Alcohols IV (1403)
ALCOHOLS IV (1) HOCH2 CH2 OCH3 (2) HOCH2 CH2 OCH2 CH3 (3) HOCH2 CH2 O(CH2 )3 CH3
MW: (1) 76.09 (2) 90.12 (3) 118.17
METHOD: 1403, Issue 3
CAS: (1) 109-86-4 RTECS: (1) KL5775000 (2) 110-80-5 (2) KK8050000 (3) 111-76-2 (3) KJ8575000
EVALUATION: FULL
PROPERTIES:
OSHA : See Table 1 NIOSH: See Table 1 ACGIH: See Table 1
SYNONYMS:
1403
Issue 1: 15 August 1990 Issue 3: 15 March 2003
See Table 1
(1) 2-methoxyethanol: methyl cellosolve, ethylene glycol monomethyl ether, EGME (2) 2-ethoxyethanol: cellosolve, ethylene glycol monoethyl ether, EGEE (3) 2-butoxyethanol: butyl cellosolve, ethylene glycol monobutyl ether, EGBE
SAMPLING
MEASUREMENT
SAMPLER:
SOLID SORBENT TUBE (Coconut shell charcoal, 100 mg/50 mg)
FLOW RATE:
0.01 to 0.05 L/min
VOL-MIN: -MAX:
(1) 6L 50 L
SHIPMENT:
Routine
SAMPLE STABILITY:
30 days @ 5°C
BLANKS:
2 to 10 field blanks per set
(2) 1L 6L
(3) 2L 10 L
TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol
DESORPTION:
1 mL methylene chloride/methanol (95:5) in an ultrasonic bath for 30 minutes
INJECTION VOLUME:
1 µL
TEMPERATURE -INJECTION: -DETECTOR: -COLUMN:
225°C 300°C 40°C (1 min) - 200°C (12°C/min)
CARRIER GAS:
He, 2.5-3.0 mL/min
COLUMN:
Capillary, fused silica, 30 m x 0.32-mm ID; crossbonded carbowax®-DA or equivalent
CALIBRATION:
Solutions of analytes in desorption solvent
RANGE:
(1) 2 to 387 µg (2) 2 to 373 µg (3) 3 to 361 µg
ACCURACY RANGE STUDIED:
See Table 2.
BIAS:
See Table 2.
OVERALL PRECISION ( Ö r T ):
See Table 2.
ACCURACY:
See Table 2.
ESTIMATED LOD: (1) 0.8 µg/sample (2) 0.7 µg/sample (3) 1.0 µg/sample PRECISION ( þ r ):
(1) 0.024 (2) 0.022 (3) 0.048
APPLICABILITY: The working range for 2-methoxyethanol was 0.095 to 204 ppm (0.33 to 64.5 mg/m3 ) for a 6-L sample volume, for 2-ethoxyethanol was 0.053 to 99 ppm (0.20 to 373 mg/m3 ) for a 1-L sample, and for 2-butoxyethanol was 0.3 to 36.8 ppm (1.5 to 180 mg/m3 ) for a 2-L sample. INTERFERENCES: Any compounds having similar retention times as the analytes of interest.
OTHER METHODS: This method is an improved update of NMAM 1403, issue 2 (15 August 1994) [1 ]. NMAM 1403 (15 August 1994) previously combined and replaced methods S76 [2], S79 [2], and S361 [3]. Other less sensitive methods include OSHA 79 [4] and OSHA 83 [5].
NIOSH Manual of Analytical Methods, Fourth Edition ALC OH OLS IV: MET HO D 140 3, Issue 3, dated 15 M arch 200 3 - Page 2 o f 5 REAGENTS:
EQUIPMENT:
1. Meth ylene C hloride, H PL C chrom ato graphic grad e.* 2. Me than ol, HP LC chro m atog raph ic grade.* 3. Desorption solvent: methylene chloride (HPLC chromatographic grade) containing 5% m eth anol. 4. 2-methoxyethanol, reagent grade. 5. 2-ethoxyethanol, reagent grade. 6. 2-butoxyethanol, reagent grade. 7. Helium, purified and filtered. 8. Hydrogen, filtered. 9. Air, compressed, purified, filtered.
1. Sam pler: glass tu be, 7 cm long, 6-m m OD , 4-mm ID, flame-sealed ends, containing two sectio ns of a ctivate d coconut s hell charcoal (100 m g/50 m g) separated b y a 2-mm ureth ane fo am plug. A silylated glass wool plug precedes the front section and follows the back sectio n. T ubes are com m ercially available from SKC, Inc. 2. Personal sa m pling pum p, 0.01 to 0.05 L/m in, connected with flexible tubing. 3. Gas chromatograph, FID, integrator, and capillary colum n (page 14 03-1). 4. Autosampler vials, 11-mm glass with crimp caps. 5. Syringes, 10-µL, 25-µL, and 1-mL. 6. Volumetric flasks, 10-mL.
- See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Methylene chloride is a carcinogen [6]. Methanol is very flamm able.
SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Break the ends of the sampler imm ediately before sampling. Attach sampler to personal sam pling pum p with flexible tubing. 3. Sa m ple at an accurately known flow rate between 0.01 and 0.05 L/m in for a total sam ple size of 6 to 50 L (2-m etho xyethano l); 1 to 6 L (2-ethox yethan ol); and 2 to 10 L (2-b utox yethan ol). NOTE: Maximum flow rate for 2-methoxyethanol and 2-butoxyethanol is 0.2 L/min. 4. Ca p the sam plers with plastic (not rub ber) cap s and pa ck sec urely for shipm ent.
SAMPLE PREPARATION: 5. Place the front and back sorbent sections of the sampler tube in separate vials. Place the glass wool preceding the front section into the vial containing the front sorbent section. Discard the remaining foam plugs. 6. Ad d 1.0 m L of the desorptio n solvent into each vial. Attac h crim p caps to each vial. 7. Plac e the sam ple vials in an u ltrasonic ba th for 3 0 m inutes .
CALIBRATION AND QUALITY CONTRO L: 8. Calibrate daily with at least six working standards to cover the analytical range. If necessary, additional stan dard s m ay be a dde d to exten d the calibra tion cu rve. a. Add know n am oun ts of a nalytes to 10-m L volum etric flas ks and dilute to the m ark with so lvent. b. Analyze together with samp les and blanks (steps 11 and 12). c. Prepare c alibration graph (pe ak area vs µg ana lyte). 9. Determine desorption efficiency (DE) at least once for each lo t of charcoal used for sampling in the calibration ranges (step 8). a. Prepare three tubes at each of five levels plus three media blanks. b. Inject a known amount of DE stock solution directly onto the front sorbent section of each charcoal tube with a microliter syringe.
NIOSH Manual of Analytical Methods, Fourth Edition ALC OH OLS IV: MET HO D 140 3, Issue 3, dated 15 M arch 200 3 - Page 3 o f 5 c.
Allow the tubes to air equilibrate for several m inutes , then cap the ends of ea ch tube a nd a llow to stan d overnight. d. Deso rb (steps 5-7) and a nalyze 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 grap h are in con trol.
MEASUREMENT: 11. Set the gas chromatograph according to manufacturer’s recomm endations and to conditions given on page 1403-1. Inject a 1-µL sample aliquot manually using the solvent flush technique or with an autosam pler. NOTE: If peak area is above the linear range of the working standards, dilute with desorption so lvent, rean alyze and ap ply the ap prop riate dilution facto r in the c alculations. 12. Me asu re pe ak area s.
CALCULATIONS: 13. Determine the m ass, µg (co rrected for D E) of a na lyte found in the sam ple front (W f) and back (W b) sorbent sec tions, and in the average m edia blank front (B f) and back (B b) sorben t sec tions. NO TE: If W b > W f/10, report breakthrough and possible sample loss. 14. Calculate conce ntration, C, of analyte in the air volume sam pled, V(L):
NO TE : m g/L = m g/m 3
EVALUATION OF METHOD: Initial Method Development Effort (Issues 1 and 2) Methods S79 (2-methoxyethanol), S361 (2-ethoxyethanol), and S76 (2-butoxyethanol) were issued on Februa ry 14, 1975 [2, 7], March 17, 1978 [3, 8, 9], an d Fe brua ry 14, 19 75 [2, 7], respectively, and validated using, respectively, 50-, 6-, and 10-L air samples of atmospheres generated by calibrated syringe drive. Storage stability of the se a lcohols was n ot determ ined. Current Method Development Effort (Issue 3) [10] Issue 3 is an update and improvement of NMAM 1403. Improvem ents in the method include the use of capillary column chromatography, lower LOD/LOQ values, a new 5 level desorption efficiency (DE) study at lower levels, and a storage stability study at 7, 14, and 30 days. The average D E determ ined for 2-m ethoxyethanol was 97 .8% (R SD = 1.0), for 2-ethoxythanol the DE was 100.2% (RSD = 1.2), and for 2-butoxyethanol the DE was 99.9% (RSD = 1.3). The average 30-day storage stability recovery at approxim ately 0.5x RE L for 2-m ethoxyethanol was 10 3.8% (R SD = 1.4), for 2-eth oxyethan ol was 105.0% (RS D = 1.6), and fo r 2-butox yethan ol was 82 .6% (RS D = 1.4). The precision and accuracy information listed in Table 2 was calculated by using the data from generated air sam ples [7, 8] an d the ana lytical data from the current update [10].
NIOSH Manual of Analytical Methods, Fourth Edition ALC OH OLS IV: MET HO D 140 3, Issue 3, dated 15 M arch 200 3 - Page 4 o f 5 REFERENCES: [1]
[2]
[3]
[4] [5] [6] [7] [8] [9]
[10] [11]
NIOSH [1994]. Alcohols IV: Method 140 3, revise d b y George Williamson. In: Eller PM, ed. NIOSH Manual of Analytical Methods, 4 th rev. ed. Cincinnati, OH: U.S. Department of Health Hum an Services, Pu blic Health Service, Cen ters for Disease C ontrol, National Institute for Occupational Safety and He alth, DHH S (N IOS H) P ublica tion N o. 94-113 . NIOSH [1977]. 2-Butoxyethanol: Method S76, and 2-Methoxyethanol: Method S79. In: Taylor DG, ed. NIOSH Ma nua l of Analytical Metho ds, 2 nd ed., Cincinnati, OH: U.S. Department of Health, Education, and W elfare, P ublic Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health, DHHS (NIOSH) Publication No. 77-157-B. NIOSH [1979]. 2-E thox yethan ol: Metho d S3 61. In : Ta ylor DG , ed. N IOSH Manual of Analytical Methods, 2 nd ed. Cincinnati, OH: U.S. Department of Health, Education, and W elfare, Public He alth Service, Centers for Disease Control, National Institute for Occupational Safety and Health, DHHS (NIOSH) Publication No. 79-141. OSHA [1990]. Meth od 79. Sa lt Lake City, UT: Oc cup ationa l Safe ty and H ealth Adm inistration : Organic Meth ods E valuation Branch, OSH A A nalytica l Laboratory. OSHA [1990]. Occupational Safety and Health Administration: Method 83. Salt Lake City, UT : Organic Meth ods E valuation Branch, OSH A A nalytica l Laboratory. NIOSH Recomm endations for Occupational Safety and Health, U.S. Department of Health and Human Services, (N IOS H) P ubl. 92 -100 (Jan uary 1992 ). Docum entation of the NIOSH Validation Tests, S76 and S79, U.S. Department of Health, Education, and W elfare, Publ. (NIOSH ) 77-185 (197 7). Backup Data, S361, available as “Ten NIOSH Analytical Methods, Set 6,” Order No. PB288-629 from NTIS, Springfield, VA 22161. NIOSH Rese arch Re port, Developm ent and Va lidation of Methods for Sampling and An alys is of W orkplace Toxic Substances, U.S. Department of Health and Human Services, Publ. (NIOSH) 80-133 (198 0). Pendergrass SM [1998]. Backup D ata R epo rt for Alcohols IV Me thod Develop m ent E ffort, NIOSH /AR DB/A CS, J anuary. NIOSH [1990]. User Check, DataChem Laboratories, NIOSH Sequence #6960-J,K (unpublished, Augus t 15).
METHOD WRITTEN BY: Issue 3 Stephanie M. Pendergrass, NIOSH/DART
Issue 1 & 2 George W illiamson, NIOSH/ DPSE; methods originally validated under Contracts 99-74-75 and 210-76-0123.
NIOSH Manual of Analytical Methods, Fourth Edition ALC OH OLS IV: MET HO D 140 3, Issue 3, dated 15 M arch 200 3 - Page 5 o f 5
TABLE 1.
Exposure Limits and Physical Properties
Compound
OSHA (p pm )
NIOSH (ppm )
ACG IH (ppm )
mg/m 3 = 1ppm @ NTP
MW
BP (°C)
Den sity @ 20°C (g/mL)
VP @ 20°C , KPa (mm Hg)
2-m eth oxyeth anol
25 (skin)
0.1 (skin)
5 (skin)
3.16
76.09
124
0.966
0.8 (6)
2-ethoxyethanol
200 (skin)
0.5 (skin)
5 (skin)
3.75
90.12
135
0.931
0.5 (4)
2-butox yeth anol
50 (skin)
5 (skin)
25 (skin)
4.91
118.17
171
0.902
0.11 (0.8)
TABLE 2. Method Evaluation Analytical Methodb
Overall Methoda Compound
Range
Accuracy
Breakthrough
Bias
@ 3
(m g/m )
2-methoxyethanol 2-ethoxyethanol 2-butoxyethanol
a) b) c) d) e)
Precision Sr T
2 x OSHA PEL
Range studied
LOD
( : g/sample)
( : g/sample)
Ave. DE
Storage Stability Measurement Precision Sr
Levels
Recovery
( : g/sample)
(% )
44-160
0.41
128 Lc
NSe
0.072
2-387
0.8
97.8
0.024
120.5
103.7
340-1460
0.11
> 10 Ld
NS
0.056
2-373
0.7
100.2
0.022
118.0
101.7
0.14
c
NS
0.071
3-361
1.3
99.9
0.024
90.0
82
124-490
> 44 L
Generated air sample data in References 7 and 8. Data for analytical method in Reference 10. Tes ting done in dry air. Te stin g done in 90% rela tive hum idity. NS = not significant
NIOSH Manual of Analytical Methods, Fourth Edition