UCRL-AR-135949 Vol. 4 Ch. 7

Volume 4: Potential Ground and Surface

Water Impacts

Chapter 7: Evaluation of Analytical Methods

for the Detection of Ethanol

 in Ground and Surface Water

Author

Carolyn Koester*

Editors

D. Rice*

G. Cannon*

Contributor

R. Depue*

December 1999

*Lawrence Livermore National Laboratory, Livermore, CA 94550

 University of California • Livermore, CA 94550

Lawrence Livermore National Laboratory
Work performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National

Laboratory under Contract W-7405-Eng-48.
UCRL-AR-135949 Vol. 4 Ch. 7 Potential Ground and Surface Water Impacts December 1999

11-99/Ethanol Ch. 7 7-i

Table of Contents

7. Evaluation of Analytical Methods for the Detection of Ethanol in Ground and

Surface Water .......................................................................................................................... 7-1

7.1. Analytical Requirements ............................................................................................. 7-1

7.1.1. Routine Detection of Trace Amounts of Ethanol in Environmental

Waters............................................................................................................. 7-1

7.1.2. Regulatory Requirements Versus Detection Limits for Fate and

Transport Studies........................................................................................... 7-2

7.2. Evaluation of Current Analytical Methods for Ethanol Detection ........................... 7-3

7.2.1. Ethanol Analysis Methods Used by Food and Biomedical

Industries........................................................................................................ 7-4

7.2.2. Ethanol Analysis Methods Used by the Environmental

Community .................................................................................................... 7-4

7.3. Handling and Preservation of Ethanol Samples......................................................... 7-5

7.4. Recommendations to Improve Sampling and Analysis of Ethanol in

Ground and Surface Water .......................................................................................... 7-6

7.4.1. Rigorous Study of Sample Preservation ...................................................... 7-6

7.4.2. Improved Extraction of Ethanol from Aqueous Samples ........................... 7-6

7.4.3. Improved Strategies for Ethanol Detection.................................................. 7-7

7.4.4. Minor Modifications to Improve Existing Methods.................................... 7-7

7.5. Summary....................................................................................................................... 7-8

7.6. References .................................................................................................................... 7-8

Table

Table 7-1. Summary of ethanol analysis methods. Data are ordered by publication

date and subgrouped by decreasing limit of detection............................................. 7-13
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7. Evaluation of Analytical Methods

for the Detection of Ethanol in

Ground and Surface Water

7.1. Analytical Requirements

7.1.1. Routine Detection of Trace Amounts of Ethanol in Environmental

Waters

Ethanol in the environment might be present in air, soil, and water. Ethanol in air partitions

to water1. In an organic soil/water system, ethanol partitions almost exclusively into the water2.

Thus, water is an important environmental reservoir for ethanol. The primary objective of this

chapter is to review methods applicable to the routine analysis of ethanol in environmental

waters. (The analysis of ethanol in air and soil is outside the scope of this document and will not

be addressed.)

The analysis of ethanol in environmental waters is difficult. In order to analyze ethanol, or

any other contaminant of interest, one must first extract (or remove) it from water. Once it is

removed from water, the contaminant must then be separated from hundreds or thousands of

other contaminants so that it can be specifically identified or detected. Once it has been

identified, the quantity of that contaminant in the water can be determined. Of these steps, the

extraction of ethanol from water is the most challenging.

Ethanol is a small, polar molecule. Ethanol associates (or hydrogen bonds) with water,

making it difficult to extract from water and difficult to measure low concentrations in the

environment. However, if ethanol can be extracted from water, sufficient methods exist to

separate, identify, and measure it.

The appropriate analytical methods to analyze (that is, extract, separate, identify, and

measure) ethanol, or any other environmental contaminant, are dictated by the intended use of

data. This review considers three uses of collected data:

• Assessment of ethanol concentrations at a spill site.

• Documentation to meet regulatory requirements.

• Understanding of the environmental fate and transport of ethanol.

 1

 Based on accepted values of Henry’s law constant for ethanol that range from 0.5 to 0.6 Pa•m3/mol (MacKay,

et al., 1995).

2

 Ethanol’s low octanol-water partition coefficient (Kow), log Kow values of –0.3 to –0.2 (MacKay et al., 1995)

indicate that ethanol partitions into water rather than remaining in soil.
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Several issues influence the selection of an analytical method that will provide the data

needed for these three uses. In all cases, the selected analytical methods must possess the

following characteristics:

• Appropriate DLs.3

• Good precision.4

• Good accuracy.5

• Easily performed and reproducible by different analysts in different laboratories.

• No false positive (interferences) or negative detections.

• Adherence to quality assurance/quality control (QA/QC) protocols.6

For any type of chemical analysis, adherence to stringent QA/QC protocols is the criterion

most critical to providing data that can be compared by different investigators. It is for this

reason that the United States Environmental Protection Agency (US EPA) has promulgated

specific analytical methods (and strict QA/QC protocols) for the monitoring of contaminants in

the environment. For example, all laboratories performing regulatory analyses must strictly

adhere to the US EPA protocols to prove regulatory compliance.

Another issue of concern is practicality. The chosen analytical methods need to be cost

effective and easily performed (with minimal manual labor). Costs of current analyses for

organic compounds range from approximately $100–$400. Thus, in order to be cost effective,

analyses of environmental samples for the presence of ethanol should fit into this price range.

7.1.2. Regulatory Requirements Versus Detection Limits for Fate and

Transport Studies

We previously stated that there are several reasons that one might wish to monitor ethanol

contamination in the environment, including (1) to assess ethanol contamination at a spill site,

(2) to document that regulatory requirements are being met or exceeded, and (3) to understand

the environmental fate and transport of ethanol. In each case, it is important to establish what

concentration of ethanol needs to be detected in order to meet the objective of the study.

For example, a regulatory concentration limit for a specific contaminant might be based on

predicted health effects and risk-assessment models. Let’s assume that the regulated limit of

Analyte X is 30 parts-per-billion (ppb) in drinking water. In order to prove that the regulatory

concentration of Analyte X is not exceeded, the method selected to analyze drinking water must

be capable of accurately and reproducibly measuring 30 ppb of ethanol. Thus, the DL (or the

minimum concentration of Analyte X that can be detected by an analytical method) required for

this analysis is 30 ppb or lower. In practice, the desired detection limit (DL) should be three to

 3

 The analyte must be detected at a sufficiently low concentration to meet the study/regulatory requirements.

4

 Multiple measurements of an analyte in the same sample will give identical results.

5

 Measured concentration of analyte reflects its true concentration in a sample.

6

 A QA/QC program encompasses procedures used to ensure that analyses are consistently performed, meet user

requirements, and that data generated by a laboratory are accurate, precise, reproducible, and defensible in a court of

law.
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five times lower (6–10 ppb) than the set regulatory limit desired in order to ensure that Analyte

X is easily detected at its regulated limit of 30 ppb.

Currently, ethanol is not considered by the federal government or by the state of California to

be a regulated compound. No guidance is available to dictate needed DLs. However, based on

the potential uses of ethanol data, we can make some good assumptions about what DLs are

needed to provide data for specific studies:

• Case 1: Assessing Ethanol Contamination at a Spill Site. The expected concentration

of ethanol in contaminated groundwater near a spill site is likely to range between 400 to

4000 parts per million (ppm) (Malcolm Pirnie, Inc., 1998). Thus, the monitoring of

ethanol-contaminated water associated with fuel spills would require methods with DLs

of 400 ppm in order to document significant ethanol contamination at a site. In addition,

the selected analytical method must detect ethanol in the presence of high concentrations

of hydrocarbons found in gasoline.

• Case 2: Documenting That Regulatory Requirements Are Met. The taste and odor

thresholds of ethanol in drinking water are 50 ppm and greater than 100 ppm,

respectively (Malcolm Pirnie, Inc., 1998). If we assume that no adverse health effects are

associated with consuming trace quantities of ethanol, we would predict that a drinkingwater standard would be set at the taste threshold of ethanol (50 ppm). Thus, a method at

least 50 ppm would be sufficient to ensure water quality. This DL is approximately a

factor of ten lower than that required to characterize ethanol contamination at a spill site.

• Case 3: Understanding Environmental Fate and Transport. In order to determine

the movement of ethanol through the environment, the environmental background levels

of ethanol at uncontaminated sites need to be assessed. Parts-per-billion concentrations

of ethanol, possibly produced by “natural” chemical and biological processes, might be

present in environmental surface and groundwaters. It is also possible that surface and

groundwaters will be indirectly impacted by the use of blended fuels. In order to

understand the native background of ethanol in the environment and to understand the

impact of ethanol from blended fuels, the lowest DLs achievable (parts per billion, or

better) would be needed.

7.2. Evaluation of Current Analytical Methods for Ethanol

Detection

Few papers have been published describing the analysis of ethanol in environmental samples.

This pretermission is, in part, because ethanol has not been considered to be a contaminant of

environmental concern. Ethanol is not included in several comprehensive references of

groundwater contaminants (Prager, 1995; Montgomery, 1996). In addition, because the human

body tolerates percent quantities of ethanol that are present in alcoholic beverages, human

consumption of trace quantities of ethanol, which might contaminate food and drinking water,

have not been of great concern.
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7.2.1. Ethanol Analysis Methods Used by Food and

Biomedical Industries

Table 7-1 summarizes the methods that have been used for ethanol analyses. It also contains

information about the analytical technique applied, the type of sample analyzed, and the limit of

detection obtained. It also indicates if the method might be useful in the analysis of

environmental waters.

The alcoholic beverage industry performs many ethanol analyses to insure the quality of its

products. Ethanol DLs for the analyses of beer and wine cited in Table 7-1 range from 1 to

50,000 ppm. However, many of these methods do not have sufficient DLs to be applied to the

analysis of ethanol in environmental samples. The method using an oxygen-electrode sensor

(5–10 ppm DLs) lacks a large dynamic range and would not be applicable to environmental

analyses. The gas-diffusion membrane coupled with amperometric detection (1-ppm DL) might

prove useful for the analysis of environmental samples; however, studies need to be performed to

determine if this method is applicable to environmental samples.

DLs for ethanol in biological fluids reported within the last five years are 10 ppm or better

(see Table 7-1). Note that these DLs are below the taste and odor thresholds for ethanol in water.

The recent methods cited used either headspace gas injection or direct injection of the biological

fluid coupled with gas chromatography combined with flame-ionization detection (GC/FID).

GC/FID is more analyte specific than many of the electrochemical methods used in the alcoholic

beverage industry. Because of their good DLs, GC/FID methods are potentially applicable to the

analysis of ethanol in environmental samples.

7.2.2. Ethanol Analysis Methods Used by the Environmental

Community

In 1986, the United States Environmental Protection Agency (US EPA) suggested that

ethanol analysis might be performed by purge-and-trap gas chromatography coupled with a

flame-ionization detector (that is, Method 8015 [US EPA, 1986]). Method 8015 listed no

method DL, linear range, precision, or accuracy data. By 1996, both US EPA Methods 8015B

and 8260B stated that purge-and-trap extraction was inappropriate for ethanol analysis (US EPA,

1996c and 1996d). Instead, these methods suggested that azeotropic distillation (that is, Method

5031 [US EPA, 1996a]) and vacuum distillation (Method 5032 [US EPA, 1996b]), were

appropriate techniques to extract and concentrate ethanol from water samples. In addition, these

methods suggested that direct aqueous injection of water into a GC/FID, or the use of a gas

chromatograph coupled with a mass spectrometer (GC/MS) was appropriate for ethanol analysis.

Again, because ethanol is not a regulated compound, the US EPA methods contained no

information regarding DL, linear range, precision, or accuracy.

While the US EPA does not endorse the use of the purge-and-trap technique for ethanol

analysis, several methods have successfully used this extraction technique. GeoChemistry of

Canoga Park, CA (recently purchased by and soon to relocate to ZymaX Envirotechnology, Inc.,

of San Luis Obispo, CA) is one of the few California laboratories known to perform ethanol

analyses for environmental samples. Global GeoChemistry (1999) uses a modified version of

Method D4815 of the American Society of Testing and Materials (ASTM, 1997) to determine

ethanol in aqueous samples. ASTM Method D4815 was developed to measure
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0.1% concentrations of ethanol in gasoline and uses two-dimensional gas chromatography (2DGC) to remove interferences. The sample is injected directly into the gas chromatograph and

first eluted through a polar, capillary gas-chromatograph column that retains all oxygenates,

including ethanol. The oxygenates are then backflushed into a nonpolar, capillary gaschromatograph column for final separation and detection by a flame-ionization or thermalconductivity detector.

The Global GeoChemistry method combines purge-and-trap extraction with two-dimensional

chromatography coupled with a flame-ionization detector. DLs for ethanol in clean water and in

water contaminated with 5% nonaqueous phase liquid (NAPL) are 200 ppb and 100 ppm,

respectively.7

Zymax Envirotechnology, Inc. (McMurphy, 1999) has modified US EPA Method 8260B to

obtain 50-ppb DLs for ethanol in water. Its method uses purge-and-trap extraction at ambient

temperature and cryofocussing prior to final analysis by GC/MS8.

Researchers at the University of Nebraska have developed a solid-phase microextraction

(SPME) method coupled with GC/MS for the determination of ethanol in water. The SPME

method uses a small fiber (~1 cm in length by ~0.3 mm in diameter), which is coated with 85 μm

of a carboxen/polydimethylsiloxane polymer, to extract ethanol from water. After it has soaked

in the sample for about 30 minutes, the fiber, now containing ethanol, is removed from the

sample and directly injected into a GC/MS so that the amount of ethanol that has been collected

can be measured. This method yields DLs for ethanol of 15 ppb (Cassada et al., 1999). This

represents the best DL that has been reported to date for the determination of ethanol in water.

Although SPME can be automated easily, this technique requires a greater level of expertise to

perform than purge-and-trap methods.

7.3. Handling and Preservation of Ethanol Samples

In addition to the instrumentation used for ethanol analysis, researchers must consider sample

collection, preservation, and storage. If a sample is not properly collected, preserved, and stored,

then the data provided by sample analyses will be of questionable quality and will not be

scientifically (or legally) defensible.

Little has been reported regarding the collection and preservation of samples containing

ethanol. The conventional US EPA methods for sample collection and storage are often applied,

even though the storage methods endorsed have not always been rigorously tested. The US EPA

recommends collecting water samples in 40-milliliter (mL), glass vials with Teflon®-lined

 7 Sample matrix affects DLs. In general, DLs will increase, or worsen, as the complexity of the sample matrix

increases. In a complex matrix, many compounds are present at much higher concentrations than the compound of

interest, and these other compounds can interfere with the analytical signal produced by the compound of interest.

To obtain the best DLs possible, analysts must separate ethanol from other unknowns that might interfere with its

detection.

8

 For optimal gas chromatographic (GC) analysis, it is necessary to introduce the analytes as a narrow band on the

head of the GC column. In practice, very volatile compounds, such as ethanol, often “smear” at the head of the GC

column. One method to reduce this band broadening is to cool the GC column to sub-ambient temperatures (or, to

temperatures that are below the boiling points of the analytes). This, in effect, traps (or focuses) volatile compounds

as a narrow band of liquid at the head of the GC column and affords optimal GC analysis.
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septum caps. No headspace should be visible in the vials after sample collection. The samples

should then be stored at 4°C for a maximum of 14 days prior to analysis. To help preserve water

samples and to minimize bacterial growth that might degrade analytes in the sample, four drops

of concentrated hydrochloric acid may be added prior to cooling (Keith, 1996). In accordance

with US EPA-recommended procedures, Global Geochemistry (1999) refrigerates water samples

but does not preserve them with acid.

Researchers working on samples of biological fluids have also refrigerated samples prior to

analysis. McCarver-May and Durisin (1997) stored blood at 4°C prior to analysis. According to

Macchai et al. (1995), ethanol was stable for seven days in urine, serum, plasma, and saliva

when stored at 4°C; and ethanol in these matrices was also stable for up to two years when stored

at -20°C. Tangerman (1997) observed that ethanol in blood was stable for two weeks when

stored at room temperature, refrigerated, or frozen. Water, blood, serum, and urine samples

containing ethanol could be stored for three months at -20°C without ethanol loss (Tangerman,

1997).

7.4. Recommendations to Improve Sampling and Analysis

of Ethanol in Ground and Surface Water

7.4.1. Rigorous Study of Sample Preservation

The best conditions for the preservation and storage of samples containing ethanol need to be

determined. The commonly used protocol of collecting water samples in 40-mL vials with

Teflon®-lined septum caps and with no headspace should be continued. Data from the

biomedical community appears to validate the commonly used practice of storing aqueous

samples at 4°C for up to 14 days prior to analysis. Because the biomedical community suggests

that frozen samples containing ethanol can be stored for periods as long as two years, it is

possible that, under certain conditions, samples collected for ethanol analysis can be stored

longer than 14 days prior to analysis. It will be important to determine if environmental samples

can be stored for long periods without loss of ethanol.

7.4.2. Improved Extraction of Ethanol from Aqueous Samples

The analysis of ethanol in environmental waters is difficult. As previously discussed, ethanol

is a small, polar molecule and is difficult to remove from water. The poor extraction efficiency

of ethanol from water is the main contributor to its poor analytical DLs. Thus, any

improvements in methods to remove ethanol from water will result in better DLs. The literature

reviewed for this study indicates that either direct injection of an aqueous solution or injection of

the headspace above an aqueous liquid can be used to obtain DLs of 10 ppm or less. Thus, these

sample introduction techniques are sufficient to detect ethanol at its taste or odor threshold. Both

of these techniques are easy and inexpensive to perform.

Other sample introduction techniques, such as purge and trap, azeotropic distillation, or

vacuum distillation, could be investigated in the search for lower ethanol DLs. Of these

techniques, azeotropic distillation and vacuum distillation are more expensive and laborintensive (and not often performed) than purge and trap, which is performed easily, costeffectively, and routinely by contract laboratories. The newer technique of solid-phase
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microextraction (Zhang, 1994), in which ethanol might be removed from water using a small

fiber coated with special material, might also merit investigation. However, solid-phase

microextraction is not currently performed routinely by contract laboratories.

7.4.3. Improved Strategies for Ethanol Detection

In order to eliminate problems with potential interferences, we recommend that gaschromatographic (GC) separation be used in all future ethanol analyses. There are two practical

strategies that can be used for the sensitive detection of ethanol in the presence of interfering

compounds. The first is to use the best possible gas-chromatography procedure to separate

ethanol from any interferences and, then, to detect ethanol with a nonspecific detector, such as a

flame-ionization detector. The second strategy is to perform a less rigorous gas-chromatographic

separation coupled with a detector that would respond specifically to ethanol but would not

respond to potentially interfering compounds. Both of these strategies merit consideration.

7.4.3.1. Use of Gas Chromatography and Nonselective Detector

In the literature reviewed, flame-ionization detectors (FIDs) were the detectors of choice for

ethanol analysis. A FID is frequently used because it responds well to a variety of organic

compounds. Because of the nonselective nature of the FID (that is, the FID provides a signal

whenever an organic compound is detected and provides no information about the nature of that

analyte), two-dimensional chromatography is recommended for use with this detector to

minimize interferences.

7.4.3.2. Use of Gas Chromatography with an Analyte-specific Detector

To improve detection specificity, we recommend investigating the coupling of a gas

chromatograph with an analyte-specific detector, such as either an atomic-emission detector

(AED) or a mass spectrometer (MS). The AED, operated in the oxygen-specific mode, can be

“blinded” to potentially interfering hydrocarbons. The MS is capable of providing a massspectral “fingerprint” unique to each organic compound. Neither the AED nor the GC/MS

would be cost prohibitive for an environmental laboratory to purchase, staff, or maintain. It

might be possible that use of the AED or MS would simplify the chromatographic requirements

such that only one GC column would be required to separate ethanol from potential

interferences.

7.4.4. Minor Modifications to Improve Existing Methods

In addition to the choice of experimental approach and instrumentation used for ethanol

analysis, there are several other analytical aspects to consider. Minor modifications to existing

methods might improve the detection of ethanol in water. For example, if conventional purgeand-trap extraction is to be used, the sample could be heated to improve ethanol extraction

efficiency. The choice of GC column dictates how efficiently ethanol can be separated from

interferences. Many different types of GC columns are available and could be tested for their

applicability to ethanol analysis. The use of cryofocussing in combination with gas

chromatography might be beneficial.
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7.5. Summary

The literature reviewed indicates that the technology currently exists to enable researchers to

detect ethanol at spill sites. Sufficient methods exist to determine ethanol at its taste threshold of

50 ppm in water. The implementation of these methods would require some study of extraction

and detection conditions and the establishment of strict QA/QC protocols. These are of great

importance in the development of a method that would be used to demonstrate regulatory

compliance. No methods reported are currently able to detect ethanol below 15 ppb in water.

Thus, much time and effort must be invested to enable the detection of trace concentrations of

ethanol. Until this is accomplished, we will be unable to completely understand the fate and

transport of ethanol in the environment. Regardless of the analytical methods selected for use, it

is recommended that a proposed method be evaluated using a variety of sample matrices—a

strategy that has been used previously to evaluate detection methods for methyl tertiary butyl

ether (MBTE) and other gasoline oxygenates (Happel et al., 1998).

7.6. References

ASTM (American Society of Testing and Materials) (1997). Method D4815. In: Annual Book of

ASTM Standards: Section 5, Petroleum Products, Lubricants, and Fossil Fuels. Vol. 05.03.

American Society of Testing and Materials, West Conshohocken, PA.

Alvarez, P. J. (1999). The Effect of Ethanol on BTEX Migration and Natural Attenuation.

Research proposal to the American Petroleum Institute, Washington DC. (personal

communication).

Cassada, D. A., Y. Zhang, D. D. Snow, and R. F. Spalding (1999). Trace analysis of ethanol and

MTBE in water using solid-phase microextraction and GC/MS (manuscript in preparation for

submittal to Analytical Chemistry).

Chan, W. H., A. W. M. Lee, and P. X. Cai (1992). Differential-pulse polarographic

microdetermination of ethanol and its application to beer analysis. Analyst 117:

1509-1512.

Chen, Z., J. Yu, and D. B. Hibbert (1997). Flow injection, amperometric determination of

ethanol in wine after solid-phase extraction. Electroanalysis 9: 541-543.

Collins, T. S., C. A. Miller, K. D. Altria, and A. L. Waterhouse (1997). Development of a rapid

method for the analysis of ethanol in wines using capillary electrophoresis. Am. J. Enol.

Vitic. 48: 280-284.

Corseuil, H. X., C. S. Hunt, R. C. F. D. Santos, and P. J. J. Alvarez (1998). The influence of the

gasoline oxygenate ethanol on aerobic and anaerobic BTX biodegradation. Wat. Res. 32:

2065-2072.

Global GeoChemistry Corporation (1999). Corporate website (online). Conaga Park, CA.

Available: <www.ggclab.com/ggctext.html>.

Happel, A. M., E. H. Beckenbach, and R. U. Halden (1998). An Evaluation of MTBE Impacts to

California Groundwater Resources. Lawrence Livermore National Laboratory, Livermore,

CA. UCRL-AR-130897.

Keith, L. H. (1996). Compilation of EPA’s Sampling and Analysis Methods. 2nd Ed. CRC

Press, Inc., Boca Raton, FL.
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Kotiaho, T., F. R. Lauritsen, H. Degn, and H. Paakkanen (1995). Membrane inlet ion mobility

spectrometry for on-line measurement of ethanol in beer and in yeast fermentation. Anal.

Chem. Acta. 309: 317-325.

Macchia, T., R. Mancinelli, S. Gentili, E. C. Lugaresi, A. Raponi, and F. Taggi (1995). Ethanol

in biological fluids—headspace GC measurement. J. Anal. Toxicol. 19:241-246.

MacKay, D., W.-Y. Shiu, and K.-C. Ma (1995). Illustrated Handbook of Physical-Chemical

Properties and Environmental Fate for Organic Chemicals, Volume 4, Oxygen, Nitrogen,

and Sulfur Containing Compounds. Lewis Publishers, Boca Raton, FL.

Malcolm Pirnie, Inc. (1998). Evaluation of the Fate and Transport of Ethanol in the

Environment. Report prepared for American Methanol Institute, Washington, DC. Malcolm

Pirnie, Inc. Oakland, CA. November. Report No. 3522-0901.

McCarver-May, D. G., and L. Durisin (1997). An accurate, automated, simultaneous gas

chromatographic headspace measurement of whole blood, ethanol, and acetaldehyde for

human In Vivo studies. J. Anal. Toxicol. 21: 134-141.

McMurphy, J. (1999). (Zymax Envirotechnology, Inc.) Personal communication describing

modified US EPA Method 8260B. August 19.

Mohns, J., and W. Künnecke (1995). Flow analysis with membrane separation and time-based

sampling for ethanol determination in beer and wine. Anal. Chem. Acta. 305: 241-247.

Montgomery, J. H. (1996). Groundwater Chemicals Desk Reference. 2nd ed. CRC Press, Inc.,

Boca Raton, FL.

Prager, J. C. (1995). Environmental Contaminant Reference Databook. Van Nostrand Reinhold,

New York, NY.

Tangerman, A. (1997). Highly sensitive gas chromatographic analysis of ethanol in whole Blood,

serum, urine, and fecal supernatants by the direct injection method. Clinical Chemistry 43:

1003-1009.

Ukeda, H., Y. Fujita, M. Sawamura, H. Kusunose, and Y. Tazuke (1993). Flow injection analysis

of ethanol based on oxygen consumption using alcohol dehydrogenase and NADH oxidase

from Bacillus-licheniformis. Anal. Sci. 9: 779-782.

US EPA (United States Environmental Protection Agency) (1986). Method 8015,

Nonhalogenated Organics Using GC/FID. In Test Methods for Evaluating Solid Waste. 3rd

Edition. United States Environmental Protection Agency, Research Triangle Park, NC (US

EPA SW-846).

US EPA (United States Environmental Protection Agency) (1996a). Method 5031, Volatile,

Nonpurgeable, Water-soluble Compounds by Azeotropic Distillation, Revision 0. In SW-846

On-line Test Methods for Evaluating Solid Waste Physical/Chemical Method, 3rd Ed.

Available: <http://www.epa.gov/epaoswer/hazwaste/test/main.htm>

US EPA (United States Environmental Protection Agency) (1996b). Method 5032, Volatile

Organic Compounds by Vacuum Distillation, Revision 0. In SW-846 On-line Test Methods

for Evaluating Solid Waste Physical/Chemical Method, 3rd Ed. Available:

<http://www.epa.gov/epaoswer/hazwaste/test/main.htm>.

US EPA (United States Environmental Protection Agency) (1996c). Method 8015B,

Nonhalogenated Organics using GC/FID, Revision 2. In SW-846 On-line Test Methods for

Evaluating Solid Waste Physical/Chemical Method, 3rd Ed. Available:

<http://www.epa.gov/epaoswer/hazwaste/test/main.htm>.
UCRL-AR-135949 Vol. 4 Ch. 7 Potential Ground and Surface Water Impacts December 1999

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US EPA (United States Environmental Protection Agency) (1996d). Method 8260B, Volatile

Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS), Revision 2. In

SW-846 On-line Test Methods for Evaluating Solid Waste Physical/Chemical Method, 3rd Ed.

Available: <http://www.epa.gov/epaoswer/hazwaste/test/main.htm>.

Watts, M. T., and O. L. McDonald (1990). The effect of sodium chloride concentration, water

content, and protein on the gas chromatographic headspace analysis of ethanol in plasma.

Amer. J. Clin. Pathology 93: 357–362.

Zhang, Z., M. J. Yang, and J. Pawliszyn (1994). Solid-phase microextraction. Anal. Chem. 66:

844A–853A.
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UCRL-AR-135949 Vol. 4 Ch. 7 Potential Ground and Surface Water Impacts December 1999

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Table 7-1. Summary of ethanol methods. Data are ordered by publication date and subgrouped by

decreasing limit of detection.

Technique Sample

Limit

of

detection

(ppm)

Useful

in

environmental

analysis? Reference

Headspace GC/FID plasma 1000 no Watts and McDonald,

1990

Derivatization to ethyl

dithiocarbonate; differential-pulse

polarography

beer 200 no Chan et al., 1992

Oxygen electrode based on NADH

oxidase from Bacillus licheniformis

and alcohol dehydrogenases

wine 5–10 no Ukeda et al., 1993

Online, membrane inlet ion mobility

spectrometry

beer 500 no Kotiaho et al., 1995

Heated (75°C) headspace GC/FID biol. fluids 10 maybe Macchia et al., 1995

Flow injection analysis coupled with

gas-diffusion membrane and

immobilized alcohol oxidase;

amperometric detection

beer, wine 1 maybe Mohns and Künnecke,

1995

Micellar electrokinetic capillary

chromatography; diode-array detection

wine 50,000 no Collins et al., 1997

Solid-phase extraction cleanup; flowinjection analysis; amperometric

detection

wine 500 no Chen et al., 1997

Heated (75°C) headspace GC/FID blood 0.3 yes McCarver-May and

Durisin, 1997

10-microliters (-μL) direct injection,

GC/FID

biol. fluids 0.1 yes Tangerman, 1997

5-μL direct injection, GC/FID water 3 yes Corseuil et al., 1998

5-μL direct injection, GC/FID water 1 yes Alvarez, 1999

Modified ASTM Method D4815

(purge & trap, 2D GC/FID)

soil, water 0.2 yes Global GeoChemistry,

1999

Modified US EPA Method 8260B with

cryofocussing

water 0.05 yes McMurphy, 1999

Solid-phase microextraction coupled

with GC/MS

water 0.015 yes Cassada, et al., 1999

Key:

2D-GC = two-dimensional gas chromatography

ASTM = American Society of Testing and Materials

US EPA = United States Environmental Protection Agency.

GC/FID = gas chromatography with flame-ionization detection

GC/MS = Gas chromatograph with a mass spectrometer.
UCRL-AR-135949 Vol. 4 Ch. 7 Potential Ground and Surface Water Impacts December 1999

11-99/Ethanol Ch. 7 7-14