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Bromine Backup Data Report, ID-108

Related Information: Chemical Sampling - Bromine
This Backup Report was revised April, 1990


Introduction

The general procedure for collection and analysis of bromine (Br2) air samples is described in OSHA method no. ID-108 (10.1). Briefly, Br2 is collected in a midget fritted glass bubbler (MFGB) containing a buffer (0.0030 M NaHCO3 / 0.0024 M Na2CO3) collection solution. In this basic solution, Br2 disproportionates to produce bromide (Br) and bromate (BrO3-) (10.2) which can be determined by ion chromatography (IC). This method has been evaluated using 30-L, 60-min samples. The concentrations tested were near the OSHA Time Weighted Average (TWA) Permissible Exposure Limit (PEL) of 0.1 ppm.

1. Experimental Protocol

The evaluation consisted of the following experiments or discussions:
  1. Analysis of a total of 18 spiked samples.
  2. Analysis of a set of 18 samples which were taken from dynamically generated test atmospheres.
  3. Determination of the collection efficiency and the breakthrough when using MFGB.
  4. Storage stability tests for six samples collected at the PEL.
  5. Determination of the detection limit of the method.
  6. Comparison of methods.
  7. Assessment of the precision and accuracy of the method.
  8. Conclusions - including a discussion of changes in the PEL since this evaluation was performed.

2. Analysis

Samples (six samples at each of three test levels) were prepared by spiking appropriate amounts of standardized Br2 into collection solutions. The spiked samples were prepared and analyzed to determine analytical precision and accuracy.
Procedure:   Samples were prepared by adding known amounts of a standardized stock Br2 solution to 10 mL of collection solution. The spikes consisted of 17.8, 35.5, and 71.1 µg of Br2, which corresponded to about 0.5, 1, and 2 times the PEL if sampling at 0.5 L/min for 60 min.
2.1. Standardization of Br2 stock solution:

A Br2 stock solution was prepared from a Br2 permeation tube by bubbling the Br2 vapor through a collection solution for a given period of time. This stock solution was then analyzed by IC. The concentration of the stock solution was 35.57 µg/mL as Br2 (29.64 µg/mL as Br).

2.2. Three sets of spiked samples were prepared by adding 0.5, 1.0, and 2.0 mL, respectively, of the Br2 stock solution into 10-mL volumetric flasks and diluted to volume with collection solution. Each set consisted of 6 samples.

2.3. The analytical procedure described in OSHA method no. ID-108 (10.1) was followed.
Results:   The results of the analytical experiment are presented in Table 1. The overall analytical recovery was 98.3% which does not indicate a need for an analytical correction factor.
3. Sampling and Analysis
Procedure:   A standard generator [Model 350, Analytical Instrument Development Inc. (AID), Avondale, PA] containing Br2 permeation tubes (from AID) was used as the source for generating dynamic test atmospheres of Br2. A sampling manifold, constructed from glass and Teflon, was attached to the generator. Samples (6 samples at each of the three test levels) were collected from the manifold using concentrations of 0.5, 1, and 2 times the OSHA TWA PEL (0.1 ppm).
3.1. The permeation rate of the Br2 permeation tubes was determined by measuring their respective weight loss at a constant temperature of 30 °C ± 0.1 °C over a given period of time. The permeation rates are shown in Table 2. Two different sizes of permeation tubes were used.

3.2. The flow rates of the diluent air and saturated gas stream of bromine from the generator were measured with a soap bubble flow meter to determine the concentration of the generated gas.

3.3. Three sets of six samples were collected individually at about 0.05, 0.1, and 0.2 ppm Br2. Samples were collected using personal sampling pumps at a sample flow rate of about 0.5 L/min for 60 min.
Results:   The results of sampling and analysis are shown in Table 3. Known (Taken) concentrations listed were calculated from the permeation tube weight loss and flows of Br2 gas and diluent air.
4. Collection Efficiency (CE) and Breakthrough
Procedure - CE:   Two MFGBs containing 10 mL of collection solution were connected in series. Six of these series samples were collected at a concentration of 0.2 ppm for 60 min at 0.5 L/min. The amount of Br2 vapor collected in each MFGB was then measured.

Results:   The CE of the first MFGB was calculated by dividing the amount of Br2 collected in the first MFGB by the total amount of Br2 collected in the first and second MFGB. The results are reported in Table 4. The CE was 100%.

Procedure - Breakthrough:   Two MFGBs in series, as mentioned above, were prepared. Three of these series samples were taken at 0.2 ppm. A flow rate of 0.5 L/min and sampling times of 60, 120, and 240 min were used.

Results:   Breakthrough was calculated by dividing the amount of Br2 collected in the second MFGB by the total amount of Br2 collected in the first and second MFGBs. The results are given in Table 5. The breakthrough was 2.4% after 240 min.
5. Storage Stability

A study was conducted to assess the storage stability of collected Br2 in the collection solution.
Procedure:   Six samples were generated as described in Section 3. The samples were transferred into 10-mL volumetric flasks. These flasks were then tightly closed and stored on top of a lab bench at normal laboratory temperatures. The samples were analyzed after 1, 5, 15, and 30 day storage periods.

Results:   The results of the storage stability study are shown in Table 6. These results indicate that samples may be stored under normal laboratory conditions for a period of at least 30 days.
6. Detection Limit
Procedure:   Samples containing small amounts of Br were prepared in the collection solution and then analyzed by IC. The Rank Sum Test was used for the determination of the qualitative detection limit. The test is a non-parametric or a distribution-free test. The quantitative limit was determined by examining the variation (CVs) in results of these samples.

Results:   The results of the Rank Sum Test are shown in Table 7. As shown, the qualitative detection limit as Br2 is 0.02 µg/mL (99% confidence level). The quantitative limit is 0.09 µg/mL as Br2, or 0.9 µg in a 10 mL sample volume. This corresponds to 0.005 ppm Br2 for a 30-L air volume. The CV at this level was about 0.11.
7. Analytical Method Comparison

The previous ion specific electrode (ISE) procedure (10.3) used by OSHA was chosen as the reference analytical method to which the results of the IC method were compared.
7.1. Analytical procedure for ISE (10.3)
7.1.1. A low level ionic strength adjuster (ISA) was prepared by diluting 20 mL ISA (5 M sodium nitrate) to 100 mL with deionized water.

7.1.2. Three sets of spiked samples were prepared by adding 5, 10, and 20 mL, respectively, of Br2 stock solution, 1 mL of ISA, and 50 µL of concentrated nitric acid into 100-mL volumetric flasks and then diluting to volume with collection solution. These samples corresponded to 1.78, 3.56, and 7.11 µg/mL Br and were compared to those samples prepared in Section 2.2.

7.1.3. Two different concentrations of Br standards were prepared from potassium bromide to check the slope (-58.0 mV) of the ISE.

7.1.4. Samples were analyzed using an Orion model 94-35A specific ion electrode and an Orion Model 901 millivolt meter.
7.2. Results:   The comparison data of the ISE reference and IC methods are shown in Table 8.

7.3. Discussion:   In basic solution, Br2 disproportionates to produce Br and BrO3 according to the following equation (10.2):

3Br2  +  6OH  ---->  5Br  +  BrO3  +  3H2O     (basic solution)

The mole ratio of Br2 per Br is 1.2. As the pH is lowered, Br and BrO3 may react with each other to gradually convert back to Br2 according to the following equation (10.4):

BrO3  +  5Br  +  6H+  ---->  3Br2  +  3H2O     (acidic solution)

Results of Br2 concentration obtained from the ISE were much lower than that from the IC, which was likely due to the change in pH after nitric acid is added. Therefore, results obtained from IC analysis are more accurate and reliable than ISE results.
8. Precision and Accuracy

The data, based on the NIOSH statistical protocol (10.5), are presented in Tables 1 and 3. The pooled coefficients of variation for spiked (CV1 [pooled]) and generated (CV2 [pooled]) samples and the overall CVT (pooled) are:

CV1 (pooled)  =  0.040, CV2 (pooled)  =  0.065, CVT (pooled)  =  0.067

The bias was -0.056 and overall error was ±19%. Overall error was calculated as:

OEi  =  ± [|mean biasi|  +  2CVi] × 100%

where  i  is the respective sample pool being examined.

9. Conclusions

The analytical, sampling and analytical, collection efficiency, breakthrough, storage stability, and detection limit experiments displayed acceptable data. A negative bias was noted for the sampling and analysis experiment conducted at two times the TWA PEL; however, the collection efficiency experiment at this concentration indicated no Br2 was passing into the next bubbler.

The MFGB sampling and IC analytical method for Br2 has shown to be an acceptable alternative to determining compliance with the OSHA PEL of 0.1 ppm (TWA). The ability of the method to determine compliance to the STEL of 0.3 ppm Br2 is dependent on the detection limit and potential breakthrough at this concentration. A detection limit of 0.9 µg or 0.018 ppm Br2 (15-min sample, 7.5-L total air volume) is more than adequate for STEL measurements. Breakthrough was not evident at 60 to 120 min and was only 2.4% at a 240-min sampling time (0.2 ppm concentration). Breakthrough is not expected to occur at 0.3 ppm for a 15-min sampling time. Therefore, it is recommended to sample for TWA or STEL samples at 0.5 L/min as demonstrated in this method.

10. References
10.1. Occupational Safety and Health Administration Technical Center: Bromine in Workplace Atmospheres by J. Ku (USDOL/OSHA-SLTC Method No. ID-108). Salt Lake City, UT. Revised 1990.

10.2. Cotton, F.A. and G. Wilkinson: Advanced Inorganic Chemistry -- A Comprehensive Text. 2nd rev. ed. New York: Interscience Publishers, 1966. pp. 569-570.

10.3. Orion Research Incorporated: Instruction Manual, Halide Electrodes, Model 94-35. Cambridge, MA: Orion Research Incorporated, 1982.

10.4. Blaedel, W.J. and V.W. Meloche: Elemental Quantitative Analysis -- Theory and Practice. 2nd ed. New York: Harper and Row, Publishers, 1963. p. 854.

10.5. National Institute for Occupational Safety and Health: Documentation of the NIOSH Validation Tests by D. Taylor, R. Kupel and J. Bryant (DHEW/NIOSH Pub. No. 77-185). Cincinnati, OH: National Institute for Occupational Safety and Health, 1977.



Table 1
Analysis - Bromine

-------- 0.5 × PEL* --------
--------- 1 × PEL* ---------
--------- 2 × PEL* ---------
µg**
Taken
µg
Found

AMR
µg**
Taken
µg
Found

AMR
µg**
Taken
µg
Found

AMR

17.8 18.9 1.062 35.5 34.2 0.963 71.1 73.4 1.032
17.8 19.3 1.084 35.5 33.6 0.946 71.1 72.5 1.020
17.8 17.2 0.966 35.5 33.0 0.930 71.1 72.5 1.020
17.8 17.0 0.955 35.5 33.8 0.952 71.1 69.8 0.982
17.8 16.6 0.933 35.5 34.5 0.972 71.1 69.8 0.982
17.8 17.0 0.955 35.5 33.8 0.952 71.1 69.6 0.979

N 6        6        6       
Mean 0.993 0.953 1.003
Std Dev 0.064 0.014 0.024
CV1 0.064 0.015 0.024


CV1 (pooled)  =  0.040 *   TWA PEL of 0.1 ppm ** µg Found and Taken are reported as Br2 AMR  =  Analytical Method Recovery  =  µg Found/µg Taken




Table 2
Permeation Rates for Bromine Tubes at 30 °C


Tube Size
Time Elapsed
(min)
Weight Loss
(µg)
Permeation Rate
(µg/min)

Large 20,080 36,080 1.797
Large 13,260 24,150 1.821
Large 44,643 79,940 1.793
Small 44,644 38,980 0.873

The average large-size tube permeation rate for Br2 was 1.803 µg/min.

The small-size tube permeation rate for Br2 was 0.873 µg/min.



Table 3
Sampling and Analysis - Bromine

Test Level ---------------------- Found -------------------- Taken
µg L Air mg/m3 ppm ppm Recovery (%)

0.5 × PEL   6.2 20.6 0.301 0.046 0.052 88.5
11.9 41.8 0.285 0.044 0.052 84.6
15.5 42.4 0.366 0.056 0.052 107.7  
13.1 36.4 0.360 0.055 0.052 105.8  
12.5 37.7 0.332 0.051 0.052 98.1
11.5 35.8 0.321 0.049 0.052 94.2

N 6       
Mean 0.050 96.5
Std Dev 0.005
CV2 0.100

1 × PEL 18.5 27.9 0.663 0.101 0.107 94.4
18.9 27.2 0.695 0.106 0.107 99.1
21.7 30.4 0.714 0.109 0.107 101.9  
22.2 28.6 0.776 0.119 0.107 111.2  
20.8 28.6 0.727 0.111 0.107 103.7  
20.8 29.5 0.705 0.108 0.107 100.9  

N 6       
Mean 0.109 101.6
Std Dev 0.006
CV2 0.055

2 × PEL 51.1 45.8 1.116 0.171 0.205 83.4
51.1 46.2 1.106 0.169 0.205 82.4
51.1 45.5 1.173 0.179 0.205 87.3
51.1 46.2 1.106 0.169 0.205 82.4
53.4 46.2 1.156 0.177 0.205 86.3
50.2 43.4 1.157 0.177 0.205 86.3

N 6       
Mean 0.172 84.7
Std Dev 0.004
CV2 0.023


Results are reported as Br2
CV2 (pooled)   =   0.065 CVT (pooled)   =   0.067
Bias   =   -0.056
Overall Error   =   ±19%




Table 4
Collection Efficiency - Bromine


Sample No.
ppm found
lst Bubbler
ppm found
2nd bubbler
Collection
Efficiency (%)

1 0.171 ND 100.0
2 0.169 ND 100.0
3 0.172 ND 100.0
4 0.169 ND 100.0
5 0.177 ND 100.0
6 0.175 ND 100.0
7 0.177 ND 100.0
Average 100.0%


ND  =  0.02 µg/mL or 0.001 ppm (30 L air volume)




Table 5
Breakthrough - Bromine

Sampling
Time, min
µg found
lst bubbler
µg found
2nd bubbler

% Breakthrough

  60 39.4 ND 0
120 76.2 ND 0
240 140     3.3   2.4


ND = 0.02 µg/mL




Table 6
Stability Test - Bromine

---------------------- Found -------------------- Taken
Sample No. µg L Air mg/m3 ppm ppm % Recovery

1 Day
1 18.500 27.900 0.663 0.101 0.107   94.4
2 18.900 27.200 0.695 0.106 0.107   99.1
3 21.700 30.400 0.714 0.109 0.107 101.9
4 22.200 28.600 0.776 0.119 0.107 111.2
5 20.800 28.600 0.727 0.111 0.107 103.7
6 20.800 29.500 0.705 0.108 0.107 100.9

N 6       
Mean 0.109 101.9
Std Dev 0.006
CV 0.055

5 Days
1 18.800 27.900 0.674 0.103 0.107   96.3
2 19.300 27.200 0.710 0.109 0.107 101.9
3 21.600 30.400 0.711 0.109 0.107 101.9
4 22.100 28.600 0.773 0.118 0.107 110.3
5 22.100 28.600 0.773 0.118 0.107 110.3
6 21.600 29.500 0.732 0.112 0.107 104.7

N 6       
Mean 0.112 104.2
Std Dev 0.006
CV 0.054

15 Days
1 18.100 27.900 0.649 0.099 0.107   92.5
2 18.500 27.200 0.680 0.104 0.107   97.2
3 20.500 30.400 0.674 0.103 0.107   96.3
4 22.100 28.600 0.773 0.118 0.107 110.3
5 20.900 28.600 0.731 0.112 0.107 104.7
6 21.300 29.500 0.722 0.110 0.107 102.9

N 6       
Mean 0.108 100.7
Std Dev 0.007
CV 0.065

30 Days
1 15.300 27.900 0.548 0.084 0.107   78.5
2 15,700 27.200 0.577 0.088 0.107   82.2
3 17.400 30.400 0.572 0.088 0.107   82.2
4 19.800 28.600 0.692 0.106 0.107   99.1
5 19.100 28.600 0.668 0.102 0.107   95.3
6 19.900 29.500 0.675 0.103 0.107   96.3

N 6       
Mean 0.095   88.9
Std Dev 0.010
CV 0.105


All results are reported as Br2




Table 7
Bromine Detection Limit - Rank Sum Test (Nstandard  =  Nblank  =  6)

Rank 0.02 µg/mL*

1 0 RB1
2 0 RB1
3 0 RB1
4 0 RB1
5 0 RB1
6 0 RB1
7 33552 Std
8 39064 Std
9 41328 Std
10   49403 Std
11   52619 Std
12   84583 Std

Rb   =   21

Confidence Level   =   99.99%

Detection Limit   =   0.02 µg/mL as Br2

* Measured by peak areas
RB1   =   Reagent Blank
Std     =   Standard, 0.02 µg/mL (as Br2)

Standards having a concentration of 0.01 µg/mL (as Br2) gave no response.




Table 8
Comparison of Analytical Methods for BromineIon Specific Electrode vs. Ion Chromatography

Ion Specific Electrode -Ion Chromatography--
µg taken µg found AMR µg found AMR

0.5 × PEL*
17.8 16.4 0.921 18.9 1.062
17.8 16.6 0.933 19.3 1.084
17.8 16.4 0.921 17.2 0.966
17.8 16.9 0.949 17.0 0.955
17.8 16.8 0.944 16.6 0.933
17.8 17.4 0.978 17.0 0.955

N 6        6       
Mean 0.941 0.993
Std Dev 0.021 0.064
CV 0.023 0.064
1 × PEL*
35.5 32.0 0.901 34.2 0.963
35.5 31.8 0.896 33.6 0.946
35.5 31.9 0.899 33.0 0.930
35.5 29.5 0.831 33.8 0.952
35.5 28.4 0.800 34.5 0.972
35.5 30.0 0.845 33.8 0.952

N 6        6       
Mean 0.862 0.953
Std Dev 0.043 0.014
CV 0.050 0.015
2 × PEL*
71.1 58.3 0.820 73.4 1.032
71.1 57.8 0.813 72.5 1.020
71.1 57.8 0.813 72.5 1.020
71.1 57.7 0.812 69.8 0.982
71.1 57.6 0.810 69.8 0.982
71.1 57.7 0.812 69.6 0.979

N 6        6       
Mean 0.813 1.003
Std Dev 0.003 0.024
CV 0.004 0.024


All results are reported as Br2
AMR   =   Analytical Method Recovery   =   µg taken/µg found
*   TWA PEL of 0.1 ppm