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(continued)

11.2 Glassware Cleaning. Before use, clean all glassware according to the procedure of Section 8.3.1.

11.3 Sample Preparation. The digestion of Be samples is accomplished in part in concentrated HClO4.

Note: The sample must be heated to light brown fumes after the initial HNO3 addition; otherwise, dangerous perchlorates may result from the subsequent HClO4 digestion. HClO4 should be used only under a hood.

11.3.1 Container No. 1. Transfer the filter and any loose particulate matter from Container No. 1 to a 150-ml beaker. Add 35 ml concentrated HNO3. To oxidize all organic matter, heat on a hotplate until light brown fumes are evident. Cool to room temperature, and add 5 ml 12 N H2SO4 and 5 ml concentrated HClO4.

11.3.2 Container No. 2. Place a portion of the water and acetone sample into a 150 ml beaker, and put on a hotplate. Add portions of the remainder as evaporation proceeds and evaporate to dryness. Cool the residue, and add 35 ml concentrated HNO3. To oxidize all organic matter, heat on a hotplate until light brown fumes are evident. Cool to room temperature, and add 5 ml 12 N H2SO4 and 5 ml concentrated HClO4. Then proceed with step 11.3.4.

11.3.3 Final Sample Preparation. Add the sample from Section 11.3.2 to the 150-ml beaker from Section 11.3.1. Replace on a hotplate, and evaporate to dryness in a HClO4 hood. Cool the residue to room temperature, add 10.0 ml of 25 percent V/V HCl, and mix to dissolve the residue.

11.3.4 Filter and Water Blanks. Cut each filter into strips, and treat each filter individually as directed in Section 11.3.1. Treat the 200-ml water blank as directed in Section 11.3.2. Combine and treat these blanks as directed in Section 11.3.3.

11.4 Spectrophotometer Preparation. Turn on the power; set the wavelength, slit width, and lamp current; and adjust the background corrector as instructed by the manufacturer's manual for the particular atomic absorption spectrophotometer. Adjust the burner and flame characteristics as necessary.

11.5 Analysis. Calibrate the analytical equipment and develop a calibration curve as outlined in Sections 10.4 and 10.5.

11.5.1 Beryllium Samples. Repeat the procedure used to establish the calibration curve with an appropriately sized aliquot of each sample (from Section 11.3.3) until two consecutive peak heights agree within 3 percent of their average value. The peak height of each sample must be greater than 10 percent of the recorder full scale. If the peak height of the sample is off scale on the recorder, further dilute the original source sample to bring the Be concentration into the calibration range of the spectrophotometer.

11.5.2 Run a blank and standard at least after every five samples to check the spectrophotometer calibration. The peak height of the blank must pass through a point no further from the origin than ±2 percent of the recorder full scale. The difference between the measured concentration of the standard (the product of the corrected peak height and the reciprocal of the least squares slope) and the actual concentration of the standard must be less than 7 percent, or recalibration of the analyzer is required.

11.5.3 Check for Matrix Effects (optional). Use the Method of Standard Additions (see Reference 2 in Section 16.0) to check at least one sample from each source for matrix effects on the Be results. If the results of the Method of Standard Additions procedure used on the single source sample do not agree to within 5 percent of the value obtained by the routine atomic absorption analysis, then reanalyze all samples from the source using the Method of Standard Additions procedure.

11.6 Container No. 2 (Silica Gel). Weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g using a balance. (This step may be conducted in the field.)

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra decimal significant figure beyond that of the acquired data. Round off figures only after the final calculation. Other forms of the equations may be used as long as they give equivalent results.

12.1 Nomenclature.

K1 = 0.3858 °K/mm Hg for metric units.

= 17.64 °R/in. Hg for English units.

K3 = 10-6 g/µg for metric units.

= 2.2046 × 10-9 lb/µg for English units.

mBe = Total weight of beryllium in the source sample.

Ps = Absolute stack gas pressure, mm Hg (in. Hg).

t = Daily operating time, sec/day.

Ts = Absolute average stack gas temperature, °K (°R).

Vm(std) = Dry gas sample volume at standard conditions, scm (scf).

Vw(std) = Volume of water vapor at standard conditions, scm (scf).

12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed, Moisture Content, Isokinetic Variation, and Stack Gas Velocity and Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5, 12.11, and 12.12, respectively.

12.3 Total Beryllium. For each source sample, correct the average maximum absorbance of the two consecutive samples whose peak heights agree within 3 percent of their average for the contribution of the solution blank (see Sections 11.3.4 and 11.5.2). Correcting for any dilutions if necessary, use the calibration curve and these corrected averages to determine the total weight of Be in each source sample.

12.4 Beryllium Emission Rate. Calculate the daily Hg emission rate, R, using Equation 104–1. For continuous operations, the operating time is equal to 86,400 seconds per day. For cyclic operations, use only the time per day each stack is in operation. The total Hg emission rate from a source will be the summation of results from all stacks.


12.5 Determination of Compliance. Each performance test consists of three sample runs. For the purpose of determining compliance with an applicable national emission standard, use the average of the results of all sample runs.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as References 1, 2, and 4–11 of Section 16.0 of Method 101 with the addition of the following:

1. Amos, M.D., and J.B. Willis. Use of High-Temperature Pre-Mixed Flames in Atomic Absorption Spectroscopy. Spectrochim. Acta. 22:1325. 1966.

2. Fleet, B., K.V. Liberty, and T. S. West. A Study of Some Matrix Effects in the Determination of Beryllium by Atomic Absorption Spectroscopy in the Nitrous Oxide-Acetylene Flame. Talanta 17:203. 1970.

17.0 Tables, Diagrams, Flowcharts, And Validation Data [Reserved]

Method 105—Determination of Mercury in Wastewater Treatment Plant Sewage Sludges

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in this part. Therefore, to obtain reliable results, persons using this method should also have a thorough knowledge of at least the following additional test methods: Method 101 and Method 101A.

1.0 Scope and Application

1.1 Analytes.



------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)................... 7439-97-6 Dependent upon
spectrophotometer and
recorder.
------------------------------------------------------------------------


1.2 Applicability. This method is applicable for the determination of total organic and inorganic Hg content in sewage sludges.

1.3 Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.

2.0 Summary of Method

2.1 Time-composite sludge samples are withdrawn from the conveyor belt subsequent to dewatering and before incineration or drying. A weighed portion of the sludge is digested in aqua regia and is oxidized by potassium permanganate (KMnO4). Mercury in the digested sample is then measured by the conventional spectrophotometric cold-vapor technique.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

5.2 Corrosive Reagents. The following reagents are hazardous. Personal protective equipment and safe procedures are useful in preventing chemical splashes. If contact occurs, immediately flush with copious amounts of water at least 15 minutes. Remove clothing under shower and decontaminate. Treat residual chemical burn as thermal burn.

5.2.1 Hydrochloric Acid (HCl). Highly toxic. Vapors are highly irritating to eyes, skin, nose, and lungs, causing severe damage. May cause bronchitis, pneumonia, or edema of lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal to humans in a few minutes. Provide ventilation to limit exposure. Reacts with metals, producing hydrogen gas.

5.2.2 Nitric Acid (HNO3). Highly corrosive to eyes, skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be delayed as long as 30 hours and still be fatal. Provide ventilation to limit exposure. Strong oxidizer. Hazardous reaction may occur with organic materials such as solvents.

6.0 Equipment and Supplies

6.1 Sample Collection and Mixing. The following items are required for collection and mixing of the sludge samples:

6.1.1 Container. Plastic, 50-liter.

6.1.2 Scoop. To remove 950-ml (1 quart.) sludge sample.

6.1.3 Mixer. Mortar mixer, wheelbarrow-type, 57-liter (or equivalent) with electricity-driven motor.

6.1.4 Blender. Waring-type, 2-liter.

6.1.5 Scoop. To remove 100-ml and 20-ml samples of blended sludge.

6.1.6 Erlenmeyer Flasks. Four, 125-ml.

6.1.7 Beakers. Glass beakers in the following sizes: 50 ml (1), 200 ml (1), 400 ml (2).

6.2 Sample Preparation and Analysis. Same as Method 101, Section 6.3, with the addition of the following:

6.2.1 Hot Plate.

6.2.2 Desiccator.

6.2.3 Filter Paper. S and S No. 588 (or equivalent).

6.2.4 Beakers. Glass beakers, 200 ml and 400 ml (2 each).

7.0 Reagents and Standards

Note: Unless otherwise indicated, it is intended that all reagents conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available; otherwise, use the best available grade.

7.1 Sample Analysis. Same as Method 101A, Section 7.2, with the following additions and exceptions:

7.1.1 Hydrochloric Acid. The concentrated HCl specified in Method 101A, Section 7.2.4, is not required.

7.1.2 Aqua Regia. Prepare immediately before use. Carefully add one volume of concentrated HNO3 to three volumes of concentrated HCl.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sludge Sampling. Withdraw equal volume increments of sludge [for a total of at least 15 liters (16 quarts)] at intervals of 30 min over an 8-hr period, and combine in a rigid plastic container.

8.2 Sludge Mixing. Transfer the entire 15-liter sample to a mortar mixer. Mix the sample for a minimum of 30 min at 30 rpm. Take six 100-ml portions of sludge, and combine in a 2-liter blender. Blend sludge for 5 min; add water as necessary to give a fluid consistency. Immediately after stopping the blender, withdraw four 20-ml portions of blended sludge, and place them in separate, tared 125-ml Erlenmeyer flasks. Reweigh each flask to determine the exact amount of sludge added.

8.3 Sample Holding Time. Samples shall be analyzed within the time specified in the applicable subpart of the regulations.

9.0 Quality Control



------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.0.......................... Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------


10.0 Calibration and Standardization

Same as Method 101A, Section 10.2.

11.0 Analytical Procedures

11.1 Solids Content of Blended Sludge. Dry one of the 20-ml blended samples from Section 8.2 in an oven at 105 °C (221 °F) to constant weight. Cool in a desiccator, weigh and record the dry weight of the sample.

11.2 Aqua Regia Digestion of Blended Samples.

11.2.1 To each of the three remaining 20-ml samples from Section 8.2 add 25 ml of aqua regia, and digest the on a hot plate at low heat (do not boil) for 30 min, or until samples are a pale yellow-brown color and are void of the dark brown color characteristic of organic matter. Remove from hotplate and allow to cool.

11.2.2 Filter each digested sample separately through an S and S No. 588 filter or equivalent, and rinse the filter contents with 50 ml of water. Transfer the filtrate and filter washing to a 100-ml volumetric flask, and carefully dilute to volume with water.

11.3 Solids Content of the Sludge Before Blending. Remove two 100-ml portions of mixed sludge from the mortar mixer and place in separate, tared 400-ml beakers. Reweigh each beaker to determine the exact amount of sludge added. Dry in oven at 105 °C (221 °F) and cool in a desiccator to constant weight.

11.4 Analysis for Mercury. Analyze the three aqua regia-digested samples using the procedures outlined in Method 101A, Section 11.0.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Cm = Concentration of Hg in the digested sample, µg/g.

Fsb = Weight fraction of solids in the blended sludge.

Fsm = Weight fraction of solids in the collected sludge after mixing.

M = Hg content of the sewage sludge (on a dry basis), µg/g.

m = Mass of Hg in the aliquot of digested sample analyzed, µg.

n = number of digested samples (specified in Section 11.2 as three).

Va = Volume of digested sample analyzed, ml.

Vs = Volume of digested sample, ml.

Wb = Weight of empty sample beaker, g.

Wbs = Weight of sample beaker and sample, g.

Wbd = Weight of sample beaker and sample after drying, g.

Wf = Weight of empty sample flask, g.

Wfd = Weight of sample flask and sample after drying, g.

Wfs = Weight of sample flask and sample, g.

12.2 Mercury Content of Digested Sample (Wet Basis).

12.2.1 For each sample analyzed for Hg content, calculate the arithmetic mean maximum absorbance of the two consecutive samples whose peak heights agree ±3 percent of their average. Correct this average value for the contribution of the blank. Use the calibration curve and these corrected averages to determine the final Hg concentration in the solution cell for each sludge sample.

12.2.2 Calculate the average Hg concentration of the digested samples by correcting for any dilutions made to bring the sample into the working range of the spectrophotometer and for the weight of the sludge portion digested, using Equation 105–1.


12.3 Solids Content of Blended Sludge. Determine the solids content of the blended sludge using Equation 105–2.


12.4 Solids Content of Bulk Sample (before blending but, after mixing in mortar mixer). Determine the solids content of each 100 ml aliquot (Section 11.3), and average the results.


12.5 Mercury Content of Bulk Sample (Dry Basis). Average the results from the three samples from each 8-hr composite sample, and calculate the Hg concentration of the composite sample on a dry basis.


13.0 Method Performance

13.1 Range. The range of this method is 0.2 to 5 micrograms per gram; it may be extended by increasing or decreasing sample size.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Bishop, J.N. Mercury in Sediments. Ontario Water Resources Commission. Toronto, Ontario, Canada. 1971.

2. Salma, M. Private Communication. EPA California/Nevada Basin Office. Alameda, California.

3. Hatch, W.R. and W.L. Ott. Determination of Sub-Microgram Quantities of Mercury by Atomic Absorption Spectrophotometry. Analytical Chemistry. 40:2085. 1968.

4. Bradenberger, H., and H. Bader. The Determination of Nanogram Levels of Mercury in Solution by a Flameless Atomic Absorption Technique. Atomic Absorption Newsletter. 6:101. 1967.

5. Analytical Quality Control Laboratory (AQCL). Mercury in Sediment (Cold Vapor Technique) (Provisional Method). U.S. Environmental Protection Agency. Cincinnati, Ohio. April 1972.

6. Kopp, J.F., M.C. Longbottom, and L.B. Lobring. “Cold Vapor” Method for Determining Mercury. Journal AWWA. 64(1):20–25. 1972.

7. Manual of Methods for Chemical Analysis of Water and Wastes. U.S. Environmental Protection Agency. Cincinnati, Ohio. Publication No. EPA–624/2–74–003. December 1974. pp. 118–138.

8. Mitchell, W.J., M.R. Midgett, J. Suggs, R.J. Velton, and D. Albrink. Sampling and Homogenizing Sewage for Analysis. Environmental Monitoring and Support Laboratory, Office of Research and Development, U.S. Environmental Protection Agency. Research Triangle Park, N.C. March 1979. p. 7.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 106—Determination of Vinyl Chloride Emissions From Stationary Sources

1.0 Scope and Application

1.1 Analytes.



------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)...... 75-01-4 Dependent upon
analytical equipment.
------------------------------------------------------------------------


1.2 Applicability. This method is applicable for the determination of vinyl chloride emissions from ethylene dichloride, vinyl chloride, and polyvinyl chloride manufacturing processes. This method does not measure vinyl chloride contained in particulate matter.

1.3 Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.

2.0 Summary of Method

2.1 An integrated bag sample of stack gas containing vinyl chloride is subjected to GC analysis using a flame ionization detector (FID).

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Resolution interferences of vinyl chloride may be encountered on some sources. Therefore, the chromatograph operator should select the column and operating parameters best suited to the particular analysis requirements. The selection made is subject to approval of the Administrator. Approval is automatic, provided that confirming data are produced through an adequate supplemental analytical technique, and that the data are available for review by the Administrator. An example of this would be analysis with a different column or GC/mass spectroscopy.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

5.2 Toxic Analyte. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, which is a carcinogen.

6.0 Equipment and Supplies

6.1 Sample Collection (see Figure 106–1). The sampling train consists of the following components:

6.1.1 Probe. Stainless steel, borosilicate glass, Teflon tubing (as stack temperature permits), or equivalent, equipped with a glass wool plug to remove particulate matter.

6.1.2 Sample Lines. Teflon, 6.4-mm outside diameter, of sufficient length to connect probe to bag. Use a new unused piece for each series of bag samples that constitutes an emission test, and discard upon completion of the test.

6.1.3 Quick Connects. Stainless steel, male (2) and female (2), with ball checks (one pair without), located as shown in Figure 106–1.

6.1.4 Tedlar Bags. 50- to 100-liter capacity, to contain sample. Aluminized Mylar bags may be used if the samples are analyzed within 24 hours of collection.

6.1.5 Bag Containers. Rigid leak-proof containers for sample bags, with covering to protect contents from sunlight.

6.1.6 Needle Valve. To adjust sample flow rates.

6.1.7 Pump. Leak-free, with minimum of 2-liter/min capacity.

6.1.8 Charcoal Tube. To prevent admission of vinyl chloride and other organics to the atmosphere in the vicinity of samplers.

6.1.9 Flowmeter. For observing sampling flow rate; capable of measuring a flow range from 0.10 to 1.00 liter/min.

6.1.10 Connecting Tubing. Teflon, 6.4-mm outside diameter, to assemble sampling train (Figure 106–1).

6.1.11 Tubing Fittings and Connectors. Teflon or stainless steel, to assemble sampling training.

6.2 Sample Recovery. Teflon tubing, 6.4-mm outside diameter, to connect bag to GC sample loop. Use a new unused piece for each series of bag samples that constitutes an emission test, and discard upon conclusion of analysis of those bags.

6.3 Analysis. The following equipment is required:

6.3.1 Gas Chromatograph. With FID potentiometric strip chart recorder and 1.0 to 5.0-ml heated sampling loop in automatic sample valve. The chromatographic system shall be capable of producing a response to 0.1-ppmv vinyl chloride that is at least as great as the average noise level. (Response is measured from the average value of the base line to the maximum of the wave form, while standard operating conditions are in use.)

6.3.2 Chromatographic Columns. Columns as listed below. Other columns may be used provided that the precision and accuracy of the analysis of vinyl chloride standards are not impaired and that information is available for review confirming that there is adequate resolution of vinyl chloride peak. (Adequate resolution is defined as an area overlap of not more than 10 percent of the vinyl chloride peak by an interferent peak. Calculation of area overlap is explained in Procedure 1 of appendix C to this part: “Determination of Adequate Chromatographic Peak Resolution.”)

6.3.2.1 Column A. Stainless steel, 2.0 m by 3.2 mm, containing 80/100-mesh Chromasorb 102.

6.3.2.2 Column B. Stainless steel, 2.0 m by 3.2 mm, containing 20 percent GE SF–96 on 60/ip-mesh Chromasorb P AW; or stainless steel, 1.0 m by 3.2 mm containing 80/100-mesh Porapak T. Column B is required as a secondary column if acetaldehyde is present. If used, column B is placed after column A. The combined columns should be operated at 120 °C (250 °F).

6.3.3 Rate Meters (2). Rotameter , or equivalent, 100-ml/min capacity, with flow control valves.

6.3.4 Gas Regulators. For required gas cylinders.

6.3.5 Temperature Sensor. Accurate to ±1 °C (±2 °F), to measure temperature of heated sample loop at time of sample injection.

6.3.6 Barometer. Accurate to ±5 mm Hg, to measure atmospheric pressure around GC during sample analysis.

6.3.7 Pump. Leak-free, with minimum of 100-ml/min capacity.

6.3.8 Recorder. Strip chart type, optionally equipped with either disc or electronic integrator.

6.3.9 Planimeter. Optional, in place of disc or electronic integrator on recorder, to measure chromatograph peak areas.

6.4 Calibration and Standardization.

6.4.1 Tubing. Teflon, 6.4-mm outside diameter, separate pieces marked for each calibration concentration.

Note: The following items are required only if the optional standard gas preparation procedures (Section 10.1) are followed.

6.4.2 Tedlar Bags. Sixteen-inch-square size, with valve; separate bag marked for each calibration concentration.

6.4.3 Syringes. 0.5-ml and 50-µl, gas tight, individually calibrated to dispense gaseous vinyl chloride.

6.4.4 Dry Gas Meter with Temperature and Pressure Gauges. Singer Model DTM–115 with 802 index, or equivalent, to meter nitrogen in preparation of standard gas mixtures, calibrated at the flow rate used to prepare standards.

7.0 Reagents and Standards

7.1 Analysis. The following reagents are required for analysis.

7.1.1 Helium or Nitrogen. Purity 99.9995 percent or greater, for chromatographic carrier gas.

7.1.2 Hydrogen. Purity 99.9995 percent or greater.

7.1.3 Oxygen or Air. Either oxygen (purity 99.99 percent or greater) or air (less than 0.1 ppmv total hydrocarbon content), as required by detector.

7.2 Calibration. Use one of the following options: either Sections 7.2.1 and 7.2.2, or Section 7.2.3.

7.2.1 Vinyl Chloride. Pure vinyl chloride gas certified by the manufacturer to contain a minimum of 99.9 percent vinyl chloride. If the gas manufacturer maintains a bulk cylinder supply of 99.9+ percent vinyl chloride, the certification analysis may have been performed on this supply, rather than on each gas cylinder prepared from this bulk supply. The date of gas cylinder preparation and the certified analysis must have been affixed to the cylinder before shipment from the gas manufacturer to the buyer.

7.2.2 Nitrogen. Same as described in Section 7.1.1.

7.2.3 Cylinder Standards. Gas mixture standards (50-,10-, and 5 ppmv vinyl chloride) in nitrogen cylinders may be used to directly prepare a chromatograph calibration curve as described in Section 10.3 if the following conditions are met: (a) The manufacturer certifies the gas composition with an accuracy of ±3 percent or better. (b) The manufacturer recommends a maximum shelf life over which the gas concentration does not change by greater than ±5 percent from the certified value. (c) The manufacturer affixes the date of gas cylinder preparation, certified vinyl chloride concentration, and recommended maximum shelf to the cylinder before shipment to the buyer.

7.2.3.1 Cylinder Standards Certification. The manufacturer shall certify the concentration of vinyl chloride in nitrogen in each cylinder by (a) directly analyzing each cylinder and (b) calibrating his analytical procedure on the day of cylinder analysis. To calibrate his analytical procedure, the manufacturer shall use as a minimum, a three point calibration curve. It is recommended that the manufacturer maintain (1) a high concentration calibration standard (between 50 and 100 ppmv) to prepare his calibration curve by an appropriate dilution technique and (2) a low-concentration calibration standard (between 5 and 10 ppmv) to verify the dilution technique used. If the difference between the apparent concentration read from the calibration curve and the true concentration assigned to the low-concentration calibration standard exceeds 5 percent of the true concentration, the manufacturer shall determine the source of error and correct it, then repeat the three-point calibration.

7.2.3.2 Verification of Manufacturer's Calibration Standards. Before using a standard, the manufacturer shall verify each calibration standard (a) by comparing it to gas mixtures prepared (with 99 mole percent vinyl chloride) in accordance with the procedure described in Section 7.2.1 or (b) calibrating it against vinyl chloride cylinder Standard Reference Materials (SRM's) prepared by the National Institute of Standards and Technology, if such SRM's are available. The agreement between the initially determined concentration value and the verification concentration value must be ±5 percent. The manufacturer must reverify all calibration standards on a time interval consistent with the shelf life of the cylinder standards sold.

7.2.4 Audit Cylinder Standards.

7.2.4.1 Gas mixture standards with concentrations known only to the person supervising the analysis of samples. The concentrations of the audit cylinders should be: one low-concentration cylinder in the range of 5 to 20 ppmv vinyl chloride and one high-concentration cylinder in the range of 20 to 50 ppmv. When available, obtain audit samples from the appropriate EPA Regional Office or from the responsible enforcement authority.

Note: The responsible enforcement agency should be notified at least 30 days prior to the test date to allow sufficient time for sample delivery.

7.2.4.2 Alternatively, audit cylinders obtained from a commercial gas manufacturer may be used provided: (a) the gas meets the conditions described in Section 7.2.3, (b) the gas manufacturer certifies the audit cylinder as described in Section 7.2.3.1, and (c) the gas manufacturer obtains an independent analysis of the audit cylinders to verify this analysis. Independent analysis is defined here to mean analysis performed by an individual different than the individual who performs the gas manufacturer's analysis, while using calibration standards and analysis equipment different from those used for the gas manufacturer's analysis. Verification is complete and acceptable when the independent analysis concentration is within 5 percent of the gas manufacturer's concentration.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph (GC) nor by those who are unfamiliar with source sampling, because knowledge beyond the scope of this presentation is required.

8.1 Bag Leak-Check. The following leak-check procedure is recommended, but not required, prior to sample collection. The post-test leak-check procedure is mandatory. Connect a water manometer and pressurize the bag to 5 to 10 cm H2O (2 to 4 in. H2O). Allow to stand for 10 min. Any displacement in the water manometer indicates a leak. Also, check the rigid container for leaks in this manner.

Note: An alternative leak-check method is to pressurize the bag to 5 to 10 cm H2O and allow it to stand overnight. A deflated bag indicates a leak. For each sample bag in its rigid container, place a rotameter in line between the bag and the pump inlet. Evacuate the bag. Failure of the rotameter to register zero flow when the bag appears to be empty indicates a leak.

8.2 Sample Collection. Assemble the sample train as shown in Figure 106–1. Join the quick connects as illustrated, and determine that all connection between the bag and the probe are tight. Place the end of the probe at the centroid of the stack and start the pump with the needle valve adjusted to yield a flow that will fill over 50 percent of bag volume in the specific sample period. After allowing sufficient time to purge the line several times, change the vacuum line from the container to the bag and evacuate the bag until the rotameter indicates no flow. Then reposition the sample and vacuum lines and begin the actual sampling, keeping the rate proportional to the stack velocity. At all times, direct the gas exiting the rotameter away from sampling personnel. At the end of the sample period, shut off the pump, disconnect the sample line from the bag, and disconnect the vacuum line from the bag container. Protect the bag container from sunlight.

8.3 Sample Storage. Keep the sample bags out of direct sunlight. When at all possible, analysis is to be performed within 24 hours, but in no case in excess of 72 hours of sample collection. Aluminized Mylar bag samples must be analyzed within 24 hours.

8.4 Post-test Bag Leak-Check. Subsequent to recovery and analysis of the sample, leak-check the sample bag according to the procedure outlined in Section 8.1.

9.0 Quality Control

9.1 Miscellaneous Quality Control



------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.3.......................... Chromatograph Ensure precision and
calibration. accuracy of
chromatograph.
11.1.......................... Audit sample Evaluate analytical
analysis. technique and
standards
preparation.
------------------------------------------------------------------------


9.2 Immediately after the preparation of the calibration curve and prior to the sample analyses, perform the analysis audit described in appendix C, Procedure 2: “Procedure for Field Auditing GC Analysis.”

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Preparation of Vinyl Chloride Standard Gas Mixtures. (Optional Procedure-delete if cylinder standards are used.) Evacuate a 16-inch square Tedlar bag that has passed a leak-check (described in Section 8.1) and meter in 5.0 liters of nitrogen. While the bag is filling, use the 0.5-ml syringe to inject 250 µl of 99.9+ percent vinyl chloride gas through the wall of the bag. Upon withdrawing the syringe, immediately cover the resulting hole with a piece of adhesive tape. The bag now contains a vinyl chloride concentration of 50 ppmv. In a like manner use the 50 µl syringe to prepare gas mixtures having 10-and 5-ppmv vinyl chloride concentrations. Place each bag on a smooth surface and alternately depress opposite sides of the bag 50 times to further mix the gases. These gas mixture standards may be used for 10 days from the date of preparation, after which time new gas mixtures must be prepared. (Caution: Contamination may be a problem when a bag is reused if the new gas mixture standard is a lower concentration than the previous gas mixture standard.)

10.2 Determination of Vinyl Chloride Retention Time. (This section can be performed simultaneously with Section 10.3.) Establish chromatograph conditions identical with those in Section 11.3. Determine proper attenuator position. Flush the sampling loop with helium or nitrogen and activate the sample valve. Record the injection time, sample loop temperature, column temperature, carrier gas flow rate, chart speed, and attenuator setting. Record peaks and detector responses that occur in the absence of vinyl chloride. Maintain conditions with the equipment plumbing arranged identically to Section 11.2, and flush the sample loop for 30 seconds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures. Then activate the sample valve. Record the injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the injection time to the time at which the peak maximum occurs. This quantity divided by the chart speed is defined as the retention time. Since other organics may be present in the sample, positive identification of the vinyl chloride peak must be made.

10.3 Preparation of Chromatograph Calibration Curve. Make a GC measurement of each gas mixture standard (described in Section 7.2.3 or 10.1) using conditions identical to those listed in Sections 11.2 and 11.3. Flush the sampling loop for 30 seconds at the rate of 100 ml/min with one of the standard mixtures, and activate the sample valve. Record the concentration of vinyl chloride injected (Cc), attenuator setting, chart speed, peak area, sample loop temperature, column temperature, carrier gas flow rate, and retention time. Record the barometric pressure. Calculate Ac, the peak area multiplied by the attenuator setting. Repeat until two consecutive injection areas are within 5 percent, then plot the average of those two values versus Cc. When the other standard gas mixtures have been similarly analyzed and plotted, draw a straight line through the points derived by the least squares method. Perform calibration daily, or before and after the analysis of each emission test set of bag samples, whichever is more frequent. For each group of sample analyses, use the average of the two calibration curves which bracket that group to determine the respective sample concentrations. If the two calibration curves differ by more than 5 percent from their mean value, then report the final results by both calibration curves.

11.0 Analytical Procedure

11.1 Audit Sample Analysis. Immediately after the preparation of the calibration curve and prior to the sample analyses, perform the analysis audit described in Procedure 2 of appendix C to this part: “Procedure for Field Auditing GC Analysis.”

11.2 Sample Recovery. With a new piece of Teflon tubing identified for that bag, connect a bag inlet valve to the gas chromatograph sample valve. Switch the valve to receive gas from the bag through the sample loop. Arrange the equipment so the sample gas passes from the sample valve to 100-ml/min rotameter with flow control valve followed by a charcoal tube and a 1-in. H2O pressure gauge. Maintain the sample flow either by a vacuum pump or container pressurization if the collection bag remains in the rigid container. After sample loop purging is ceased, allow the pressure gauge to return to zero before activating the gas sampling valve.

11.3 Analysis.

11.3.1 Set the column temperature to 100 °C (210 °F) and the detector temperature to 150 °C (300 °F). When optimum hydrogen and oxygen (or air) flow rates have been determined, verify and maintain these flow rates during all chromatography operations. Using helium or nitrogen as the carrier gas, establish a flow rate in the range consistent with the manufacturer's requirements for satisfactory detector operation. A flow rate of approximately 40 ml/min should produce adequate separations. Observe the base line periodically and determine that the noise level has stabilized and that base line drift has ceased. Purge the sample loop for 30 seconds at the rate of 100 ml/min, shut off flow, allow the sample loop pressure to reach atmospheric pressure as indicated by the H2O manometer, then activate the sample valve. Record the injection time (the position of the pen on the chart at the time of sample injection), sample number, sample loop temperature, column temperature, carrier gas flow rate, chart speed, and attenuator setting. Record the barometric pressure. From the chart, note the peak having the retention time corresponding to vinyl chloride as determined in Section 10.2. Measure the vinyl chloride peak area, Am, by use of a disc integrator, electronic integrator, or a planimeter. Measure and record the peak heights, Hm. Record Am and retention time. Repeat the injection at least two times or until two consecutive values for the total area of the vinyl chloride peak agree within 5 percent of their average. Use the average value for these two total areas to compute the bag concentration.

11.3.2 Compare the ratio of Hm to Am for the vinyl chloride sample with the same ratio for the standard peak that is closest in height. If these ratios differ by more than 10 percent, the vinyl chloride peak may not be pure (possibly acetaldehyde is present) and the secondary column should be employed (see Section 6.3.2.2).

11.4 Determination of Bag Water Vapor Content. Measure the ambient temperature and barometric pressure near the bag. From a water saturation vapor pressure table, determine and record the water vapor content of the bag, Bwb, as a decimal figure. (Assume the relative humidity to be 100 percent unless a lesser value is known.)

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Am = Measured peak area.

Af = Attenuation factor.

Bwb = Water vapor content of the bag sample, as analyzed, volume fraction.

Cb = Concentration of vinyl chloride in the bag, ppmv.

Cc = Concentration of vinyl chloride in the standard sample, ppmv.

Pi = Laboratory pressure at time of analysis, mm Hg.

Pr = Reference pressure, the laboratory pressure recorded during calibration, mm Hg.

Ti = Absolute sample loop temperature at the time of analysis, °K (°R).

Tr = Reference temperature, the sample loop temperature recorded during calibration, °K (°R).

12.2 Sample Peak Area. Determine the sample peak area, Ac, as follows:


12.3 Vinyl Chloride Concentration. From the calibration curves prepared in Section 10.3, determine the average concentration value of vinyl chloride, Cc, that corresponds to Ac, the sample peak area. Calculate the concentration of vinyl chloride in the bag, Cb, as follows:


13.0 Method Performance

13.1 Analytical Range. This method is designed for the 0.1 to 50 parts per million by volume (ppmv) range. However, common gas chromatograph (GC) instruments are capable of detecting 0.02 ppmv vinyl chloride. With proper calibration, the upper limit may be extended as needed.

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 References

1. Brown D.W., E.W. Loy, and M.H. Stephenson. Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company in Louisville, KY. Region IV, U.S. Environmental Protection Agency, Surveillance and Analysis Division, Athens, GA. June 24, 1974.

2. G.D. Clayton and Associates. Evaluation of a Collection and Analytical Procedure for Vinyl Chloride in Air. U.S. Environmental Protection Agency, Research Triangle Park, N.C. EPA Contract No. 68–02–1408, Task Order No. 2, EPA Report No. 75–VCL–1. December 13, 1974.

3. Midwest Research Institute. Standardization of Stationary Source Emission Method for Vinyl Chloride. U.S. Environmental Protection Agency, Research Triangle Park, N.C. Publication No. EPA–600/4–77–026. May 1977.

4. Scheil, G. and M.C. Sharp. Collaborative Testing of EPA Method 106 (Vinyl Chloride) that Will Provide for a Standardized Stationary Source Emission Measurement Method. U.S. Environmental Protection Agency, Research Triangle Park, N.C. Publication No. EPA 600/4–78–058. October 1978.

17.0 Tables, Diagrams Flowcharts, and Validation Data.



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Method 107—Determination of Vinyl Chloride Content of In-Process Wastewater Samples, and Vinyl Chloride Content of Polyvinyl Chloride Resin Slurry, Wet Cake, and Latex Samples

Note: Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph (GC) nor by those who are unfamiliar with source sampling, because knowledge beyond the scope of this presentation is required. This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in this part. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least the following additional test methods: Method 106.

1.0 Scope and Application

1.1 Analytes.



------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Vinyl Chloride (CH2:CHCl)...... 75-01-4 Dependent upon
analytical equipment.
------------------------------------------------------------------------


1.2 Applicability. This method is applicable for the determination of the vinyl chloride monomer (VCM) content of in-process wastewater samples, and the residual vinyl chloride monomer (RCVM) content of polyvinyl chloride (PVC) resins, wet, cake, slurry, and latex samples. It cannot be used for polymer in fused forms, such as sheet or cubes. This method is not acceptable where methods from section 304(h) of the Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water Pollution Control Amendments of 1972 as amended by the Clean Water Act of 1977) are required.

1.3 Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.

2.0 Summary of Method

2.1 The basis for this method relates to the vapor equilibrium that is established at a constant known temperature in a closed system between RVCM, PVC resin, water, and air. The RVCM in a PVC resin will equilibrate rapidly in a closed vessel, provided that the temperature of the PVC resin is maintained above the glass transition temperature of that specific resin.

2.2 A sample of PVC or in-process wastewater is collected in a vial or bottle and is conditioned. The headspace in the vial or bottle is then analyzed for vinyl chloride using gas chromatography with a flame ionization detector.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 The chromatograph columns and the corresponding operating parameters herein described normally provide an adequate resolution of vinyl chloride; however, resolution interferences may be encountered on some sources. Therefore, the chromatograph operator shall select the column and operating parameters best suited to his particular analysis requirements, subject to the approval of the Administrator. Approval is automatic provided that confirming data are produced through an adequate supplemental analytical technique, such as analysis with a different column or GC/mass spectroscopy, and that these data are made available for review by the Administrator.

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

5.2 Toxic Analyte. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, which is a carcinogen. Do not release vinyl chloride to the laboratory atmosphere during preparation of standards. Venting or purging with VCM/air mixtures must be held to a minimum. When they are required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory. After vials have been analyzed, the gas must be vented prior to removal of the vial from the instrument turntable. Vials must be vented through a hypodermic needle connected to an activated charcoal tube to prevent release of vinyl chloride into the laboratory atmosphere. The charcoal must be replaced prior to vinyl chloride breakthrough.

6.0 Equipment and Supplies

6.1 Sample Collection. The following equipment is required:

6.1.1 Glass bottles. 60-ml (2-oz) capacity, with wax-lined screw-on tops, for PVC samples.

6.1.2 Glass Vials. Headspace vials, with Teflon-faced butyl rubber sealing discs, for water samples.

6.1.3 Adhesive Tape. To prevent loosening of bottle tops.

6.2 Sample Recovery. The following equipment is required:

6.2.1 Glass Vials. Headspace vials, with butyl rubber septa and aluminum caps. Silicone rubber is not acceptable.

6.2.2 Analytical Balance. Capable of determining sample weight within an accuracy of ±1 percent.

6.2.3 Vial Sealer. To seal headspace vials.

6.2.4 Syringe. 100-ml capacity.

6.3 Analysis. The following equipment is required:

6.3.1 Headspace Sampler and Chromatograph. Capable of sampling and analyzing a constant amount of headspace gas from a sealed vial, while maintaining that vial at a temperature of 90 °C ±0.5 °C (194 °F ±0.9 °F). The chromatograph shall be equipped with a flame ionization detector (FID). Perkin-Elmer Corporation Models F–40, F–42, F–45, HS–6, and HS–100, and Hewlett-Packard Corporation Model 19395A have been found satisfactory. Chromatograph backflush capability may be required.

6.3.2 Chromatographic Columns. Stainless steel 1 m by 3.2 mm and 2 m by 3.2 mm, both containing 50/80-mesh Porapak Q. Other columns may be used provided that the precision and accuracy of the analysis of vinyl chloride standards are not impaired and information confirming that there is adequate resolution of the vinyl chloride peak are available for review. (Adequate resolution is defined as an area overlap of not more than 10 percent of the vinyl chloride peak by an interferant peak. Calculation of area overlap is explained in Procedure 1 of appendix C to this part: “Determination of Adequate Chromatographic Peak Resolution.”) Two 1.83 m columns, each containing 1 percent Carbowax 1500 on Carbopak B, have been found satisfactory for samples containing acetaldehyde.

6.3.3 Temperature Sensor. Range 0 to 100 °C (32 to 212 °F) accurate to 0.1 °C.

6.3.4 Integrator-Recorder. To record chromatograms.

6.3.5 Barometer. Accurate to 1 mm Hg.

6.3.6 Regulators. For required gas cylinders.

6.3.7 Headspace Vial Pre-Pressurizer. Nitrogen pressurized hypodermic needle inside protective shield.

7.0 Reagents and Standards

7.1 Analysis. Same as Method 106, Section 7.1, with the addition of the following:

7.1.1 Water. Interference-free.

7.2 Calibration. The following items are required for calibration: (continued)