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A COMPARISON OF SPECTROPHOTOMETRIC AND GAS CHROMATOGRAPHIC MEASUREMENTS OF HEAVY PETROLEUM PRODUCTS IN SOIL SAMPLES

FARHAD NADIM1 , SHILI LIU1 , GEORGE E. HOAG1 , JIANPING CHEN1 , ROBERT J. CARLEY1 and PETER ZACK2
1 University of Connecticut, The Environmental Research Institute, Longley Building, 270 Middle Turnpike (Rte 44), Box U-5210, Storrs, CT, 06269, U.S.A.; 2 Connecticut Department of

Environmental Protection, Waste Bureau, Leaking Underground Storage Tank Program. 79 Elm Street, Hartford, CT, 06106, U.S.A. ( author for correspondence, e-mail: farhad.nadim@po.state.ct.us) (Received 18 August 1999; accepted 1 February 2001) Abstract. Laboratory studies were conducted to compare the infrared spectrophotometry (TPH-IR) and gas chromatography (TPH-GC) measurements of total petroleum hydrocarbon in soil samples. Real world soil samples containing #2 to #6 fuel oils, mechanical lubricating oil, diesel fuel, kerosene, jet fuel and weathered gasoline were extracted with trichlorotriuoroethane (Freon-113) and methylene chloride. The extractants were analyzed using gas chromatography with ame ionization detection (GC-FID) and infrared spectroscopy (TPH-IR) methods. A paired statistical t-test was applied to compare the average of paired differences in the analytical results. Statistical tests were evaluated with graphical presentation of the results. In general, a trend was observed in the measured concentrations. Total petroleum hydrocarbon (TPH) concentrations measured with TPHIR had the highest readings. The same samples extracted with methylene chloride and analyzed with GC-FID showed lower concentrations than the TPH-IR method while the GC-FID analysis of the same samples extracted with Freon-113 produced the lowest concentrations. Laboratory experiments indicated that TPH concentrations measured with the TPH-IR method were higher than the actual quantities of petroleum hydrocarbon in the soil samples. Keywords: freon-113, hydrocarbon contamination, petroleum product, statistical test

1. Introduction Being a major industrial nation, the United States uses over 250 billion gallons of oil and petroleum products each year on average. At every point in the oil production, distribution and consumption process, oil is invariably stored in storage tanks. The potential for an oil spill is high, and the effects of spilled oil often pose threats to the environment. Leaking underground and aboveground storage tanks, improper disposal of petroleum wastes, and accidental spills are major routes of soil and groundwater contamination with petroleum products. In order to delineate soil contamination and achieve regulatory cleanup levels, there is a need for accurate determination of TPH concentration in soil samples. There are two common practices for the measurement of TPH in soil samples: use of gas chromatography with ame ionization detection (GC-FID) and the use of infrared spectroscopy (TPH-IR).
Water, Air, and Soil Pollution 134: 97109, 2002. 2002 Kluwer Academic Publishers. Printed in the Netherlands.

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1.1. TPH MEASUREMENTS WITH GAS CHROMATOGRAPHY FLAME IONIZATION DETECTION (GC-FID) The use of gas chromatography is becoming a more commonly used method for the determination of TPH in soil samples (Parr et al., 1996). Accordingly, the Massachusetts Department of Environmental Protection has set two categories for the determination of petroleum hydrocarbon in soil and water samples. Volatile Petroleum Hydrocarbon (VPH) Method covers gasoline-range volatile hydrocarbons (C5 to C12). This method is based on a purge-and-trap, gas chromatography procedure. Photoionization detector (PID) and ame ionization detector (FID) achieves detection. Extractable Petroleum Hydrocarbon (EPH) Method measures extractable hydrocarbons in soil and water samples with an approximate molecular weight range of C9 to C36. Samples are extracted with methylene chloride, fractionated with silica gel to obtain an aliphatic fraction and a separate aromatic fraction. The aliphatic fraction is analyzed by GC-FID to obtain C9-C18 and C19C36 aliphatic range data while the aromatic fraction is analyzed by PID to obtain C11-C22 aromatic hydrocarbon range and target polynuclear aromatic hydrocarbon (PAH) results. The precision of the measurements can be monitored with the aid of surrogate standards (such as chloro-octadecane and ortho-terphenyl), internal standards (such as 5-alpha-androstane), and matrix spike standard that is prepared from ve or more analytes from each analyte group independently from the calibration standards (Massachusetts-DEP, 1995). The GC-FID may be calibrated to specied standards and has the ability to quantify industrial compounds. There are less interferences with the GC-FID method and the analytical costs are less than the TPH-IR method. Compared to TPH-IR, TPH determination with GC-FID is a time consuming procedure. Calibration of the GC instrument, preparation of the samples and interpretation of the data requires tangible time and effort. 1.2. TPH MEASUREMENT WUTH TPH-IR ( METHOD 418.1) One of the common methods used for quantication of petroleum hydrocarbons in soil and water samples is the EPA Method 418.1 (U.S. EPA, 1978; U.S. EPA, 1996b). A full review of the method and its limitations may be found in the works of Sanford and Weston (1992), Bruce et al. (1995), and Parr et al. (1996). Method 418.1 is used for the detection of total petroleum hydrocarbon (TPH) in water samples using infrared spectrometry. By substituting a soxhlet extraction procedure for the separatory funnel procedure, this method may be modied and used for the analysis of total petroleum hydrocarbon in solid matrices. After the extraction of oil and grease from a sample, silica gel is added to the extract to separate out the total petroleum hydrocarbons. Silica gel adsorbs the polar material such as vegetable oils and animal fat. The method considers all oil and grease materials that are not eliminated by silica gel adsorption as petroleum hydrocarbons. Sodium sulfate is added to the sample during the extraction pro-

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cedure and in the ltration process to eliminate any existing moisture in the sample (U.S. EPA, 1995). Proper sample drying with sodium sulfate (or other drying agent) prior to solvent addition is essential for good extraction efciency. An Infrared Spectrophotometer (TPH-IR) quanties the extracted petroleum hydrocarbon by measuring the concentration of C-H bonds and their bonding frequency. The IR- absorbence of the extracted sample is measured at 3.41 m, and then compared to the IR-absorbence of a known standard. According to the Beers law within a certain limit there is a linear relationship between absorption and concentration. All compounds with carbon-hydrogen linkages have absorption bands between 3.0 and 3.65 m wavelength due to C-H stretching vibrations. Benzenes C-H absorption band at 3.3 m is strong and it is a unique band. There are several limitations associated with the TPH-IR method that could be outlined in the following categories. Compounds with high degree of volatility are lost during analysis; with Freon-113 heavy hydrocarbon molecules (such as hydrocarbon molecules found in #4 and #6 fuel oils) are not fully extracted; due to the presence of strong oxidizers in some samples (such as samples with traces of fertilizers) reduction of polar hydrocarbon to non-polar hydrocarbon causes high and false TPH readings, and presence of suspended particles can be a problem in some samples, but if the sample is properly ltered at the conclusion of the extraction step they should not normally be a problem. The TPH-IR method lacks analytical specication because the petroleum hydrocarbons measured by the TPH-IR method are all compounds in the same sample that are extractable with Freon-113, unabsorbed with silica gel and have IR-absorbences at 3.41 m.

2. Study Objectives In this study we compared the TPH-IR and GC-FID applications for the quantication of total petroleum hydrocarbons for different types of oil samples utilizing an easily applicable statistical test. Laboratory studies were conducted to compare the data obtained from TPH-IR and GC-FID-TPH for a widely used petroleum based oils, such as #2 to #6 heating fuel oils, mechanical lubricating oil, diesel, kerosene, jet fuel and weathered gasoline. The solvents used for this study were methylene chloride and trichlorotriuoroethane (Freon-113). Through this study the extraction efciencies of Freon-113 and methylene chloride for different grades of fuel oil and their subsequent quantitation with an infrared analyzer (IR) and a gas chromatograph were determined. Real world soil samples contaminated with various petroleum products were extracted with Freon-113 and methylene chloride (MeCl2 ) and were analyzed with a GC-FID and an IR-spectrophotometer. The physical and chemical properties of heavy petroleum products used in this study are given in Table I and the types of petroleum products in soil contaminants are given in Table III.

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TABLE I Some physical and chemical properties of petroleum products Petroleum product Gasoline Diesel Kerosene Jet Fuel No. 2 No. 4 No. 6 Crankcase Oil Lubricating Oil Light Crude Oil IR-Reference Oil Carbon range C6 C10 C8 C21 C8 C16 C8 C16 C8 C21 C8 C30 C20 C78 C22 C50 C20 C40 Oil Specic C6 C16 Specic gravity 0.72 0.78 0.84 at 24 C 0.83 at 15 C 0.82 at 15 C 0.84 at 24 C 0.93 at 15 C 0.95 at 15 C Oil Specic 0.87 at 24 C 0.80 at 24 C NA Boiling point range 60 C 170 C 260 C 360 C 190 C 260 C 190 C 260 C 260 C 360 C Oil Specic Oil Specic Oil Specic Oil Specic Oil Specic NA

From Woodruff et al. (1995), and Potter (1996).

3. Experimental Procedure 3.1. I NSTRUMENTATION A gas chromatograph Model HP-5890, Series II Plus was used for sample analysis. HP-3365 Series II, Chem-Station version 8.03.34 and HP-GC ENVIROQUANT G-1045A-8.00001 were used for quantitation of hydrocarbon compounds. The column used was a capillary column, 30 m long, 0.53 mm ID, and lm thickness of 0.5 m (DB-1, J and W Scientic). The initial oven temperature was set at 40 C for 2 min and raised to 290 C at 15 C min1 , then held at 290 C for 10 min. The detector temperature was set at 320 C. The total run time was 28.5 min. For spectral analysis of the Freon extracted fuel, a MIRAN-1A infrared analyzer was used. 3.2. C ALIBRATION OF THE GAS CHROMATOGRAPHY Based on USEPA Method-8015, the average response factor of n-alkane mixture dissolved in isooctane was used to convert the total peak area of a sample chromatogram to TPH concentration. The straight chain alkane mixture contained C9 to C36 hydrocarbon components. The chromatography program was set to demonstrate sufcient separation between the solvent and the rst alkane peaks. The last alkane component C36 eluted at about 27.5 min. C36 was used as the retention time marker for oil identication. Samples were injected into the gas chromatography in a splitless mode through an automatic liquid sampler (HP Model 7673)

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at injection temperature of 290 C. The performance of the instrument was checked with intermittent blanks, laboratory duplicates and calibration standards. The average response factor of target analytes was calculated as follows: Fi = Ai Ci

Fa = ( Fi )/n %D = [(Fi Fa )/Fa ] 100 Response for individual n-alkane components in the sample, in total peak area counts. Fi = Response factor of an individual alkane Ci = The mass (g) of alkane injected into the GC column Fa = The average response factor of alkane standard, count g1 n = number of peaks For initial calibration of the GC-FID, the n-alkane mixture was used at ve different concentrations (i.e., 50 g mL1 , 100 g mL1 , 200 g mL1 , 500 g mL1 and 1000 g mL1 ). The concentration range of 50 g mL1 - 1000 g mL1 was used to t into the working range of the detector and to cover the expected range of concentrations found in real samples. Based on USEPA Method-8015 and in order to check the linearity of the alkanes response factors by GC-FID, the average response factors of ve GC-FID injections of the straight chain alkane at ve different concentrations (50 g mL1 1000 g mL1 ) were calculated and the results are tabulated in Table II. The relative standard deviations (RSD = Standard Deviation/Fa) of the response factors were calculated for each component of the straight chain alkane and the percent RSD for all components were below 10%. The calibration results show that over the concentration range of C9 to C36 petroleum hydrocarbon the GC-FID response is linear. The tailing of the solvent peak may have caused the higher RSD for Nonane. Concentration of TPH in soil samples was calculated as follows: Concentration (gkg 1 ) = [(Ax /Fa )(Vt /Vs )D]/W Where: Ax = Vt = Vs = D = W = Response for the analyte in the sample, in total peak area counts. Volume of extract, mL. Volume of sample extracted, L. Dilution factor, if no dilution was made: D = 1 (dimensionless). Weight of the extracted sample (kg). Depending upon the specic application of the data the wet or dry weight may be used. The injection volume of sample extract is the same as that of the calibration standard. Where: Ai =

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TABLE II Performance check of the GC-FID instrument and the linearity of alkanes Alkane Average response factor Fa 6464 6858 7010 6972 6951 6908 6888 6993 6664 6842 7181 6985 7163 6663 7017 Standard Deviation (SD) 541 113 113 92 89 55 34 79 160 144 342 115 157 98 81 Relative standard Deviation 8.4 1.6 1.6 1.3 1.3 0.8 0.5 1.1 2.4 2.1 4.8 1.7 2.2 1.5 1.2

Nonane(9) Decane(10) Dodecane(12) Tetradecane(14) Hexadecane(16) Octadecane(18) Eicosane(20) Docosane(22) Tetracosane(24) Hexacosane(26) Octacosane(28) Triacontane(30) Dotriacontane(32) Tetratricontane(34) Hexatriacontane(36) RSD% = SD/Fa 100.

3.3. M ETHOD PERFORMANCE CHECK WITH GC-FID Nineteen soil samples with sandy texture ( 10 g each) were taken from a site with no history of petroleum hydrocarbon contamination. Sixteen samples were spiked with a mixture of #2 oil, #6 oil, kerosene and motor oil (100 g of each). The total mass of oil in the spiking solution was 400 g. Three soil samples were used as controls. All soil samples were kept in jars with Teon sealed caps for 48 hr in room temperature of 24 C. Samples were then extracted with methylene chloride using EPA Ultrasonic Extraction Method-3550 (U.S. EPA, 1995) and analyzed by GC-FID. Each sample was extracted three times with approximately 10 mL of MeCl2 and the extracts were placed in a 100-mL grade-A volumetric ask. By adding MeCl2 to the ask the solvent level was brought up to the 100 mL marker. The average recovery of all sixteen spiked samples was 103%. The standard deviation was 12% and the RSD value ranged from 11 to 20%. TPH levels in the control samples were all below the detection limits of the GC-FID instrument. 3.4. D ETECTION LIMITS The method detection limit (MDL) may be dened as the minimum concentration of a substance that can be measured and reported with 99% condence that the

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Figure 1. Comparison of IR absorbences for different fuel oils and the reference oil.

value is above zero (U.S. CFR-40, 1998). Applying the method detection limit (MDL) study, the method detection limit for the straight chain alkane and four oil samples extracted from the sixteen soil samples were measured and the limits ranged from 0.052 mg kg1 for #2 fuel oil to 0.714 mg kg1 for straight chain alkanes. 3.5. C ALIBRATION OF THE INFRARED SPECTROPHOTOMETER Following EPA Method 8440 the standard solution was made by mixing 15 mL n-hexadecane (C16), 15 mL isooctane (C8), and 10 mL of chlorobenzene (C6) as the reference oil in a 50 mL glass stoppered bottle. Calibration of the TPH-IR instrument was done by preparing ve standards from the reference oil over the concentration range of 25 mg L1 to 500 mg L1 . Concentrations exceeding 500 mg L1 were beyond the detection range of the instrument. 3.6. M ETHOD PERFORMANCE CHECK WITH TPH-IR The TPH-IR absorbences for different oils were measured and the results are shown in Figure 1. Figure 1 indicates that as the concentration of the oil in Freon-113 increases the difference in IR-absorbences for different fuel grades becomes larger (#6 oil and kerosene have the lowest and the highest absorbences respectively). Figure 1 shows that for all of the petroleum products used in this study, the reference oil had the lowest response.

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3.7. S OIL EXTRACTION PROCEDURE Eight soil samples were taken from the walls and bottom of excavation areas of underground storage tanks used to store petroleum products. All soil samples had a sandy texture with traces of silt and clay. Samples were numbered as sample-1 through sample-8. Samples 2,3,4,5,6, and 8 were collected from unsaturated soil and samples 1 and 7 were taken from the region of subsurface that had periodically been saturated with uctuating groundwater table. Samples were extracted with Freon-113 and methylene chloride. The extractants were analyzed with TPH-IR and GC-FID. In order to calculate the concentration of petroleum hydrocarbon in the soil samples, the IR instrument was calibrated with the reference oil that was mentioned in the Calibration of the Infrared Spectrophotometer section. Soil samples were extracted with ultrasonic extraction method (U.S. EPA Method3550, 1995). Approximately 10 g of soil was taken and thoroughly mixed with 10 g of anhydrous sodium sulfate inside a 100 mL (grade-A, Fisher Scientic) glass beaker until it was like free owing powder. Sonication was performed in specied pulse mode and the tip was positioned about 0.5 cm below the solvent surface with a Fisher Sonic Dismembrator (Model-300) at 50% power for 3 min. Three extractions were performed with each solvent. During the extraction procedure it was observed that Freon-113 did not completely dissolve the #6 fuel oil. Methylene chloride seemed to completely solubilize #6 fuel oil and this phenomenon was clearly visible in the glass beakers used for extraction. Extracting solvent was poured into a grade-A 100 mL volumetric ask through a glass funnel that was packed with anhydrous sodium sulfate. For Freon-113 and MeCl2 extractions, approximately three grams of silica gel (60200 mesh, Davidson Grade 950) was added to each sample extract in the 100 mL volumetric ask to eliminate the non-petroleum oil. Mixtures were stirred for 5 min on a magnetic stirrer.

4. Discussion The MeCl2 -extracted soil samples were analyzed with GC-FID and the Freon-113 extracts were analyzed with GC-FID and TPH-IR. Three 10 g portions of each soil sample were taken and extracted in triplicate with Freon-113 and with methylene chloride. In order to compare the results obtained from the analysis of the eight soil sample extracts with methylene chloride and Freon-113, a paired statistical t-test (95% condence interval and 2 degrees of freedom) was used to compare the average of paired differences. A paired statistical test is usually done when two experiments are performed to independently make a series of tests (Lyman 1988; McBerthouex and Brown 1994). Instead of testing the null hypothesis that states the difference in the mean of two samples is zero: a b = 0, we looked at the problem in terms of the condence interval of the average of differences.

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Figure 2. TPH concentration in soil samples measured with three independent methods. Error bars represent one standard error of the mean values.

If the condence interval of the average of differences included the value zero, then we concluded that there was no evidence in the data pointing at a statistically signicant difference between the two samples. Comparisons of the average values are presented in Table III. The concentration of TPH measured by TPH-IR had the highest value in all samples except sample 1 and sample 7 where GC-FID measurements of methylene chloride extracts were higher (Figure 2). For soil samples contaminated with motor oil, statistical comparison of the average of differences between GC-FID methylene chloride (MeCl2 ) extracts and TPH-IR measurements do not indicate a signicant difference between the two analytical tests. Statistical tests done on soil samples 8 and 5 indicate that between all analytical results there is a signicant difference between all three methods of measurements. The same test shows that there is no signicant difference between the GC-FID-Freon and TPH-IR measurements in soil sample 7. Statistical comparison of TPH-IR and GC-FID-MeCl2 indicates that from eight soil samples tested with the two methods, four samples show signicantly higher concentrations measured with the TPH-IR method. Comparison of TPH-IR and

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TABLE III Statistical comparison of TPH concentrations in soil samples measured with three independent methods Comparison of TPH-IR with GC-FID-MeCl2 Methods Soil sample Upper level (CI) 1 0.06 2 1.11 3 3.49 4 11.43 5 3.85 6 2.25 7 2.08 8 3.31 Comparison of TPH-IR with GC-FID-freon methods Soil sample Upper level (CI)

Oil type Motor Oil Motor Oil Kerosene and HF6 HF2b and HF6 HF2 HF2 Motor Oil HF2

Lower level (CI) 1.02 0.60 0.17 5.43 3.51 0.02 2.53 1.37

Test results No difference No difference Signicantly highera Signicantly higher Signicantly higher No difference No difference Signicantly higher

Oil type Motor Oil Motor Oil Kerosene and HF6 HF2 and HF6 HF2 HF2 Motor Oil HF2

Lower level (CI)c

Test results Signicantly higher Signicantly higher No difference Signicantly higher Signicantly higher Signicantly higher No difference Signicantly higher

Oil type Motor Oil Motor Oil Kerosene and HF6 HF2 and HF6 HF2 HF2 Motor Oil HF2

1 1.92 0.28 2 2.05 1.33 3 2.75 0.58 4 10.69 5.16 5 4.34 3.57 6 1.97 0.57 7 2.22 0.31 8 3.70 2.27 Comparison of GC-FID-MeCl2 with GC-FID-Freon Methods Soil sample Upper level (CI) Lower level (CI) 1 2 3 4 5 6 7 8 2.28 2.57 1.97 0.01 0.52 0.29 1.83 0.29 0.87 0.30 4.12 0.76 0.03 0.61 4.20 1.00

Test results Signicantly higher Signicantly higher No difference No difference Signicantly higher No difference No difference Signicantly higher

a Signicantly higher means the results of the rst method (according to the order noted in the table)

were signicantly higher than the results of the second method. b HF2 is heating fuel #2 and HF6 is heating fuel #6. c CI = Condence interval = 95%; /2 = 0.05/2 = 0.025, = (31) = 2 degrees of freedom and t( ,0.025) = 4.303.

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GC-FID-Freon extract measurements indicates that in six of eight samples, the concentration of TPH measured with the TPH-IR method is signicantly higher than GC-FID-Freon and the other two samples do not show any signicant difference in the measurements. Comparison of GC-FID-Freon and GC-FID-MeCl2 shows that for four samples, TPH concentrations measured with GC-FID-MeCl2 are signicantly higher than GC-FID-Freon-113 analysis. For analytical measurements of TPH in the soil samples a trend is observed that can be summarized as follows: TPH measurement of petroleum hydrocarbon contaminated soils using Freon-113 extraction and subsequent TPH-IR measurements show higher concentrations than methylene chloride extraction of same soil samples analyzed with GC-FID, which in turn produces higher concentration readings than Freon-113 extraction of the same soil samples analyzed with GC-FID. One possible explanation for higher readings by TPH-IR may be that the Method418.1 reference oil was used to calibrate the TPH-IR instrumentation. Therefore the TPH-IR analysis may have overestimated the petroleum hydrocarbon concentrations to varying degree depending on the nature of the TPH concentration (Figure 1). It was expected to see the TPH-IR results from samples 1,2,3 and 7 to also be substantially higher than the GC-FID results (Figure 2). However, it is possible that these samples had higher moisture content and were not thoroughly dried using sodium sulfate. Therefore the Freon extraction efciency was reduced far enough to compensate for the over estimation inherent in the IR analysis with 418.1 reference oil calibration. It should be noted that drying of soil samples is a critical step for accuracy and precision of both GC-FID and TPH-IR analysis of soil samples (Crawford, 1999). If the TPH-IR method is to be used as a tool for TPH measurements with Freon113 or with another solvent that is approved by U.S. EPA, comparative studies must be conducted with other approved TPH methods to assure that false positive readings are not produced with this method.

5. Conclusions Total Petroleum Hydrocarbon (TPH) concentrations of soil samples taken from the bottom and walls of excavated areas of former underground storage tanks storing motor oil, kerosene, #2 and #6 fuel oil were quantied with TPH-IR and GC-FID methods. The GC-FID method was applied for the methylene chloride (MeCl2 ) and the trichlorotriuoroethane (Freon-113) extracts. Therefore, three sets of quantitative results were obtained for eight soil samples (i.e. TPH-IR, GC-FID-Freon and GC-FID-MeCl2 ). Using a paired statistical t-test the average of paired differences of the quantitative results were compared. Comparing the TPH-IR and the GC-FIDMeCl2 methods indicated that TPH concentrations measured with TPH-IR method were higher than the GC-FID-MeCl2 and GC-FID-Freon methods. Considering the linearity of the alkanes response factors by GC-FID during calibration of the

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system and the performance check of the GC-FID instrument, it is very likely that the TPH readings with the TPH-IR method were higher than the actual TPH concentrations. The GC-FID method could be more time consuming and may require more efforts in preparation of samples than the TPH-IR method. Solvent extraction and use of GC-FID can have a few advantages over the TPH-IR method. Petroleum hydrocarbon compounds undergo physical and chemical processes in the subsurface and their initial mole fraction may change because weathering degrades the lighter compounds. GC-FID chromatograms may be used to identify the nature and sources of weathered hydrocarbon compounds in sites with history of petroleum related contamination. The GC/FID performance can be checked through the use of surrogates and standards. A gas chromatograph equipped with a ame ionization detector (GC-FID) may be considered to be a suitable tool for TPH detection and quantitation, due to the fact that most environmental laboratories use it for daily sample analysis. Due to the low extraction efciency of Freon-113 for high molecular weight hydrocarbons, TPH-IR may be a suitable screening method for soils that are contaminated with lighter (C8 - C21) hydrocarbon compounds (such as diesel and no. 2 heating fuel). This method does not specify the class of petroleum hydrocarbon and is highly sensitive to interference from non-hydrocarbon materials that naturally exist in soil. Use of TPH-IR method would most often result in concentrations higher than real values and the false positive readings could lead to extra and unnecessary cleanup costs. The GC-FID can identify the source of hydrocarbon contamination and errors associated with the method results are normally low and controllable. Due to the ban on the production of Freon-113 in the United State, EPA method 418.1 with application of Freon-113 as the extraction solvent may not be practical anymore in the near future. If other solvents such as high-grade tetrachloroethylene are going to be substituted for Freon-113, the associated costs of solvent purchasing and disposal should also be considered when comparing to a GC-FID based TPH analysis.

Acknowledgments The authors would like to thank the Waste Management Bureau of the State of Connecticuts Department of Environmental Protection. Special thanks go to Mr. Richard Crowley of the Environmental Research Institute for his laboratory assistance and to two anonymous referees for their constructive comments on this manuscript.

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