descriptive use only and do not constitute endorsements by USDOL-OSHA. Similar products from other sources can be substituted.
OSHA Technical Center Salt Lake City, Utah 1. Introduction This method describes the collection of airborne particulate mercury on
0.8-µm
This method is an adaptation of an analytical technique proposed by Hatch and Ott (8.1.). Particulate mercury contained in air samples, as well as wipe and bulk samples have always been analyzed at the OSHA Salt Lake Technical Center (OSHA-SLTC) using CV-AAS. Elemental mercury vapor is sampled and analyzed using techniques described in reference 8.2. 1.2. Principle Airborne and non-airborne particulate mercury compounds and mercury-containing dust are collected, respectively, on 0.8-µm MCE and wipe filters. Bulk material is collected by grab sampling. Air filter, wipe, and bulk samples are initially dissolved using concentrated nitric and sulfuric acids. A potassium permanganate solution is added to help dissolve the sample matrix. A hydroxylamine hydrochloride solution is then added to reduce the excess potassium permanganate. Finally, stannous chloride is added to an aliquot of the sample to reduce the mercury to the vapor state. This vapor is then driven into an absorption cell of a flameless atomic absorption spectrophotometer for analysis. 1.3. Advantages and Disadvantages
1.3.2. This method has adequate sensitivity for measuring workplace exposure to mercury-containing dust and particulate mercury compounds. 1.3.3. Sample preparation for analysis involves simple procedures. 1.3.4. Particulate organo-mercury compounds may also be collected using 0.8 µm MCE filters. 1.3.5. Elemental mercury vapor cannot be collected on the 0.8 µm MCE filters. If elemental mercury vapor is suspected to be present, a sample using HydrarR or hopcalite solid sorbent as the collection medium should be separately taken (8.2.). 1.4. Workplace Exposure Occupations with potential exposure to mercury and its compounds are listed (8.3.):
Note: Information listed within this section is a synopsis of current knowledge of the physiological effects of mercury and is not intended to be used as a basis for OSHA policy.
Exposure to elemental mercury vapor can occur via the respiratory tract and skin. Possible symptoms from an acute exposure include severe nausea, vomiting, abdominal pain, bloody diarrhea, kidney damage, and death. These symptoms usually present themselves within 10 days of exposure. Potential symptoms from a chronic exposure include inflammation of the mouth and gums, excessive salivation, loosening of the teeth, kidney damage, muscle tremors, jerky gait, spasms of the extremities, personality changes, depression, irritability, and nervousness (8.3., 8.4.). 1.6. Properties (8.3.-8.5.) Elemental mercury (CAS No. 7439-97-6) is a silver-white, heavy, mobile, liquid metal at room temperature. Some physical properties and data for mercury are:
Many different inorganic and aryl compounds of mercury exist. One of the more common aryl compounds is phenyl mercuric acetate (C6H5HgOCOCH3) which is used as a fungicide:
2. Range
The qualitative and quantitative detection limits for the analytical procedure are 0.01 µg and 0.02 µg mercury, respectively (8.6.). 2.2. Working Range The range of the analytical procedure has been determined to be 0.1 to 2 µg mercury. Using the analytical conditions specified, a nonlinear response was noted above 2 µg. 3. Method Performance
3.2. An additional test to determine method performance was conducted using spikes of phenyl mercuric acetate (PMA) on 24 MCE filters (8.8.). The filters were spiked with PMA solutions containing 50 to 200 µg total mercury. The recovery for 18 of the samples was 103.3% and a coefficient of variation of 0.086. The remaining six samples were subjected to a retention efficiency test where air was drawn through the spiked filters for 3 h. The filters were then analyzed. Results indicated the filters sufficiently retained the PMA . 4. Interferences Organic-free deionized water should be used during sample and standard preparation. Any compound with the same absorbance wavelength as mercury (253.7 nm) can be a positive interference. Some volatile organic compounds (i.e. benzene, toluene, acetone, carbon tetrachloride) absorb at this wavelength and are considered analytical interferences. They occur as contaminants in the reagents used during sample preparation. These compounds are not expected to be retained on an MCE filter during sample collection. Analytical interferences are rendered insignificant by using organic-free deionized water and at least reagent grade chemicals or by blank subtraction. Increasing the concentration of nitric acid in the samples or standards appears to produce an elevated background signal. The nitric acid concentration in the samples and standards should not be greater than 10%. 5. Sampling - Particulate Mercury For the sampling and analysis of mercury vapor, consult reference 8.2.
5.1.2. Gel bands (Omega Specialty Instrument Co., Chelmsford, MA) for sealing cassettes. 5.1.3. Sampling pumps capable of sampling at 2 liters per minute (L/min). 5.1.4. Assorted flexible tubing. 5.1.5. Stopwatch and bubble tube or meter for pump calibration. 5.2. Equipment - Wipe Samples Smear tabs (part no. 225-24, SKC Inc., Eighty Four, PA), or wipe filters (Whatman no. 41 or no. 42 filters, Whatman LabSales Inc., Hillsboro, OR). 5.3. Equipment - Bulk Samples Scintillation vials, 20-mL (part no. 74515 or 58515, Kimble, Div. of Owens-Illinois Inc., Toledo, OH) with polypropylene or Teflon cap liners. If possible, submit bulk or wipe samples in these vials. Tin or other metal cap liners should not be used since amalgamation can occur between the metal and mercury. 5.4. Sampling Procedure - Air Samples
5.4.2. Calibrate each personal sampling pump with a prepared cassette in-line to approximately 2 L/min. 5.4.3. Attach prepared cassettes to calibrated sampling pumps (the backup pad should face the pump) and place in appropriate positions on the employee or workplace area. 5.4.4. Collect the samples for at least 5 min. 5.4.5. Place plastic end caps on each cassette after sampling. Attach an OSHA-21 seal around each cassette in such a way as to secure the end caps. 5.5. Sampling Procedure - Wipe Samples A skin designation has been assigned to these mercury-containing compounds.
5.5.2. Moisten the wipe filters with deionized water prior to use. 5.5.3. If possible, wipe a surface area covering 100 cm2. 5.5.4. Fold the wipe sample with the exposed side in. 5.5.5. Transfer the wipe sample into a 20-mL scintillation vial and seal with vinyl or electrical tape. Securely wrap an OSHA-21 seal length-wise from vial top to bottom. 5.6. Sampling Procedure - Bulk Samples In order of laboratory preference, bulk samples may be one of the following: 1) a high-volume filter sample,
5.6.2. The type of bulk sample should be stated on the OSHA 91 and cross-referenced to the appropriate air sample(s). 5.7. Shipment
5.7.2. Send the samples to the laboratory as soon as possible with the OSHA 91A paperwork requesting particulate mercury analysis. 5.7.3. Bulk samples should be shipped separately from air samples. They should be accompanied by Material Safety Data Sheets if available. Check current shipping restrictions and ship to the laboratory by the appropriate method. 6. Analysis
6.1.2. Handle acid solutions with care. Avoid direct contact of acids with work area surfaces, eyes, skin, and clothes. Flush acid solutions which contact the skin or eyes with copious amounts of cold water. 6.1.3. Prepare solutions containing hydrochloric acid in an exhaust hood and store in narrow-mouthed bottles. 6.1.4. Keep B.O.D. bottles containing stannous chloride/hydrochloric acid solutions capped when not in use to prevent inhalation of noxious vapors. 6.1.5. Exercise care when using laboratory glassware. Do not use chipped pipets, volumetric flasks, beakers or any glassware with sharp edges exposed. 6.1.6. Never pipet by mouth. 6.1.7. Always purge the mercury from the CV-AAS into an exhaust vent. 6.1.8. Occasionally monitor the CV-AAS for mercury vapor leaks using an appropriate direct-reading instrument. 6.2. Equipment - Cold Vapor Analysis (Note: Specific equipment is listed for illustration only)
6.2.2. Mercury hollow cathode lamp or electrodeless discharge lamp and power supply. 6.2.3. Biological Oxygen Demand (B.O.D.) bottles, borosilicate glass, 300 mL. 6.2.4. Peristaltic pump, 1.6 to 200 mL range, and controller, 1-100 rpm range (Masterflex model 7553-30 with model 7015 head, Cole-Parmer, Chicago, IL). 6.2.5. Quartz absorption cell, 22 mm (7/8 in) o.d. X 152 mm (6
in) long (part no. 6.2.6. Heating tape. 6.2.7. Variable transformer 50-60 Hz, single phase, 10 A, 120 V input, 0-140 V output, 1.4 kW (Superior Electric, Bristol, CT). 6.2.8. Tygon peristaltic pump tubing (part no. N06409-15, Cole-Parmer), and glass tubing. 6.2.9. Aerator (part no. 0303-3102, Perkin-Elmer). 6.2.10. Chart recorder. 6.2.11. Desiccant (Drierite, W.A. Hammond Drierite Co., Xenia, OH). 6.2.12. Volumetric flasks, volumetric pipets, beakers, and other laboratory glassware. 6.2.13. Automatic pipets, adjustable, 0.1 to 5.0 mL range (models P-1000 and P-5000, Rainin Instruments Co., Woburn, MA). 6.2.14. Exhaust vent. 6.2.15. Automatic pipets, glass or Teflon, unlubricated (cat. no. 050-03-908-1, Brinkmann Dispensette, Brinkmann Instruments, Westbury, NY). 6.2.16. Phillips beakers, 250 mL. 6.2.17. Hot plate (used only for cleaning glassware, not for sample digestions). 6.2.18. Analytical balance (0.01 mg). 6.3. Reagents - All reagents should be at least reagent grade. Potassium permanganate (KMnO4) Hydroxylamine hydrochloride (NH2OH.HCl) Stannous chloride (SnCl2)
6.3.2. Hydrochloric acid (HCl), concentrated (36.5 to 38%), with a mercury concentration less than 0.005 ppm. 6.3.3. Hydroxylamine hydrochloride
(NH2OH.HCl) solution,
20%: Dissolve 200 g
NH2OH.HCl in DI
H20 and dilute to 1 L. A glass automatic
pipet is useful in dispensing this reagent. Rinse the automatic
pipet dispenser with 6.3.4. Mercury standard stock solution, 1,000 µg/mL: Use a
commercially available certified standard or, alternatively,
dissolve 1.0798 g of dry mercuric oxide (HgO) in 50 mL of 1:1
hydrochloric acid and then dilute to 1 Lwith 6.3.5. Nitric acid (HNO3), concentrated (69 to 71%), with a mercury concentration less than 0.005 ppm. 6.3.6. Nitric acid, 1:1: Carefully add equal portions of
concentrated HNO3 and 6.3.7. Nitric acid, 10%: Carefully add 100 mL of concentrated
HNO3 to 900 mL of 6.3.8. Potassium permanganate (KMnO4)
solution, 5%: Dissolve 50 g KMnO4 in 1 L
6.3.9. Stannous chloride (SnCl2)
solution, 10%: Dissolve 20 g SnCl2 in 100
mL concentrated HCl. Slowly and carefully pour this solution into
100 mL 6.3.10. Sulfuric acid (H2SO4), concentrated (95 to 98%), with a mercury concentration less than 0.005 ppm. 6.3.11. Sulfuric acid
(H2SO4), 5 M:
Cautiously add 278 mL concentrated
H2SO4 to
approximately 600 mL 6.4. Glassware Preparation
6.4.2. Clean the B.O.D. bottles and stoppers with 1:1
HNO3 and thoroughly rinse with 6.4.3. Rinse all other glassware with 10% HNO3 and then with DI H2O prior to use. 6.5. Standard Preparation
6.5.2. Prepare working mercury standards (ranging from 0.1 to 2.0 µg) and reagent blanks immediately prior to use. A few standards at each concentration should be prepared. Add an appropriate aliquot of the 1 µg/mL standard to a clean B.O.D. bottle containing enough 10% HNO3 to bring the total volume to 100 mL. A suggested dilution scheme is given:
6.6. Sample Preparation Sample digestion is performed at room temperature under oxidizing conditions to avoid loss of mercury.
6.6.2. Add 5 mL conc. HNO3 to each Phillips beaker and allow to stand for a few min. Subsequently add 15 mL of 5 M H2SO4 followed by the appropriate amount of 5% KMnO4 to each sample to completely oxidize any additional organic material:
Swirl the samples frequently to break up the collection media and allow the samples to digest at least 1 h at room temperature. 6.6.3. Add the appropriate amount of 20% NH2OH.HCl to each Phillips beaker:
The solution and suspended matter in each Phillips beaker should lose the dark-brown or purple color resulting from the KMnO4 treatment and become clear. If it does not, add NH2OH.HCl crystals directly to the beaker until clear. 6.6.4. Quantitatively transfer the sample solution from each
Phillips beaker to a 6.7. Analysis - Instrument Parameters
6.7.2. Wrap the heating tape around the quartz cell and then turn on the variable transformer. The heat setting on the tape should be sufficient to prevent water vapor condensation in the absorption cell. 6.7.3. Place the aerator in a B.O.D. bottle which contains approximately ½ to 1 inch of desiccant. Operate the peristaltic pump for approximately 30 min at full speed to remove any water vapor from the system. 6.7.4. Operate the hollow cathode or electrodeless discharge mercury lamp at the manufacturer's recommended current or power rating. 6.7.5. Use the following settings (Note: The mentioned instrument settings are for specific models used at the OSHA-SLTC. If instrumentation other than what is specified in Section 6.2. is used, please consult the instrument manufacturer's recommendations.):
6.7.6. Optimize the ENERGY meter reading at 253.7 nm. 6.7.7. Align the beam of the mercury lamp so it passes directly through the center of the quartz cell windows. This can be accomplished by adjusting the burner height, depth, and angle knobs to give a minimum ABSORBANCE reading. 6.7.8. Operate the peristaltic pump at full speed. Rinse the
aerator with 6.7.9. Perform the following steps to obtain a baseline signal near an absorbance of zero: 1) start the chart recorder, 6.8. Analytical Procedure
6.8.2. Standards: Immediately before analyzing, prepare standards according to instructions listed in Section 6.5.2. 6.8.3. Deliver 5 mL of the 10% SnCl2 solution with an automatic pipet to a B.O.D. bottle containing a standard, reagent blank, or sample to be analyzed. Immediately place the aerator into the solution with the peristaltic pump operating at full speed. 6.8.4. Record the maximum absorbance reading and label the signal produced on the strip chart. 6.8.5. Stop the pump, remove the B.O.D. bottle from the CV-AAS
and stopper it. Rinse the aerator with 6.8.6. If the absorbance reading of a sample is greater than the highest standard at any time during analysis, immediately remove the B.O.D. bottle from the CV-AAS. Purge the system following the procedure listed in Section 6.8.5. Take a smaller aliquot or dilute the high concentration sample and re-analyze. Make any necessary sample dilutions with 10% HNO3 and use the appropriate dilution factor when calculating results. 6.8.7. Repeat Sections 6.8.3. through 6.8.5. for each prepared standard, reagent blank, or sample. 6.9. Analytical Recommendations
6.9.2. It is also recommended to analyze an entire series of standards (including the reagent blank) at the beginning and end of the sample analysis to ensure standard readings are reproducible. As a general guideline, standard readings should be within ±10% throughout the analysis. 6.9.3. A standard near the concentration range of the samples should be analyzed after every four to five samples. 6.9.4. Quality control (QC) samples should be prepared and analyzed using the same matrix and analytical conditions as the samples. If possible, the QC samples should be generated from an independent source. 6.9.5. Approximately 10% of the samples should be reanalyzed. 7. Calculations
7.2. Determine the amount (µg) of mercury, A, corresponding to the peak absorbance in each analyzed sample aliquot from this curve. 7.3. Calculate the total amount (µg) of mercury, W, in each sample:
Where: 7.4. Calculate the total concentration of mercury in each sample using the appropriate equation:
7.5. Reporting Results
7.5.2. Wipe sample concentrations are reported as total micrograms or milligrams mercury. 7.5.3. Bulk sample results are reported as approximate percent by weight mercury. Due to differences in sample matrices between bulks and standards, bulk results are approximate. 8. References
8.2. Occupational Safety and Health Administration Technical Center: Mercury Vapor in Workplace Atmospheres (OSHA-SLTC Method No. ID-140). Salt Lake City, UT. Revised 1991. 8.3. National Institute for Occupational Safety and Health:
Criteria for a Recommended Standard -- Occupational Exposure to
Inorganic Mercury (DHEW/NIOSH Pub. No. 8.4. Windholz, M., ed.: The Merck Index. 10th ed. Rahway, NJ: Merck & Co. Inc., 1983. 8.5. Sax, N.I. and R.J. Lewis Sr., ed.: Hawley's Condensed Chemical Dictionary, 11th ed.; New York: Van Nostrand Reinhold Co., 1987. 8.6. Occupational Safety and Health Administration Analytical Laboratory: Detection Limit Study for Mercury Cold Vapor Analysis by C. Merrell. Salt Lake City, UT. 1987 (unpublished). 8.7. Occupational Safety and Health Administration Analytical Laboratory: Quality Control Data - Mercury-Spiked Filter Cold Vapor Analysis by B. Babcock. Salt Lake City, UT. 1987 (unpublished). 8.8. Occupatioml Safety and Health Administration Analytical Laboratory: Phenyl Mercuric Acetate (PMA) Procedure by S. Edwards. Salt Lake City, UT. 1981 (unpublished).
![]()
|