasoline

11.8a and b.

Gray scale photos of Hanby Method with ppm level of unleaded qasoline.

FIELD

SCREENING

METHODOLOGY

165

80.0

60.0

40.0

20.0

O.O~~--~--+-~--~--+-~--~---r--~
250 340 430 520
in soil.

610

700nm

Wavelength
Figu re 11.9. Reflectance spectra for benzene

Table

11.2.

Comparison

of the Hanby

Method

vs GC-PID

for Volatiles Measured

in Soil

Actual

Concentration (mg/Kg) 50 150 350

Concentration (mg/Kg) GC-PID 46.6 150.2 377.8

Hanby 50+/ - 20 150+ / - 40 350+ / - 50

has been described in detail previously .14 The features of the XRF analyzer include: the wide variety of metals which can be analyzed, the minimum amount of sample preparation (no acid dissolution), and the rapid analysis onsite. The requirements for analytical equipment have been divided into three analytical

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