HEXAVALENT CHROMIUM
OSHA Technical Center Salt Lake City, Utah 1. Introduction This method describes the air sampling and subsequent analysis of workplace exposures to chromic acid and chromate compounds. Analysis is conducted by differential pulse polarography (DPP).
This method has been developed at the OSHA Salt Lake City Technical Center
The classical method of Cr(VI) analysis is colorimetry using
The extraction of Cr(VI) in basic solution and subsequent analysis by colorimetry using DPC has been reported (8.3.). The extraction technique used in this method is a modification of that suggested in reference 8.3. In this method the analytical technique for Cr(VI) is DPP. Polarographic techniques have been previously reported for the analysis of chromium species (8.5., 8.6.). 1.2. Principle
1.2.2. The reaction between chromates and carbonate is illustrated by the following equation (8.3.): MCrO4 + CO3(2 »)< ----> MCO3 + CrO4(2 ») where M = metals (i.e. lead, zinc, cadmium, ...) In the presence of a large excess of carbonate, equilibrium is quantitatively shifted to the right. The chromate compounds (soluble and insoluble) are converted to their corresponding carbonates. 1.3. Advantages and Disadvantages
1.3.2. In addition to the Cr(VI) analysis, it is possible to determine other soluble compounds such as lead and zinc salts in the same solution. 1.3.3. By using alkaline extraction conditions (pH 10 to 11), sample recovery is improved by preventing Cr(VI) losses which may occur in a more acidic extraction media. Both water soluble and insoluble Cr(VI) compounds are soluble in this alkaline extraction medium. 1.3.4. The sensitivity is adequate for measuring workplace atmospheric concentrations of Cr(VI) and is less sensitive to interferences noted when using the colorimetric/DPC procedure (8.2., 8.7.). Potential interferences with the polarographic determination may be rendered insignificant by altering analytical conditions such as changing the supporting electrolyte solution. 1.3.5. Polarographic instruments have a wide analytical range. This diminishes the need for withdrawing aliquots or diluting the samples in order to be within the linear analytical range of the instrument. 1.3.6. A disadvantage is the polarographic instrument may not be available in some analytical laboratories; however, the extracted samples may be acidified and then analyzed using a modified colorimetric/DPC method (please see Section 7 of reference 8.8. for further information). Spiked samples using compounds known to be present in the sample matrix should be taken through this alternate procedure first to determine if any loss of Cr(VI) occurs during acidification. Detection limits should also be determined. 1.4. Uses Occupations having a potential exposure to compounds containing Cr(VI) as well as a list of different chromate compounds are listed in reference 8.10. 2. Range and Detection Limit (8.8.)
This method has the sensitivity necessary to determine compliance with either the
OSHA Transitional or the Final Rule PEL. Samples for Final Rule determinations
should be taken with at least 2.2. The qualitative and quantitative detection limits for 10-mL sample solution volumes were 0.19 µg and 0.58 µg as CrO3, respectively. 3. Method Performance (8.8.)
The DPP analytical method has been evaluated using a time weighted average concentration of
0.009 mg/m3 as CrO3
3.2. A comparison of methods using spiked samples containing PbCrO4 showed that results obtained by a modified colorimetric/DPC method were duplicated for the DPP method. There was no significant bias between the two methods (8.8.). 3.3. A collection efficiency of 0.945 ¦ 0.035 has been previously determined for chromic acid mist collected on PVC filters (8.11.).
3.4. Quality control samples were prepared by spiking aqueous solutions of potassium
dichromate on PVC filters. These samples were analyzed along with survey samples at
4. Interferences
4.2. The effect of many interferences can be minimized by changing the operating
conditions of the polarograph. Additional polarographic confirmation of a cation in a
sample may be performed in a second electrolyte and observing if the new 5. Sampling
Filter holder consisting of a two- or three-piece cassette, 5.1.2. Gel bands (Omega Specialty Instrument Co., Chelmsford, MA) for sealing cassettes. 5.1.3. Sampling pumps capable of sampling at 2 L/min. 5.1.4. Assorted flexible tubing. 5.1.5. Stopwatch and bubble tube or meter for pump calibration. 5.1.6. Scintillation vials (for bulk samples), 20-mL, part no. 74515 or 58515, (Kimble, Div. of Owens-Illinois Inc., Toledo, OH) with polypropylene or Teflon cap liners. 5.2. Sampling Procedure
5.2.2. Calibrate each personal sampling pump with a prepared cassette
5.2.3. 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. Collect the samples using a total air volume of at least 5.2.4. For Time Weighted Average samples: If the filter becomes overloaded while sampling, consecutive samples using shorter sampling periods should be taken.
5.2.5. Wipe samples can be taken using PVC filters as the wipe media. Wear clean,
impervious, disposable gloves when taking each wipe sample. If possible, wipe
a surface area covering 100 cm¦. Fold the wipe sample with the exposed side
in and then transfer into a 5.2.6. If bulk samples are necessary, collect the bulk samples using a grab sampling technique suitable for the particular material(s) in use. If possible, transfer any bulk samples into 20-mL scintillation vials. 5.3. Shipment
5.3.2. Seal scintillation vials with vinyl or electrical tape. Securely wrap an
OSHA-21 5.3.3. 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. When handling any chemicals, a labcoat, safety glasses or goggles, and gloves should be worn. 6.1.3. The buffer/extraction/electrolyte (BEE) solution is basic and somewhat corrosive. Clean up any spills immediately. This solution should be stored in polyethylene bottles since precipitated salts form readily during evaporation and will cause glass stoppers to seize. Samples prepared in glassware should be analyzed and properly disposed of as soon as possible. 6.1.4. Mercury is used as the working electrode in DPP. Always exercise caution to prevent any potential spills of mercury. Containment vessels should surround the polarograph and spill control devices should be available when handling or working with mercury. 6.1.5. Refer to the Standard Operating Procedure (SOP) (8.13.) and instrument manuals for proper operation of the polarographic instrument and safety precautions. 6.1.6. Extra care should be used when handling perchloric acid (HClO4). Perchloric acid should only be used in a hood that has been approved for HClO4 use. In this hood: Working with HClO4 is very hazardous. Be sure to wear safety glasses, a labcoat, and gloves. Always add nitric acid (HNO3) with HClO4 when digesting samples. Watch the samples during HClO4 digestion carefully since there is a chance they could ignite. Always keep HNO3 nearby when using HClO4. In the event of sample media ignition, quickly douse the sample with a small portion of HNO3. 6.2. Equipment
6.2.2. Glass polarographic cells, 15-mL.
6.2.3. Nitrogen purification system: Gas purifier for deoxygenating nitrogen,
[(Oxiclear, part no. 6.2.4. Hot plate and exhaust hood. 6.2.5. Phillips beakers, borosilicate, 125-mL, with watch glass covers.
6.2.6. Filtration apparatus: Vacuum, vacuum flask, and PVC filters, 6.2.7. Teflon-coated magnetic stirring bar and stirrer. 6.2.8. Micro-analytical balance (0.01 mg). 6.2.9. Polyethylene bottles, 100-mL to 1-L size. 6.2.10. Volumetric and micropipettes, volumetric flasks, beakers, and general laboratory glassware. Do not use glassware for sample analysis of chromate compounds if it was: 6.3. Reagents - All chemicals should be reagent grade or better.
6.3.2. Deionized water (DI H2O) with a specific conductance of less than 10 µS. 6.3.3. Sodium carbonate (Na2CO3), anhydrous. 6.3.4. Sodium bicarbonate (NaHCO3).
6.3.5. Buffer/extraction/electrolyte (BEE) solution (pH approximately 10.5): Dissolve 100 g of Na2CO3 and 20 g of NaHCO3 in about 500 mL DI H2O contained in a 6.3.6. Potassium dichromate (K2Cr2O7), or potassium chromate (K2CrO4).
6.3.7. Cr(VI) Stock Standard (1,000 µg/mL): Dissolve 2.829 g K2Cr2O7 or 3.735 g K2CrO4 in DI H2O and dilute to the mark in a 6.3.8. Cr(VI) standard (100 µg/mL): Dilute 10 mL of the Cr(VI) stock standard to 100 mL with DI H2O. Prepare this solution every three months. 6.3.9. Cr(VI) working standard (10 µg/mL): Dilute 10 mL of the Cr(VI) 100 µg/mL standard to 100 mL with the BEE solution. Transfer to a polyethylene bottle. Prepare this solution daily. 6.3.10. Cr(VI) working standard (1 µg/mL): Dilute 10 mL of the Cr(VI) 10 µg/mL working standard to 100 mL with the BEE solution. Transfer to a polyethylene bottle. Prepare this solution daily. 6.3.11. Nitric acid (HNO3), concentrated (69 to 71%). 6.3.12. Nitric acid 6 M: Carefully dilute 384 mL of concentrated (conc.) HNO3 to 1 L using DI H2O. 6.3.13. Nitric acid, 10% (v/v): Carefully dilute 100 mL of conc. HNO3 to 1 L using DI H2O. 6.3.14. Perchloric acid (HClO4), conc. (69 to 71%). 6.3.15. Hydrogen peroxide (H2O2), 30%. 6.3.16. Mercury, triple distilled, for the working electrode. 6.4. Sample Preparation
6.4.2. Adjust the hot plate to a temperature below the boiling point of the BEE solution. 6.4.3. If bulk samples are submitted, weigh out a representative aliquot of each bulk on separate blank PVC filters.
6.4.4. Carefully remove the PVC filter from the cassette or balance, place it
6.4.5. Allow the solutions to cool to room temperature. Quantitatively transfer each
solution to a 10- or 6.4.6. If the solution is cloudy and/or other metal analyses are desired, filter the solution through a PVC filter in a vacuum filtration apparatus. If necessary, prepare and analyze samples for other metals using the appropriate techniques. An example would be to determine the total metal content of the sample residue by atomic absorption or inductively coupled plasma spectroscopy. 6.4.7. For samples taken from spray painting operations, digest the extracted filters containing the paint residue according to the following procedure:
6.5. Standard Preparation Prepare a series of Cr(VI) standards in the analytical range of 0.050 to 10 µg/mL. Make appropriate serial dilutions of the Cr(VI) working standards with the BEE solution. 6.6. Analytical Procedure
Soak polarographic cells in 6 M HNO3 (preferably overnight), rinse thoroughly with
DI H2O, and 6.6.2. Set the operating conditions for the instrument as follows (Note: If other types of instruments are used, refer to their operating and service manuals for comparable settings):
6.6.3. Refer to reference 8.13. or other instrument manuals for operating procedures.
6.6.4. Transfer a sample or blank to a polarographic cup. If the final solution volume
was 6.6.5. Purge each standard, blank, or sample between 30 to 240 s with purified nitrogen. 6.6.6. Analyze the reagent blank (10 mL of BEE solution), the standards, and the samples by measuring the peak current (nA). A standard should be analyzed after every five or six samples. 6.6.7. Wash the polarographic electrodes thoroughly with DI H2O after each sample is analyzed.
6.6.8. Record the peak current (nA) and potential for each determination. A
differential pulse polarogram of 6.6.9. If the peak current from a sample is above the largest standard used, an aliquot should be taken from the sample and diluted to 10 mL with BEE solution and analyzed. A dilution factor for this sample is applied when calculating results (Section 7.2.). 6.6.10. Other metals such as lead and zinc may be determined in the same solution if required. Approximate peak potentials of -0.630 V for Pb and -1.350 V for Zn were found when these species were present in the BEE solution. 7. Calculations
7.2. Determine the air concentration of CrO3 in each extraction sample according to the following equation:
7.3. For digested spray paint samples analyzed according to OSHA method no. ID-121, the calculations above may be used without the gravimetric factor or use calculations mentioned in that method to determine the amount of total chromium. 7.4. For bulk samples, calculate the total composition (in %) of CrO3 in each sample using:
Where:
7.5. Report air sample results (from base extractions) to the industrial hygienist as mg/m¦ CrO3. 7.6. For spray paint samples, also report results obtained from the digestion of the residue. Report each result from digested samples as mg/m¦ chromium metal and insoluble salts. Each result can be combined with the result in Section 7.5. by the industrial hygienist if the paint used during sampling does not contain other chromium compounds. Before combining results, the industrial hygienist has to perform the following calculation: CrO3(residual) mg/m3 = Cr metal (mg/m3) + 1.923 Then:
7.7. Report bulk sample results to the industrial hygienist as approximate per cent CrO3. 8. References
8.2. National Institute for Occupational Safety and Health: NIOSH Manual of
Analytical Methods. 2nd ed., Vol. 3 (DHEW/NIOSH Pub. No.
8.3. Thomsen, E. and R.M. Stern: A Simple Analytical Technique for the Determination
of Hexavalent Chromium in Welding Fumes and Other Complex Matrices. Scand. J.
of Work, Environ. and Health 5:
8.4. Molina, D. and M.T. Abell: An Ion Chromatographic Method for Insoluble
Chromates in Paint Aerosol. Am. Ind. Hyg. Assoc. J. 48:
8.5. Dubois, L. and J.L. Monkman: Polarographic Determination of Heavy Metals in Air
Samples. Am. Ind. Hyg. Assoc. J. 25:
8.6. Urone, P.F., M.L. Druschel and H.K. Anders: Polarographic Microdetermination
of Chromium in Dusts and Mists. Anal. Chem. 22:
8.7. Abell, M.T. and J.R. Carlberg: A Simple Reliable Method for the Determination of
Airborne Hexavalent Chromium. Am. Ind. Hyg. Assoc. J. 35:
8.8. Occupational Safety and Health Administration Technical Center: Hexavalent
Chromium Backup Data Report
8.9. Dutkiewicz, R., J. Konczalik and M. Przechera: Assessment of the Colorimetric
Methods of Determination of Chromium in Air and Urine by Means of Radioisotope
Techniques. Acta Pol. Pharm. 26:
8.10. National Institute for Occupational Safety and Health: Criteria for a Recommended Standard -- Occupational Exposure to Cr(VI) (DHEW/NIOSH Pub. No.
8.11. National Institute for Occupational Safety and Health: Documentation of the
NIOSH Validation Tests. Backup Data Report, Chromic Acid & Chromates, No. S317
(Contract No. 8.12. Occupational Safety and Health Administration Analytical Laboratory: Quality Control Data - Chromate Analysis by B. Babcock. Salt Lake City, UT. 1987 (unpublished). 8.13. Occupational Safety and Health Administration Technical Center: Standard Operating Procedure for Polarography. Salt Lake City, UT. In progress (unpublished). 8.14. Princeton Applied Research: Application note 108, Why Dearation... and How. Princeton, NJ: Princeton Applied Research, 1974.
8.15. Occupational Safety and Health Administration Technical Center: Metal and
Metalloid Particulates in Workplace Atmospheres (Atomic Absorption)
8.16. Beyerman, K.: The Analytical Behavior of Minutest Chromium Quantities, Part I. Z. Anal. Chem. 190:
8.17. Beyerman, K.: The Analytical Behavior of Minutest Chromium Quantities, Part II. Z. Anal. Chem. 190:
Polarogram of a 1 µg/mL Cr(VI) Standard
NA = nanoamperes
|