A Sensitive and Selective Method for the
Analysis of Hydrazines in Water and Soil
Table 1. Concentration Range of
Calibration Curve (ng/mL)
Introduction
• Hydrazines (hydrazine, monomethylhydrazine and 1,1dimethylhydrazine) are most commonly known for their use as
rocket propellants
• The use of LC/MS/MS for hydrazines analysis is not reported
• Recovery of hydrazines in soil samples is challenging , especially
from some site specific matrices
Objective
• Develop LC/MS/MS method for hydrazines analysis
Hydrazine Monomethylhydrazine &
1,1-Dimethylhydrazine
0.1
0.5
0.25
1.25
0.5
2.5
1
5
2.5
12.5
5
25
10
50
25
125
Cal. 1
Cal. 2
Cal. 3
Cal. 4
Cal. 5
Cal. 6
Cal. 7
Cal. 8
Table 2. Recovery of Hydrazines from Spiked Tap Water1,2
Milli Q water + spike
Tap water + spike-1
Tap water + spike-2
Tap water + spike-3
• Hydrazine, monomethylhydrazine and 1,1-dimethylhydrazine in
aqueous samples or soil extracts are derivatized with carbonyl
compound to form the corresponding hydrazones.
• The resulting solution is analyzed by LC/MS/MS operated in
positive atmospheric pressure chemical ionization (APCI) mode.
• Separation and detection is performed using a Thermo Scientific
Accela Autosampler and quaternary U-HPLC pump equipped with
TSQ Quantum Access Triple Quadrupole mass spectrometer
Monomethylhydrazine
Y = -33648.7+154661*X+235.192*X^2 R^2 = 0.9985 W: 1/X
25000000
Area Ratio
Method
20000000
15000000
10000000
5000000
• Small quantity of sample (1 mL aqueous sample or 1 gram soil
sample) is required
0
0
50
100
ng/mL
Results
1,1-Dimethylhydrazine
Y = -21207.7+104018*X+104.895*X^2 R^2 = 0.9996 W: 1/X
Figure 1. Example Chromatogram (TIC and SRM) of
Calibration Standard (Level 5)
NL: 3.09E5
TIC MS
13Oct-094827-26-15
5.25
100
6.94
80
60
Spiking experiment was conducted in tap water containing no
measurable analytes
2
Hydrazine was spiked at 12.5 ng/mL. Monomethylhydrazine and
1,1-dimethylhydrazine was spiked at 62.5 ng/mL.
10000000
9.16
20
2.96 4.14 4.66
5.76
5.25
0.60 1.37
0
100
7.23 8.69
9.32
11.73 12.53
14.08 15.38 16.29 17.72
0
NL: 3.09E5
TIC F: + c APCI SRM
ms2
135.207@cid20.00
[77.399-77.401] MS
13Oct-094827-26-15
80
0
50
40
4.66
0
100
5.76
NL: 2.41E5
TIC F: + c APCI SRM
ms2
149.210@cid14.00
[106.269-106.271] MS
13Oct-094827-26-15
6.94
80
3500000
20
6.46
0
100
7.23
NL: 6.74E4
TIC F: + c APCI SRM
ms2
209.128@cid17.00
[106.299-106.301] MS
13Oct-094827-26-15
9.16
80
Hydrazine
60
Area Ratio
40
2500000
8.69
0
0
2
4
6
8
9.32 9.81 11.73 12.53
10
Time (min)
12
14.08 15.38 16.29 17.72
14
16
4
Hydrazine was spiked as 125 ng/g. Monomethylhydrazine and 1,1dimethylhydrazine was spiked as 625 ng/g.
Conclusions
• The sensitivity of the tandem mass spectrometer allows for
reductions in sample preparation volumes – a “green”
analytical technique
2000000
1500000
1000000
500000
40
20
Spiking experiment was conducted in soil samples containing no
measurable analytes
• The use of tandem mass spectrometer provides greater
confidence for quantification of hydrazines
3000000
1,1-Dimethylhydrazine
60
3
100
Hydrazine
Y = 11206.4+131165*X-68.334*X^2 R^2 = 0.9998 W: Equal
20
Ottawa Sand + Spike
Soil A + Spike-1
Soil A + Spike-2
Soil B + Spike-1
Soil B + Spike-2
Soil C + Spike-1
Soil C + Spike-2
Soil D + Spike-1
Soil D + Spike-2
Soil E + Spike-1
Soil E + Spike-2
Soil F+ Spike-1
Soil F+ Spike-2
Soil G+ Spike-1
Soil G+ Spike-2
Monomethyl 1.1-Dimethyl Hydrazine
Hydrazine
Hydrazine
116
116
104
21
55
35
19
52
35
24
51
48
25
54
52
23
57
44
21
43
44
66
88
70
87
104
90
26
51
57
29
63
58
40
77
58
40
75
57
30
46
71
29
43
71
ng/mL
Monomethylhydrazine
60
Table 3. Recovery of Hydrazines from Spiked Soil Sample3,4
5000000
TIC
40
Relative Abundance
Area Ratio
RT: 0.00 - 17.99
15000000
Monomethyl 1.1-Dimethyl Hydrazine
Hydrazine
Hydrazine
59
80
94
61
80
80
57
73
79
59
76
80
1
• Develop extraction procedure to recover hydrazines from soil
samples
Figure 2. Calibration Curve of Hydrazine,
Monomethylhydrazine and
1,1-Dimethylhydrazine
Jia Wang and Chuck Neslund
Lancaster Laboratories
2425 New Holland Pike
Lancaster PA 17601
0
5
10
15
ng/mL
20
25
• Soil extraction procedure overcomes previous recovery
difficulties on site specific matrices