Posts Tagged ‘EPA Method 25’

VOC Measurement – EPA Reference Method 25 Modifications

EPA Method 25 determines volatile organic compounds in stationary source emissions. The VOCs are measured as total gaseous non-methane organics (TGNMO) and reported as carbon. Separate measurements are necessary to determined exempt NMO compounds and the average MW/CW.

An emission sample is withdrawn from the stack at a continuous rate through a heated filter and dry ice chilled condensate trap via an evacuated sample tank. After sampling is finished, the TGNMO are calculated by independently analyzing the condensate trap and sample tank fractions and combining the analytical results. The organic content of the condensate trap fraction is detected by oxidizing the NMO to carbon dioxide (CO2) and quantitatively collecting in the effluent in an evacuated vessel; then a portion of the CO2 is reduced to CH4 and measured by an FID. The organic content of the sample tank fraction is measured by injecting a portion of the sample into a gas chromatographic column to separate the NMO from carbon monoxide (CO), CO2, and CH4; the NMO are oxidized to CO2,reduced to CH4, and measured by an FID. In this manner, the variable response of the FID associated with different types of organics is eliminated.

EPA Method 25 accurately measures:

TGNMO, from 50 to 100,000 ppmC

CH4, ppm (M18)

CO, ppm (M10B)

CO2, ppm (M3A)

With proper modifications EPA Method 25 can also correctly measure:

TGNMO, 20 to >2,000,000 ppmC,

100,000 ppmC even in high moisture-CO2 gas

C2H5, ppm (Method 18)

% H20 (M4), mg TGNMO/ml H20

% O2 and N2 (Method 3A)

TGNMO in hot (>600°F) gases

TGNMO in gas streams with organic-laden aerosols/droplets

METHOD 25 for VOC > 500,000 ppmC:

• Use a chilled micro-impinger ahead of Method 25 trap during sample collection or recovery.

• Determine condensed VOC gravimetrically.

• Method 25 can measure exempt compounds in condensate.

• The MW/CW can be measured directly.

• Limited to samples with >1g organic condensate in the chilled micro-impinger.

EPA METHOD 25 MODIFICATIONS

METHOD 25 FOR LOW VOC 20-50 ppmC

• Use ultra-clean practices.

• Lower blank to 10±2.5 ppmC

• Retrieve large gas samples.

• Analyze 2 field blanks and apply blank-correction.

• Perform warm purge on all samples.

• NCASI (National Council for Air and Stream Improvement) has performed numerous wood-fired boiler VOC Method 25 tests with this modification.

EPA METHOD 25 FOR ETHANE

• Adjust M25 GC integrator windows.

• NG is -5% ethane by volume and -10% of carbon.

• Ethane can be a big part of the VOC.

• Some sources have low VOC and high NG

EPA METHOD 25 FOR H20

• H20 to ±3%

• Water trap with calibrated scale.

• For steam vents with polar & non-polar VOC, report mg VOC/ml H20.

EPA METHOD 25 for % O2, N2, CO2

• GC/TCD of sample tank per M25C.

EPA METHOD 25 for hot gas, >600°F

• Reduce time sample gas spends in hot probe to • Use a 50 cm long, narrow-bore 1/8 inch OD Inconel extension on the end of the M25 probe.

EPA METHOD 25 FOR ORGANIC AERESOLS

• Isokinetic (M5) front half extract M25 sample from behind heated filter.

What is a Volatile Organic Compound (VOC)?

According to the EPA, Volatile organic compounds (VOC) means any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions, except those designated by EPA as having negligible photochemical reactivity.

VOCs are organic chemical compounds whose composition makes it possible for them to evaporate under normal atmospheric conditions of temperature and pressure.

Volatile Organic Compounds are found in household and commercial products such as waxes, cosmetics, paints, varnishes and some cleansers. They are present in gasoline, kerosene and other fuels. Cigarette smoke and pesticides may also contain VOCs. VOC examples include benzene, methylene chloride, hexane, toluene, trichloroethane, styrene, heptane, and perchloroethylen.

Regulating VOCs – Information from the US EPA website on VOCs indicates that emissions of VOCs to the outdoors are regulated by EPA mostly to prevent the formation of ozone, a constituent of photochemical smog. Many VOCs form ground-level ozone by “reacting” with sources of oxygen molecules such as nitrogen oxides (NOx), and carbon monoxide (CO) in the atmosphere in the presence of sunlight. However, only some VOCs are considered “reactive” enough to be of concern. VOCs that are non-reactive or of negligible reactivity to form ozone under these conditions are exempted from the definition of VOCs used by EPA in its regulation. Since first establishing the list of exempt compounds in 1977, the EPA has added several to the list, and frequently has several petitions for additional compounds undergoing review. In addition, some states have their own definitions and lists of exempted compounds. Thus, for regulatory purposes, the specific definition of VOCs can change by what is excluded from that definition.

During source emission tests, or stack tests, VOCs are typically measured using one of several EPA Test Methods including:

EPA Method 18 – The major organic components of a gas mixture are separated by gas chromatography (GC) and individually quantified by flame ionization, photoionization, electron capture, or other appropriate detection principles. The retention times of each separated component are compared with those of known compounds under identical conditions. Therefore, the analyst confirms the identity and approximate concentrations of the organic emission components beforehand. With this information, the analyst then prepares or purchases commercially available standard mixtures to calibrate the GC under conditions identical to those of the samples. The analyst also determines the need for sample dilution to avoid detector saturation, gas stream filtration to eliminate particulate matter, and prevention of moisture condensation.

EPA Method 25 – This method is applicable for the determination of volatile organic compounds (VOCs) (measured as total gaseous nonmethane organics (TGNMO) and reported as carbon) in stationary source emissions. An emission sample is withdrawn from the stack at a constant rate through a heated filter and a dry ice chilled condensate trap by means of an evacuated sample tank. After sampling is completed, the TGNMO are determined by independently analyzing the condensate trap and sample tank fractions and combining the analytical results. The organic content of the condensate trap fraction is determined by oxidizing the NMO to carbon dioxide (CO2) and quantitatively collecting in the effluent in an evacuated vessel; then a portion of the CO2 is reduced to CH4 and measured by an FID. The organic content of the sample tank fraction is measured by injecting a portion of the sample into a gas chromatographic column to separate the NMO from carbon monoxide (CO), CO2, and CH4; the NMO are oxidized to CO2,reduced to CH4, and measured by an FID. In this manner, the variable response of the FID associated with different types of organics is eliminated.

EPA Method 25A – This method is applicable for the determination of total gaseous organic concentration of vapors consisting primarily of alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The concentration is expressed in terms of propane (or other appropriate organic calibration gas) or in terms of carbon. A gas sample is extracted from the source through a heated sample line and glass fiber filter to a flame ionization analyzer (FIA). Results are reported as volume concentration equivalents of the calibration gas or as carbon equivalents.