CR (Gus) Manning, Brynna J. Quarles, and Michael Jordan
CH3CO-OOH
A More Effective Sterilizing Agent
than Hydrogen Peroxide (HP),
and also more toxic
Strong irritant for eyes, mucous membranes,
and respiratory system
Safety Comparison of
Vapor-Phase Oxidants
PAA
ACGIH TLV = 0.4 ppm
IDLH = 0.6 ppm
HP
OSHA PEL = 1.0 ppm
IDLH = 75 ppm
When Peracetic Acid decomposes, it liberates
Hydrogen Peroxide
CH3CO-OOH + HOH
CH3CO-OH + HO-OH
PAA Acetic Acid + Hydrogen Peroxide
It had been claimed that PAA dissipates quickly
leaving HP, and, ultimately Acetic Acid & Water
CH3CO-OOH + HOH
CH3CO-OH + HO-OH
PAA Acetic Acid + Hydrogen Peroxide
2 HO-OH
2 H2O + ½ O2
The quick decomposition seems an overstatement
as significant PAA residuals are likely to remain.
Actually there is an equilibrium among
PAA, Water, Acetic Acid, HP, and Oxygen
CH3CO-OOH + HOH
2 HO-OH
CH3CO-OH + HO-OH
2 H2O + ½ O2
OSHA Methods ID 006 & ID 126 SG
HP Sampling
Impinger Containing
TiOSO4 Solution
HP Analysis
UV Absorbance of Yellow
Solution (410 nm)
or Pulse Polarography
Using OSHA Methods ID 006 or ID 126 SG, PAA reacts
identically to HP ... 100% interference
There is no OSHA or NIOSH Method for PAA.
• HP and PAA are both strong free-radical oxidizing agents.
• Almost any reagent that reacts with one will react with the other
• PAA & HP are likely too unstable to analyze via Chromatography
Simultaneous Sampling of Peroxyacetic Acid and Hydrogen Peroxide in
Workplace Atmospheres, G. Hecht, M. Hery, G. Hubert, and I. Subra
Ann. Occup. Hyg, Vol., No. 8, 715-721, 2004
Describes use of reagents capable of reacting with PAA
but not with HP … under certain conditions
MTS
Methyl
p‐tolysulfide
MTSO
Methyl
p‐tolysulfoxide
MTSOO
Methyl
p‐tolysulfone
Simultaneous Sampling of Peroxyacetic Acid and Hydrogen Peroxide in
Workplace Atmospheres, G. Hecht, M. Hery, G. Hubert, and I. Subra
Ann. Occup. Hyg, Vol., No. 8, 715-721, 2004
MTS
MTSO
X
PAA HP
Impinger
PAA + HP
Sampling Tube
MTSO
MTSOO
Described in:
G. Hecht, M. Hery, G. Hubert, and I. Subra
Ann. Occup. Hyg, Vol., No. 8, 715-721, 2004
Sample HP and PAA Separately:
HP + PAA
TiOSO4
Coated Filter
PAA
MTSO
Sampling Tube
MTSOO
Cassette & Tube in Series
Dynamic Generation from Solution of Peracetic Acid
PAA
Samplers
Critical
Orifice
Sampler
Syringe
Pump
Exposure
Chamber
Heating
Flask
Simultaneous Sampling for HP and PAA
Impinger Reference Method (MTS Soln)
Sample Description
Target Exposure 20 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 10 ppm x 60 min
" " " "
" " " "
" " " "
Target Exposure 5 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 2 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 1 ppm x 50 min
" " " "
" " " "
" " " "
S.R. Time
(time) (min)
1.03
40
1.03
40
1.03
40
1.03
40
40
1.03
60
1.03
60
1.03
60
1.03
60
60
1.03
40
1.03
40
1.03
40
1.03
40
40
1.03
40
1.03
40
1.03
40
1.03
40
40
1.03
50
1.03
50
1.03
50
1.03
50
Target Exposure 0.5 ppm x 60 min
" " " "
" " " "
" " " "
1.03
1.03
1.03
1.03
Target Exposure 1 ppm x 130 min
" " " "
" " " "
" " " "
1.03
1.03
1.03
1.03
Target Exposure 0.5 ppm x 133 min
" " " "
" " " "
" " " "
1.03
1.03
1.03
1.03
50
60
60
60
60
60
130
130
130
130
130
133
133
133
133
133
MTSOO on Tube 226‐193
Vol Amt Found Concn
Concn
(µg)
(L)
(mg/M3) (ppm)
41.2
490
11.9
3.82
41.2
400
9.7
3.12
41.2
410
10.0
3.20
41.2
410
10.0
3.20
61.8
61.8
61.8
61.8
480
370
330
440
7.77
5.99
5.34
7.12
41.2
41.2
41.2
41.2
390
440
440
400
9.5
10.7
10.7
9.7
41.2
41.2
41.2
41.2
240
270
280
250
5.83
6.55
6.80
6.07
51.5
51.5
51.5
51.5
220
220
210
230
4.27
4.27
4.08
4.47
61.8
61.8
61.8
61.8
120
120
130
120
1.94
1.94
2.10
1.94
133.9
133.9
133.9
133.9
320
340
350
320
2.39
2.54
2.61
2.39
137.0
137.0
137.0
137.0
200
240
210
250
1.46
1.75
1.53
1.82
Expsre
(ppm‐hr)
2.55
2.08
2.13
2.13
3.34
2.22
2.50
1.92
1.72
2.29
2.50
1.92
1.72
2.29
2.11
2.11
3.04
3.43
3.43
3.12
2.03
2.29
2.29
2.08
3.26
2.17
1.87
2.11
2.18
1.95
1.25
1.40
1.46
1.30
2.03
1.35
1.37
1.37
1.31
1.44
1.14
1.14
1.09
1.20
1.37
1.14
0.62
0.62
0.68
0.62
0.62
0.62
0.68
0.62
0.64
0.64
0.77
0.82
0.84
0.77
1.66
1.77
1.82
1.66
0.80
1.73
0.47
0.56
0.49
0.59
1.04
1.25
1.09
1.30
0.53
1.17
S.R.
(time)
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
1.03
Time
(min)
30
30
30
30
30
60
60
60
60
60
40
40
40
40
40
40
40
40
40
40
50
50
50
50
50
55
55
55
55
55
130
130
130
130
130
133
133
133
133
133
Vol
(L)
30.9
30.9
30.9
30.9
MTSO in Impinger
Amt Found Concn
(µg)
(mg/M3)
2100
68.0
1900
61.5
1900
61.5
1700
55.0
61.8
61.8
61.8
61.8
2200
2200
2200
2100
35.60
35.60
35.60
33.98
41.2
41.2
41.2
41.2
720
780
680
720
17.5
18.9
16.5
17.5
41.2
41.2
41.2
41.2
370
370
340
360
8.98
8.98
8.25
8.74
51.5
51.5
51.5
51.5
310
280
300
290
6.02
5.44
5.83
5.63
56.7
56.7
56.7
56.7
250
250
240
250
4.41
4.41
4.24
4.41
133.9
133.9
133.9
133.9
500
540
510
480
3.73
4.03
3.81
3.58
137.0
137.0
137.0
137.0
360
330
330
300
2.63
2.41
2.41
2.19
Concn
(ppm)
21.8
19.8
19.8
17.7
Expsre
(ppm‐hr)
10.9
9.9
9.9
8.8
20.5
10.2
11.4
11.4
11.4
10.9
11.4
11.4
11.4
10.9
11.3
11.3
5.62
6.09
5.31
5.62
3.75
4.06
3.54
3.75
5.66
3.77
2.89
2.89
2.65
2.81
1.92
1.92
1.77
1.87
2.81
1.87
1.94
1.75
1.87
1.81
1.61
1.46
1.56
1.51
1.84
1.53
1.42
1.42
1.36
1.42
1.30
1.30
1.25
1.30
1.40
1.29
1.20
1.30
1.22
1.15
2.60
2.81
2.65
2.50
1.22
2.64
0.84
0.77
0.77
0.70
1.87
1.72
1.72
1.56
0.77
1.7
Sample Description
Target Exposure 20 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 10 ppm x 60 min
" " " "
" " " "
" " " "
Target Exposure 5 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 2 ppm x 40 min
" " " "
" " " "
" " " "
Target Exposure 1 ppm x 50 min
" " " "
" " " "
" " " "
Target Exposure 0.5 ppm x 60 min
" " " "
" " " "
" " " "
Target Exposure 1 ppm x 130 min
" " " "
" " " "
" " " "
Target Exposure 0.5 ppm x 133 min
" " " "
" " " "
" " " "
Time
Vol
(time) (min)
1.030
40
1.030
40
1.030
40
1.030
40
40
1.030
60
1.030
60
1.030
60
1.030
60
60
1.030
40
1.030
40
1.030
40
1.030
40
40
1.030
40
1.030
40
1.030
40
1.030
40
40
1.030
50
1.030
50
1.030
50
1.030
50
50
1.030
60
1.030
60
1.030
60
1.030
60
60
1.030
130
1.030
130
1.030
130
1.030
130
130
1.030
133
1.030
133
1.030
133
1.030
133
133
S.R.
(L)
41.2
41.2
41.2
41.2
Abs 410nm Amt Found
(H2O2)
(µg)
Concn
Concn
Expsre
200
225
203
208.8
(mg/M3)
4.9
5.5
4.9
5.1
(ppm‐hr)
2.32
2.61
2.35
2.42
1.720
1.630
1.670
1.640
370.7
351.3
359.9
353.4
6.00
5.68
5.82
5.72
41.2
41.2
41.2
41.2
0.438
0.409
0.436
0.422
94
88
94
90.9
2.3
2.1
2.3
2.2
41.2
41.2
41.2
41.2
0.158
0.148
0.155
0.152
34.0
31.9
33.4
32.8
0.83
0.77
0.81
0.80
51.5
51.5
51.5
51.5
0.115
0.129
0.131
0.112
24.8
27.8
28.2
24.1
0.48
0.54
0.55
0.47
61.8
61.8
61.8
61.8
0.125
0.114
0.128
0.118
26.9
24.6
27.6
25.4
0.44
0.40
0.45
0.41
133.9
133.9
133.9
133.9
0.268
0.268
0.265
0.243
57.8
57.8
57.1
52.4
0.43
0.43
0.43
0.39
137.0
137.0
137.0
137.0
0.127
0.163
0.167
0.186
27.4
35.1
36.0
40.1
0.20
0.26
0.26
0.29
(ppm)
3.48
3.91
3.53
3.63
3.64
4.30
4.08
4.18
4.10
4.16
1.64
1.53
1.64
1.58
1.60
0.59
0.56
0.58
0.57
0.57
0.35
0.39
0.39
0.34
0.37
0.31
0.29
0.32
0.30
0.30
0.31
0.31
0.31
0.28
0.30
0.14
0.18
0.19
0.21
0.18
0.929
1.043
0.940
0.969
61.8
61.8
61.8
61.8
2.43
4.30
4.08
4.18
4.10
4.16
1.10
1.02
1.09
1.06
1.07
0.40
0.37
0.39
0.38
0.38
0.29
0.32
0.33
0.28
0.30
0.31
0.29
0.32
0.30
0.30
0.67
0.67
0.66
0.61
0.65
0.32
0.41
0.42
0.47
0.40
PAA Found Using Different Methods of Hecht et al.
PAA Found Using Different Methods of Hecht et al.
The PAA Tube was supposed to agree with the
Impinger Reference, but was significantly lower.
Instead, the sum of the [PAA Tube] + [HP Cassette]
agreed with the Impinger Reference Method.
Based on liquid spikes, the Impinger Method
responded proportionally to PAA, but had negligible
response to HP. (I.e., the reference method worked)
This suggests the Impinger Reference Method was
accurate, while substantial amounts of PAA are being
collected by the HP Cassette and erroneaouly reported
as Hydrogen Peroxide.
Sample HP and PAA Separately:
TiOSO4
HP + PAA
Coated Filter
MTSO
PAA
Sampling Tube
MTSOO
According to G. Hecht et al., sampling must be conducted at
>1.0 L/min in order to avoid reaction between HP & TiOSO4
It is nearly impossible to achieve > 1.0 L/min though the
Cassette + Tube using normal sampling pumps.
We think the Cassette needs to be sampled at >> 1.0 L/min.
HP + PAA
TiOSO4
Coated Filter
Selective HP Analysis
Investigate results at sampling rates 1.0 – 3.0 L/min
HP + PAA
MTSO
MTSOO
Sampling Tube
Analysis of [PAA + HP]
Determine PAA as = [ PAA + HP ] – [ HP ]