(C4H9O)3P=O MW: 266.32 CAS: 126-73-8 RTECS: TC7700000
METHOD: 5034, Issue 1 EVALUATION: PARTIALIssue 1: 15 August 1994
OSHA :0.5 ppmNIOSH:0.2 ppmACGIH:0.2 ppm
(1 ppm = 10.9 mg/m3 @ NTP)PROPERTIES: liquid; boiling point 293 C; density 0.98 g/mL @ 20 C; VP very low @ 20 C; vapor density 9.2 (air=1); flash point 166 C (closed cup)
SYNONYMS:phosphoric acid, tributyl ester; tri-n-butyl phosphate; TBP; Celluphos 4
SAMPLING
SAMPLER:FILTER (0.8-µm mixed cellulose estermembrane); above 23 C, use two filtercassettes in seriesTECHNIQUE:ANALYTE:EXTRACTION:INJECTIONVOLUME:DETECTOR:MEASUREMENT
GC, FPD with a phosphorus filtertributyl phosphate10 mL diethyl etherFLOW RATE:1 to 3 L/minVOL-MIN: -MAX:SHIPMENT:2 L @ 0.5 ppm100 Lseparate front and backup cassettes if two wereused; seal cassettes firmly with plugs5 µLH2, 70 mL/min; Air 150 mL/min240 C240 °C150 °CSAMPLE STABILITY:BLANKS:not determined2 to 10 field blanks per setTEMPERATURE-INJECTION: -DETECTOR: -COLUMN:CARRIER GAS:COLUMN: N2, 50 mL/minACCURACYRANGE STUDIED:BIAS:2.7 to 12.6 mg/m3 [1](100-L samples)- 0.3%CALIBRATION:6-ft x -in ID stainless steel, with 3%OV-101 on 100/120 mesh Supelcoportstandard solutions of tributyl phosphatein diethyl ether6 to 1500 µg per sample2 µg per sample [1]0.0146 @ 234 to 973 µg per sample [1]ˆ):0.076 [1]OVERALL PRECISION (S rTACCURACY:± 16.8% RANGE:ESTIMATED LOD: ):PRECISION (S rAPPLICABILITY: The working range is 0.006 to 1.4 ppm (0.06 to 15 mg/m3) for a 100-L air sample. This method may be
adapted to other phosphates of relatively low volatility with appropriate changes in chromatographic conditions.
INTERFERENCES: Any phosphorus-containing compound that has the same retention time as the analyte is an interference.A non-polar capillary column may be used for better resolution.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
OTHER METHODS: This revises Method S208 [2]. Analytical methods for tributyl phosphate (TBP) have been reviewed [3].Another packed-column GC procedure has been described recently [4]. TBP has been determined in air by capillary-columnGC/NPD preceded by sampling on a glass fiber filter or XAD-7 resin [5]. GC/MS [6], LC/MS [7], and LC/TID (thermionic detection)[8] have all been shown to be useful methods for the analysis of TBP in environmental samples. Finally, a continuous phosphorusgas analyzer has been used to monitor TBP in air [9].
REAGENTS:1.2.3.4.5.6.
Diethyl ether*, anhydrous, reagent grade.Tributyl phosphate*, reagent grade.Hydrogen, purified
Compressed air, prefilteredNitrogen, purified
Calibration stock solution, tributyl phosphate indiethyl ether
EQUIPMENT:
1.Sampler: 37-mm mixed cellulose ester
membrane filter (0.8-µm pore size) supportedby cellulose backup pad in three-piece filterholder.
NOTE:Backup filter unit is needed when
sampling at temperatures above23 °C.
2.Personal sampling pump, 1 to 3 L/min, with
flexible polyethylene or PTFE tubing.
3.Gas chromatograph equipped with a flame
photometric detector, phosphorus filter, andcolumn (p. 5034-1).
4.Electronic integrator or some other suitable
method for measuring peak areas. 5.Tweezers.
6.Jars: 2 oz ointment jars for sample extraction,
squat form with aluminum-lined screw caps. 7.Syringes, 10-µL and other convenient sizes. 8.Volumetric flasks, 10-mL and other convenient
sizes.
9.Pipets, 10-mL and other convenient sizes.
*See Special Precautions
SPECIAL PRECAUTIONS: Store diethyl ether away from heat, light, and sources of ignition in a well-ventilated area. Do not leave container open. Diethyl ether can oxidize in air to form explosiveperoxides, a reaction accelerated by light. Distillation and evaporation can concentrate unstableperoxides in the residue, a potentially explosive condition [10].
Avoid inhalation of tributyl phosphate vapors and contact with eyes, skin, and clothing [11,12]. Handleonly in a hood.
SAMPLING:1.2.
Calibrate each personal sampling pump with the representative filter cassettes in line.
Remove cassette plugs and connect cassette filter to the personal sampling pump with flexibletubing.
NOTE:If ambient temperature is above 23 °C, use two filter cassettes connected in series with
a short piece of flexible tubing for sample collection. Some tributyl phosphate may existas vapor above 23 °C.
Sample at an accurately known flow rate of 1 to 3 L/min for a total sample size of 2 to 100 L.Separate front and backup filter cassettes (if two cassettes were used). Firmly seal collectedsample cassettes with plugs, and pack securely for shipment.
3.4.
SAMPLE PREPARATION:5.
Transfer the filter and backup pad to an ointment jar using tweezers.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
TRIBUTYL PHOSPHATE: METHOD 5034, Issue 1, dated 15 August 1994 - Page 3 of 46.7.
Pipet 10.0 mL of diethyl ether into each jar. Seal the jar immediately to minimize evaporation.Allow samples to stand for at least 30 min with occasional agitation.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
TRIBUTYL PHOSPHATE: METHOD 5034, Issue 1, dated 15 August 1994 - Page 4 of 4
CALIBRATION AND QUALITY CONTROL:8.
Calibrate daily with at least six working standards over the range of 2 to 1000 µg per sample.a.Add known amounts of calibration stock solution to 10-mL volumetric flasks and dilute to
volume with diethyl ether.
b.Analyze working standards together with samples and blanks (steps 11 and 12). This will
minimize the effect of variations in FPD response with time.NOTE 1:The FPD response is very sensitive to minor variations in hydrogen flow rate
and, therefore, it is recommended that calibration standards be carefullyinterspersed with the samples.
NOTE 2:Use of an internal standard is recommended to minimize errors caused by
sample solvent evaporation and FPD response variations.
c.Prepare a calibration graph of area vs. µg of tributyl phosphate per 10 mL of sample. Determine recovery in the concentration range of interest for each lot of filters used forsampling. Prepare three filters at each of five levels plus three media blanks.a.Spike aliquot of calibration solution onto each filter.
b.After air-drying, extract filters with 10 mL diethyl ether (steps 5 through 7).c.Analyze together with working standards (steps 11 and 12).d.Prepare graph of recovery vs. µg tributyl phosphate.
Analyze three quality control blind spikes and three analyst spikes to ensure that the calibrationgraph and recovery graph are in control.
9.
10.
MEASUREMENT:11.
Set gas chromatograph according to manufacturer's recommendations and to conditions givenon page 5034-1. Inject 5-µL sample aliquot using solvent flush technique or with autosampler.NOTE:If peak area is above linear range of the calibration graph, dilute with diethyl ether,
analyze, and apply appropriate dilution factor in calculations.
Measure peak area.
12.
CALCULATIONS:13.14.
Determine mass, µg (corrected for recovery), of tributyl phosphate found in the sample (W) andthe average media blank (B).
Calculate concentration of tributyl phosphate in the actual air volume sampled, V (L):
EVALUATION OF METHOD:
TRIBUTYL PHOSPHATE: METHOD 5034, Issue 1, dated 15 August 1994 - Page 5 of 4
REFERENCES:[1][2][3]
Backup Data Report for Tributyl Phosphate, in Documentation of the NIOSH Validation Tests,prepared under NIOSH Contract CDC-99-74-45 (1977).
NIOSH Manual of Analytical Methods, 2nd. ed., V. 3, S208, U.S. Department of Health,Education, and Welfare, Publ. (NIOSH) 77-157-C (1977).
Davis, W., Navratil, J., Lasztity, A., and Horvath, Z., Analytical Methods [for Tributyl Phosphate],in Science and Technology of Tributyl Phosphate, Vol. 1, pp 267-327, Schulz, W. and Navratil,J., Eds., CRC, Boca Raton, FL, 1984.
Kuno, Y., Hina, T., Akiyama, T., and Matsui, M., Simultaneous Determination of TributylPhosphate and Dibutyl Phosphate in Spent Fuel Reprocessing Streams by GasChromatography, J. Chromatogr., 537 (1-2): 489 (1991).Haraguchi, K., Yamashita, T., and Shigemori, N., Sampling and Analysis of Phosphoric AcidTriesters in Ambient Air, Taiki Osen Gakkaishi, 20 (6): 407 (1985).Ishikawa, S., Taketomi, M., and Shinohara, R., Determination of Trialkyl and Triaryl Phosphatesin Environmental Samples, Water Res., 19 (1): 119 (1985).Barceló, D., Application of Thermospray Liquid Chromatography/Mass Spectrometry for
Determination of Organophosphorus Pesticides and Trialkyl and Triaryl Phosphates, Biomed.Environ. Mass Spectrom., 17 (5): 363 (1988).Barceló, D., Maris, F., Frei, R., de Jong, G., and Brinkman, U., Determination of Trialkyl andTriaryl Phosphates by Narrow-Bore Liquid Chromatography with on-line Thermionic Detection,Intern. J. Environ. Anal. Chem., 30 (1-2): 95 (1987).Parker, G., Continuous Quantitative Analysis of Low Concentrations of Tributyl Phosphate (TBP)Vapors in Flowing Air Streams, Am. Ind. Hyg. Assoc. J., 41 (3): 220 (1980).Material Safety Data Sheet for Diethyl Ether, No. 343, General Electric Company, Schenectady,N.Y., August, 1979.
Material Safety Data Sheet for Tributyl Phosphate, No. 521, General Electric Company,Schenectady, N.Y., October, 1983.
Material Safety Data Sheet for Tributyl Phosphate, No. P1180.2, Van Waters & Rogers, Inc.(U.S.), Seattle, Washington, August 27, 1989.
[4]
[5][6][7]
[8]
[9][10][11][12]
METHOD REVISED BY:
Robert P. Streicher, Ph.D., NIOSH/DPSE.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
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