Advisory Opinion
Innovative Technology: Gas Chromatography Field Analysis
Date of Opinion: November 29, 2000
The purpose of this Advisory Opinion is to raise awareness of field portable gas chromatography (GC) technology and its on-site application in the Northeast.(1) This Advisory Opinion is intended to communicate Technology Review Committee (TRC) interest in the use of field portable GC technology to potential users of hazardous waste site characterization technology, such as consultants, as well as to project managers within the various state site cleanup programs. The Advisory Opinion is also intended to educate consultants and the state regulators who oversee projects about the factors that can affect the proper use of field portable GC technology.
All seven of the Northeast states participated in the development of this Advisory Opinion consensus statement. In addition, the technical information was reviewed by U.S. EPA Region I and vendors of GC technology. However, it should be noted that this Advisory Opinion is not intended to be an "approval" of this technology. The appropriateness of the use of GC technology will need to be determined on a site-by-site basis. Potential users should contact officials in the state in which the project is located to determine if there are any state-specific requirements that could apply.
Project Background:
Recognizing the need to overcome barriers to the acceptance of technology innovation, the six New England States, EPA Region I - New England, the Northeast Waste Management Officials' Association (NEWMOA) and the New England Governors' Conference signed a Memorandum of Agreement (MOA) in March 1998 to promote interstate regulatory cooperation for waste site assessment and cleanup technologies. Subsequently, NEWMOA has worked closely with EPA Region I and the Northeast Hazardous Substances Research Center (NHSRC) to increase the understanding of the factors that discourage the use of innovative technologies. NEWMOA held meetings and conference calls with NEWMOA's Waste Site Cleanup Workgroup and co-sponsored, with NHSRC, a Stakeholders Workshop held in May 1998 called "Increasing the Use of Innovative Technologies on Small Hazardous Waste and Petroleum Sites." The focus of this Workshop was on building consensus among the stakeholders regarding measures to reduce or eliminate obstacles to the use of innovative site assessment technologies.
At the May 1998 Stakeholder Workshop, participants identified the lack of an interstate forum in the Northeast to actively review technologies and communicate both public and private sector use of innovative technologies as a major impediment to the overall marketability of the newer field analytical, characterization and monitoring technologies. To address this need, NEWMOA has established the TRC, made up of one or more staff members from each of the Northeast states to coordinate state review, issue advisory opinions and disseminate information on the use of innovative technologies.
Benefits of Field-Based Site Characterization:
Regulatory and institutional barriers to the adoption of innovative hazardous waste site assessment technologies can result in increased expenditures to evaluate and remediate contaminated sites. Because innovative technologies have the potential to clean up and protect the environment and the public's health in a more cost-effective and efficient manner, finding ways to encourage their increased use is crucial. Some examples of the potential benefits of using field analytical methods to support a field investigation or cleanup verification program include:
Overview of Technology:
Field portable GC can be used for analysis of volatile organic compounds (VOCs) in water, soil, soil gas and ambient air. In theory, a field portable GC could be used to analyze for semi-volatile organic compounds (SVOC) such as pesticides and PCBs; however due to sample preparation needs, SVOC analysis in the field is not common. A field portable GC could be appropriate for use at hazardous waste sites to:
Gas chromatography is a separation technology, not an analytical technology in itself. After the sample is separated into its constituent compounds by the GC, it is analyzed by a follow-on detection technology. The GC processes gaseous samples and therefore, water and soil samples must be prepared to drive the contaminants into gaseous phase. The various detection technologies are discussed after the GC technology itself is presented. Sample preparation is discussed in a section after the detection technologies.
Gas Chromatography
Gas chromatography is used to separate a mixture of closely-related compounds into the individual compounds for measurement. For example, GC is often used to separate a mixture of VOCs into the individual compounds. The sample is typically introduced into the instrument through the injection port using a syringe. The injection port is heated so the analytes are vaporized and are then mixed with an inert gas called the mobile phase or carrier gas, usually nitrogen, helium or hydrogen.
The mobile phase carries the sample through a coiled tubular column where analytes interact with the material on the inside of the column called the stationary phase. The analytes are kept in the gaseous state by using an oven to keep the column temperature above the boiling point of the analytes. The rate at which the mobile phase moves through the column can be varied, higher rates are associated with faster analysis times, but lower resolution of the results. The length and diameter of the column can also vary. Typical column length is 30 to 60 meters. The shorter the column the faster the analysis time, but the lower the resolution. Columns are typically between 0.25 and 0.32 millimeters (mm) in diameter, with high resolution columns between 0.15 and 0.20 mm. Capillary columns are usually made of fused silica due to its strength and flexibility.
The stationary phase is chosen so that the components of the sample distribute themselves between the mobile and stationary phase to varying degrees. Those components that are strongly retained by the stationary phase move through the column more slowly than components that have a lower affinity for the stationary phase. The stationary phase is an organic liquid compound that is either coated on or covalently bonded to the silica surface of a capillary column. The polarities of the compounds of interest dictate the choice of stationary phase, under the rule "like dissolves like." Commonly used stationary phases include:
polydimethyl siloxane (commonly referred
to as OV-1 of SE-30) for PCB or PAH separation carbowax - used for free
acids, alcohols, and glycols
OV-17 - for pesticides and glycols
OV-210 - for chlorinated aromatics, nitroaromatics,
and alkyl substituted benzenes
OV-3 or SE-52 for halogenated organics.
Dual column analysis is often used to confirm the identification of a compound(s) indicated by single column analysis. Dual column analysis means that two columns are used, each with a different stationary phase to increase the GCs ability to separate a wider range of compounds.
Environmental samples can have high concentrations or other constituents that can ruin column performance and require its replacement. Samples with the potential for high concentrations are typically diluted before introduction to the GC. A field screening technique, such as using an flame ionization detector (FID) or photoionization detector (PID) alone, can help identify samples that are likely to contain high concentrations. For PCB analysis of oily samples, components of the oil can ruin column performance. Another rare, but potential problem is that excessive oven temperatures can cause the stationary phase to elute from the column, called column bleed which fouls the follow-on detector, requiring its replacement.
Detectors
As a consequence of the differences in analyte mobility, the sample components separate into discrete bands that can be analyzed qualitatively and quantitatively by the follow-on detection device. The compound is identified and its concentration determined by comparison to the results obtained by running a known standard through the equipment, or in the case of an mass spectrometer (MS) detector, by comparison to a built-in library. The compound is identified on a chromatograph by its distinctive retention time - how long it takes to emerge from the GC - and is quantified by measuring the area under peak. Older equipment produces a paper chromatogram as output and does not store data long-term, whereas newer equipment typically requires the integrated use of a personal computer for data storage, management and output.
There are several detection technologies
available and the five most appropriate for hazardous waste site characterization
and remediation are described below:
| mass spectrometer (MS): could be used for quantitative analysis of VOCs and SVOCs.(3) As the analyte enters the MS, it is ionized, typically by a 70 electron volt (ev) electron beam. Generally, the resulting fragmentation of the analyte produces a mass spectrum that represents the chemical structure of the analyte. The analyte is identified by comparing the resulting mass spectrum to a reference library. More specifically, the loss of an electron during ionization generates a charged molecular ion, usually with the same molecular weight as the analyte molecule. Excess energy from the beam further fragments the molecular ion to fragment (daughter) ions with lower mass to charge ratio. The positive ions and ion fragments produced by electron impact are attracted through the slits of the ion source and the mass analyzer. These ions are mass analyzed for differentiation according to their mass-to-charge ratios. The mass sorted ions are detected by an electron multiplier and the resulting signal is sent to a data system for processing. |
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| photoionization detector (PID): uses a special ultraviolet lamp to energize and ionize the separated compounds as they pass through the PID. The ions collect at positively charged electrodes where the change in current is measured and compared with standards for compound identification. The ultraviolet lamp energy can range from 9.5 to 11.7 eV, with 10.2 eV the most common. A 10.2 eV lamp can ionize compounds with ionization potentials below 10.2 eV, such as BTEX compounds and hexane. Chlorinated compounds with double bonds, such as trichloroethylene and tetrachloroethylene have lower ionization potentials and can be detected with the lower energy lamps. Chlorinated compounds with single bonds, such as methylene chloride and 1,1,1-trichloroethane require the higher energy lamps for ionization. |
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| flame ionization detector (FID): mixes the carrier gas containing the separated compounds with hydrogen in the presence of a flame. Hydrocarbons and other molecules which ionize in the flame are attracted to a collector electrode located to the side of the flame. The resulting electron current is amplified and converted into millivolts. |
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| electron capture detector (ECD): contains radioactive nickel-63 that emits beta particles (electrons) which collide with the carrier gas. These collisions ionize the molecules to form a stable cloud of free electrons in the ECD cell. When an electronegative molecule such as a halogenated molecule enters the cell, it immediately combines with one of the free electrons, temporarily reducing the number of free electrons. This temporary reduction is measured by the detector. An ECD is highly sensitive to electronegative molecules such as halogenated compounds and those that contain nitrogen. |
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| electrolytic conductivity detector (ELCD): Organic compounds form combustion products as they are mixed with hydrogen gas over a nickel catalyst at 1,000 oC in a quartz tube furnace. The resulting change in electroytic conductivity is monitored by the ELCD. An ELCD is a halogen-specific detector that readily detects chlorinated pesticides, halogenated solvents, PCBs and dioxins. |
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Sample Preparation
The GC processes gaseous samples and therefore, water and soil samples must be prepared so as to drive the contaminants into gaseous phase. Descriptions of sample preparation for VOC and SVOC analysis are presented below. For contaminant mixtures containing both SVOC and VOC, two separate samples would need to be collected and analyzed with one undergoing the SVOC sample preparation process and the other undergoing the VOC process.
VOC Analysis: Soil samples first
undergo an extraction procedure to move the contaminants into a liquid.
Soil sample preparation can vary depending on the analyte concentration
and the soil type. For low concentration samples (200 ppm) reagent grade
water is often used to place the analytes into solution. Methanol is commonly
used for samples with higher concentrations. One of two common techniques
are used to move the contaminants from a liquid (either a water sample
or the liquid from soil extraction) into the gaseous phase: static headspace
or purge and trap. A third method for transfering sample contaminants from
a liquid into the GC that shows promise for field application is solid
phase microextraction (SPME). This technique is discussed further in the
SVOC analysis section.
| Static headspace: Static headspace requires minimal sample preparation. Static headspace relies on Henry's Law which states that the vapor pressure of the solute in the headspace is proportional to its mole fraction in solution. Therefore, analysis of the headspace determines the VOC concentration of a liquid sample without time consuming solvent extractions. Automated headspace samplers are available in which all samples are heated to the same temperature (typically in the range of 40 to 80oC) for the same amount of time (typically 10 to 30 minutes) to allow the sample to come to equilibrium. The headspace vial is pressurized and allowed to equilibrate. The headspace is vented into the sample loop where it is allowed to equilibrate again before it is drawn into the GC. |
| Purge and trap: In the purge and trap method, helium is bubbled through the sample at ambient temperature so the volatiles are transferred from the matrix to the vapor phase. The volatiles are then swept through a sorbent column where they are trapped. Then the column is heated and backflushed with helium to desorb the compounds which are transferred to the GC. |
Comparison Between Static Headspace
and Purge and Trap
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There are two emerging extraction techniques that appear to be promising techniques for field use because they are rapid, use little or no solvent, simple, and inexpensive: solid-phase extraction (SPE) and solid phase microextraction (SPME). SPE is primarily limited to water samples, although it can be used as a cleanup technique for liquid extracts of solid samples. SPME has become popular in the last few years because it can be used for both VOCs and SVOCs and no solvent is required.
SPME requires that the sample is in a liquid or gaseous form, so soil samples must undergo an extraction procedure prior to SPME. SPME is a adsorption/desorption technique that uses a silica fiber coated with a polymer to adsorb organic analytes from the headspace of a liquid sample. The polymer coated fiber is then introduced to the GC injector where the analytes are thermally desorbed. It is important that the analyst allow the sample to come to equilibrium (usually 2-30 minutes) and maintain consistent sampling times to obtain reliable results. Selectivity can be altered by changing the type of polymer coating or the thickness of the coating to match the analytes of interest. In general a thick coating is better for VOCs and a thin coating for SVOCs. More information about SPME can be found at www.sigma.sial.com in the Supelco section.(5)
Thermal desorption of SVOCs is a technique to move the contaminants directly from a soil sample into the gaseous phase. A quantity of soil is placed in a chamber where it is heated to a high temperature, driving the SVOCs from the soil into the gas where it is drawn into the GC. Thermal desorption is convenient for field use because it is simple, rapid, and requires no solvent. However, the samples enter the GC at much higher temperatures than most other techniques and modifications are needed to account for this.
Independent Verification and Use in the Northeast:
Several different GC and GC/MS units have been evaluated in the EPA's Environmental Technology Verification (ETV) Program. The Technology Verification Statements for the evaluated units as well as more information about the ETV Program itself can be obtained at http://www.epa.gov/etv or by calling U.S. EPA Region I at (617) 575-CEIT. Three GC/MS technologies were evaluated as their own category under the Site Characterization and Monitoring Technologies Pilot, and two GC technologies and one GC/MS where evaluated under the Well-Head Monitoring - VOCs category within the same pilot.
GC technology has been used for site characterization or cleanup monitoring at over 25 Superfund sites, including several Department of Defense (DOD) and Department of Energy (DOE) facilities.(6) U.S. EPA Region I has used portable GCs, usually with PID and ECD detectors for "hot spot" identification at numerous sites since the 1980's and reports a throughput of up to 50 samples per day (includes QA/QC sample analysis). EPA Region I also uses portable GCs for removal verification. EPA Region I has also used portable GC/MS technology at several sites in New England.
Some of Northeast states, notably Connecticut, Massachusetts, New York, and Vermont, have successfully used GC technology, with PID, FID, ECD and ELCD detectors, during site characterization and/or remediation. Connecticut has a state-certified mobile laboratory that uses GC/MS. Massachusetts has also used portable GC/MS at three DOD sites, including Hanscom Air Force Base (HAFB). At HAFB, screening analysis using a GC/MS was done in the field and quantitative GC/MS analysis was performed in an on-site mobile laboratory trailer. A detailed case study of the HAFB was prepared by the U.S. EPA (EPA-542-R-98-006) and is available at www.clu-in.org in the Site Characterization section.
Recommendations:
The TRC has determined that, if used properly, field portable GC technology combined with an appropriate detector, can provide useful data that should improve site characterization and/or cleanup verification. The intended use of the data and data quality objectives (DQOs) must be determined prior to the field event and agreed to by the appropriate regulatory authority. The TRC recommends the following items to improve or insure product performance; however, users should recognize that each particular GC - detector combination might have additional requirements:
The NEWMOA Technology Review Committee
has issued this Advisory Opinion on this 29th day of November,
2000.
Christine Lacas, Connecticut DEP |
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________________________________ Paul Kulpa, Rhode Island DEM |
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For More Information Please Contact:
| In Connecticut:
Christine Lacas Department of Environmental Protection Bureau of Water Management 79 Elm Street Hartford, CT 06106 (860) 424-3766 |
In Maine:
Mark Hyland Department of Environmental Protection Bureau of Remediation and Waste Management 17 State House Station Augusta, ME 04333 (207) 287-7673 |
| In Massachusetts:
Dorothy Allen Department of Environmental Protection Bureau of Waste Site Cleanup One Winter Street Boston, MA 02108 (617) 292-5795 |
In New Hampshire:
Robert Minicucci Department of Environmental Services Waste Management Division 6 Hazen Drive Concord, NH 03301 (603) 271-2941 |
| In New York:
James Harrington Department of Environmental Conservation Division of Environmental Remediation 50 Wolf Road Albany, NY 12233 (518) 457-0337 |
In Rhode Island:
Paul Kulpa Department of Environmental Management Office of Waste Management 235 Promenade Street Providence, RI 02908 (401) 222-2797 |
| In Vermont:
Richard Spiese Department of Environmental Conservation Waste Management Division 103 South Main Street Waterbury, VT 05671 (802) 241-3888 |
At NEWMOA:
William Cass NEWMOA 129 Portland Street, 6th Floor Boston, MA 02114 (617) 367-8558, ext. 301 |
| At EPA New England:
Carol Kilbride U. S. EPA Center for Environmental Industry and Technology One Congress Street, Suite 1100 Boston, MA 02114 (617) 918-1831 |
1. In this document, the Northeast states are: Connecticut, Maine, Massachusetts, New Hampshire, New York, Rhode Island and Vermont.
2. provided 10 percent of samples are sent to a fixed laboratory for confirmatory analysis and appropriate quality assurance/quality control (QA/QC) is performed, including a correlation study.
3. Dioxin analysis requires the use of a high resolution MS which is currently not practical for field use.
4. Appropriate QA/QC measures and analysis is required for definitive identification.
5. Mention of any company or product name should not be considered an endorsement by NEWMOA, NEWMOA member states, or the U.S. EPA.
6. U.S. EPA, Field Analytical and Site Characterization Technologies, Summary of Applications, EPA-542-R-97-011, November 1997.
7. Less stringent QA/QC could be appropriate for field screening and/or determining which samples are best to send to a fixed laboratory - check with your regulatory authority.
8. New York specifies that the correlation co-efficient is 0.95.
9. New York specifies that the relative percent difference (RPD) is 30 percent.
10. New York specifies that the peak area for each target compound should be less than half the area of the reported detection limit.