GLYCOLS 5523

FORMULA: Table 1 MW: Table 1 CAS: Table 1 RTECS: Table 1

METHOD: 5523, Issue 1 EVALUATION: PARTIAL Issue 1: 15 May 1996

OSHA : No PEL PROPERTIES: See Table 1

NIOSH: No REL
ACGIH: C 50 ppm (ethylene glycol)
(1 ppm = 2.54 mg/m3 @ NTP)

NAMES & SYNONYMS: (1) ethylene glycol: 1,2-ethanediol; (2) propylene glycol: 1,2-propanediol
(3) 1,3-butylene glycol: 1,3-butanediol (4) diethylene glycol: 2-hydroxyethyl ether, 2,2'-
oxydiethanol

SAMPLING MEASUREMENT

SAMPLER: XAD-7 OVS tube TECHNIQUE: GAS CHROMATOGRAPHY, FID

(glass fiber filter, 13-mm; XAD-7,
200mg/100mg) ANALYTES: compounds above

DESORPTION: 2 mL methanol; ultrasonicate 30 min

FLOW RATE: 0.5 to 2 L/min
INJECTION
VOL-MIN: 5L VOLUME: 1 µL
-MAX: 60 L
TEMPERATURE-INJECTION: 250 C
SHIPMENT: pack cold for shipment -DETECTOR: 300 C
-COLUMN: 40 C, 8 C/min to 230 C
SAMPLE
STABILITY: 28 days @ 5 C [1] CARRIER GAS: He2 @ 2.4 to 2.6 mL/min
ethylene glycol 14 days @ 5 C [1]
COLUMN: Rtx-35 fused silica capillary, 30 m,
BLANKS: 2 to 10 field blanks per set 0.53-mm ID, 3-µm film

ACCURACY CALIBRATION: solutions of glycols in methanol

RANGE STUDIED: see EVALUATION OF METHOD RANGE: 15 to 800 µg/sample

BIAS: see EVALUATION OF METHOD ESTIMATED LOD: see Table 2

OVERALL PRECISION ( ): not determined PRECISION ( r): 0.04 to 0.09 [1]

rT

ACCURACY: not determined

APPLICABILITY: Under the GC parameters given in the method, the glycols listed above are baseline separated and can be identified
based on retention time and quantified. Hexylene glycol can be determined by this method; however, no sampling or analytical evaluation
has been conducted.

INTERFERENCES:No specific interferences were identified. The method yields baseline separation for all analytes.

OTHER METHODS: This method replaces NMAM 5500 [2], which was found deficient in the collection of ethylene glycol in aerosol form.
Also ethylene glycol was not separated from propylene glycol by the chromatography.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 GLYCOLS: METHOD 5523, Issue 1, dated 15 May 1996 - Page 2 of 5

REAGENTS: EQUIPMENT:

1. Ethylene glycol, reagent grade.* 1. Sampler: XAD-7 OVS tube, 13-mm OD,
2. Propylene glycol, reagent grade.* containing two sections of XAD-7 (200 mg
3. 1,3-Butylene glycol, reagent grade.* front/100 mg back section) separated by
4. Diethylene glycol, reagent grade.* polyurethane foam plug. A glass fiber filter
5. Triethylene glycol, reagent grade.* plug precedes the front section and a
6. Tetraethylene glycol, reagent grade.* polyurethane foam plug follows the back
7. Methanol, chromatographic grade.* section. Tubes are commercially available
8. Calibration stock solution, 10 mg/mL: Weigh (SKC, Inc., #226-57).
aliquots of each glycol and dissolve in 2. Personal sampling pump, 0.5 to 2 mL/min, with
methanol. flexible connecting tubing.
9. Helium, purified. 3. Gas chromatograph, flame ionization detector,
10. Hydrogen, prepurified. integrator, and column (page 5523-1).
11. Air, filtered. 4. Ultrasonic bath.
5. Vials, autosampler, with PTFE-lined caps.
* See SPECIAL PRECAUTIONS 6. Vials, 4 mL, with screw caps.
7. Syringes, 10-µL and other sizes as needed,
readable to 0.1 µL.
8. Flasks, volumetric, various sizes.
9. Pipets, various sizes.

SPECIAL PRECAUTIONS: Inhalation of glycol mists causes respiratory irritation, shortness of breath,
and coughing. Methanol is flammable and a dangerous fire risk. Work with these compounds in a well-
ventilated hood.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Remove front and rear caps from the tube immediately before sampling. Attach sampler to personal
sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.5 and 2 L/min for a total sample size of 5 to 60 L.
4. Cap the samplers and pack securely in dry ice for shipment.

SAMPLE PREPARATION:

5. Place front sorbent section and glass fiber filter in a 4-mL screw cap vial. Place backup sorbent section
in a separate vial. Discard foam plugs.
6. Add 2 mL of methanol to each vial and cap.
7. Place vials in an ultrasonic bath for 30 min to aid desorption.

CALIBRATION AND QUALITY CONTROL:

8. Calibrate daily with at least six working standards over the range of interest. Three standards (in
duplicate) should cover the range from LOD to LOQ.
a. Add known amounts of calibration stock solution to methanol in 10-mL volumetric flasks and dilute
to the mark.
b. Analyze together with samples and blanks (steps 11 and 12).
c. Prepare calibration graph (peak area or height vs. µg glycol).
9. Determine desorption efficiency(DE) at least once for each lot of OVS tubes used for sampling in the
calibration range (step 8).
a. Prepare three samplers at each of six levels plus three media blanks.
b. Inject a known amount of calibration stock solution directly onto the
filter of OVS tubes. Draw air

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 GLYCOLS: METHOD 5523, Issue 1, dated 15 May 1996 - Page 3 of 5

through the sampler at 1 L/min for 60 min.

c. Cap the ends of the tubes and allow to stand overnight.
d. Desorb (steps 5 through 7) and analyze together with standards and blanks (steps 11 and 12).
e. Prepare a graph of DE vs. µg analyte recovered.

10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration graph
and DE graphs are in control.

MEASUREMENT:

11. Set gas chromatograph according to manufacturer’s recommendations and to conditions given on page
5523-1. Inject 1-µL sample aliquot manually using solvent flush technique or with autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with methanol, reanalyze
and apply the appropriate dilution factor in the calculations.
12. Measure peak areas.

CALCULATIONS:

13. Determine the mass, µg (corrected for DE), of each glycol found in the sample front (W f) and back
(Wb) sorbent sections, and in the average media blank front (B
f) and back (Bb) sorbent sections.
NOTE: If Wb > Wf /10, report breakthrough and possible sample loss.
14. Calculate concentration, C, of each analyte in the air volume sampled, V (L):

(Wf Wb Bf Bb)
C ,mg/m 3
V

EVALUATION OF METHOD:

The method was evaluated for six glycols (ethylene, propylene, 1,3-butylene, diethylene, triethylene, and
tetraethylene). Desorption efficiency (DE) was determined by spiking known amounts of each glycol in
methanol solution onto the glass fiber filter plug of the XAD-7 OVS tubes, drawing air through the spiked
tubes at 1 L/min for 60 min, and analyzing. Recovery data along with LODs and LOQs for each analyte are
listed in Table 2. When stored at 5 C, ethylene glycol samples on XAD-7 OVS tubes were stable for 14
days, and the other glycols were stable up to 28 days. Glycol aerosols were generated at three concentration
levels (6 samples per concentration) from a ROSCO™ Model 1500 Fog Machine. Precision [as calculated
from the pooled relative standard deviation ( r)] and mean bias for the glycols are as follows:

Range Studied
Analyte (µg/sample) Precision ( r) Bias
Ethylene glycol 33 to 218 0.043 -15%
Propylene glycol 26 to 187 0.062 -3.2%
1,3-butylene glycol 34 to 178 0.054 -0.5%
Diethylene glycol 68 to 219 0.047 -0.2%
Triethylene glycol 33 to 201 0.075 -4.0%
Tetraethylene glycol (2 levels) 32 to 197 0.035 +20%

The low recovery for ethylene glycol possibly may be attributed to increased volitility when sampled at
1 L/min [1]. Although hexylene glycol is separated by the chromatographic conditions given in the method,
no evaluation of sampling or analytical parameters was done for this compound.

REFERENCES:

[1] Pendergrass, S.M. [1994]. Development of a sampling and analytical methodology for the

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 GLYCOLS: METHOD 5523, Issue 1, dated 15 May 1996 - Page 4 of 5

determination of glycols in air: Application to theatrical smokes. Unpublished paper presented at

Pittsburgh Conference, Chicago, IL, March 1994.
[2] NIOSH [1984]. Ethylene glycol: Method 5500. In: Eller PM, Ed. NIOSH manual of analytical
methods, 3rd ed. Cincinnati, OH: U.S. Department of Health and Human Services, HHS (NIOSH)
Publication No. 84-100.

METHOD WRITTEN BY:

Stephanie M. Pendergrass, MRSB, DPSE

TABLE 1. GLYCOLS GENERAL INFORMATION

Analyte Formula MW CAS # RTECS # Properties

Ethylene C2H6O2 62.07 107-21-1 KW2975000 liquid; BP 197.2 C; FP -13 C; d

glycol 1.113 g/mL @ 20 C; nD 1.4310; vp
0.007 kPa (0.05 mm Hg) @ 20 C;
explosive limits 3.2 to 15.3% v/v in
air

Propylene C3H8O2 76.10 57-55-6 TY2000000 liquid; BP 188 C; FP -60 C ; d

glycol 1.038 g/mL @ 20 C; nD 1.4320; vp
0.009 kPa (0.07 mm Hg) @ 20 C;
explosive limits 2.6 to 12.5% v/v in
air

1,3-Butylene C4H10O2 90.12 107-88-0 EK0440000 liquid; BP 207.5 C; d 1.0059 g/mL

glycol @ 20 C; nD 1.4400; vp 0.06 mm Hg
@ 20 C

Diethylene C4H10O3 106.12 111-46-6 ID5950000 liquid; BP 245 C; FP -6.5 C; d

glycol 1.118 g/mL @ 20 C; nD 1.4460 @
25 C; vp <0.01 mm Hg @ 20 C;
explosive limits 3 to 7% v/v in air

Triethylene C6H14O4 150.17 112-27-6 YE4550000 liquid; BP 285 C; FP -5 C; d 1.125

glycol g/mL @ 20 C; nD 1.4550; vp <0.001
mm Hg @ 20 C; explosive limits 0.9
to 9.2% v/v in air

Tetraethylene C8H18O5 194.23 112-60-7 XC2100000 liquid; BP 327.3 C; FP -4 C; d

glycol 1.125 g/mL @ 20 C; nD 1.4577; vp
>0.001 mm Hg @ 20 C

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 GLYCOLS: METHOD 5523, Issue 1, dated 15 May 1996 - Page 5 of 5

TABLE 2. GLYCOL RECOVERY DATA

Desorption Efficiency Spikesa

b
Analyte LOD LOQ r
(µg/sample) (µg/sample 100 µg 200 µg
) (% Recovery) (% Recovery)

Ethylene 7 22 93.4 101 0.059

glycol

Propylene 6 13 83.4 92.5 0.064

glycol

1,3-Butylene 6 12 98.8 102 0.072

glycol

Diethylene 16 48 94.6 114 0.041

glycol

Triethylene 14 42 85.3 98.7 0.043

glycol

Tetraethylene 14 42 111 141 0.092

glycol

a
n = 6 for each spiking level
b
Pooled Relative Standard Deviation

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition