Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

An analytical method for the eld investigation

of environmental amines released by industrial
processes

Chih-Chia Wang a , Lung-Yu Sung b, , Pei-Ling Wu b , Sin-Yu Ke a ,

Shu-Xin Ng a , Rih-Sheng Jian a , Ei-Wen Lo c , Chia-Jung Lu a,
a Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan
b Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan
c Department of Occupational Safety and Health, China Medical University, Taichung, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: This paper reports the establishment and eld-test results of a method for analyzing low
Received 9 September 2015 levels of amine mixtures in the ambient air near industrial processes. Seven amines that
Received in revised form 13 March are commonly used in industrial processes were selected as target contaminants. Two-stage
2016 Teon impingers that were lled with deionized water were used as the samplers. The recov-
Accepted 6 April 2016 eries of all amines were between 93.2% (trimethyl amine) and 103.4% (propyl amine). The
Available online 13 April 2016 collected samples were then analyzed via ion-chromatograph with a conductivity detec-
tor. We separated the seven amines by operating the column at two different temperatures
Keywords: (35.0 and 17.5 C). The detection limits of this method ranged from 0.11 to 0.48 ppb, which
Ambient air is sufcient for environmental odor control. The accuracy, sample preservation time and
Organic amines interference of other chemicals when using this method were also studied. The eld tests
Odorous compounds of this method in the environment outside an electronic chemical plant detected three target
Impinger sampler amines at low ppb levels. A level of trimethyl amine of more than 100 ppb was quantied
Ion chromatography inside another PCB production plant using the same method. This solvent-free sampling
and cost-effective method can sufciently analyze low concentrations of amines in the
environment, which makes it suitable for large-scale investigations.
2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction The livestock industry is one of the major contributors to amine

pollution in the environment (ONeill and Phillips, 1992; Ngwabie et al.,
Odorous chemicals in the air can often cause discomfort and stimulus 2007). Amines and other hazardous gases can be produced via either
reaction to the sensory systems of humans. Unlike most occupational the degradation of proteins in diary waste (Das et al., 2015; Arun and
exposure to fugitive volatile organic compounds (VOCs), which repre- Sivashanmugam, 2015) or from the feces of animals (Rappert and
sent chronic threats (Hassim et al., 2010; Hassim and Hurme, 2010), Mller, 2005; Liu et al., 2015; Zhang et al., 2015). Amine compounds
odorous gases can cause an acute reaction and an immediate dam- have a smell that is similar to that of urine and rotten sh or meat.
age to health (Lee and Wexler, 2013). Long-term exposure to low levels Airborne amines have also been found in the environment near animal
of odorous gases can eventually lead to anorexia, amnesia and other husbandry (Filipy et al., 2006; Schade and Crutzen, 1995; Sintermann
neural dysfunctions (Ge et al., 2011a). et al., 2014) and diary industries (Rabaud et al., 2003). Amines are
Among various odorous substances, amines represent an impor- important raw materials of many chemical industries that produce sur-
tant category due to the high frequency of usage in various industries. factants, emulsiers and hair-removal gels. Amines are also used in the

Corresponding author. Tel.: +886 2 77346132; fax: +886 2 29324249.

Corresponding author.
E-mail addresses: [email protected] (L.-Y. Sung), [email protected] (C.-J. Lu).
http://dx.doi.org/10.1016/j.psep.2016.04.005
0957-5820/ 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335 329

production of many products that are used daily such as medicines,

cosmetics, pesticides, dyes, and adhesives (Zhao et al., 2002; Pinheiro
et al., 2004). There are also new ndings regarding the chemical reac-
tion and particle formation in the atmosphere (Ge et al., 2011b, 2014;
Kulmala et al., 2013). A eld investigation of alkylamines in ambient
aerosols using an aerosol time-of-ight mass spectrometer (ATOFMS)
has also been reported recently (Healy et al., 2015). Therefore, the detec-
tion and prevention of amine contamination has become an important
issue for industries and the environments that surround them.
Various sampling techniques have been applied for collecting
amines in the environment: headspace (Maris et al., 1999), impinger
(Verriele et al., 2012), denuder (Chang et al., 2003; Ku et al., 2010),
ion-exchange resin cartridge (Dawson et al., 2014), and solid-phase
microextraction (SPME) (Namiesnik et al., 2003). Airborne amines are
usually analyzed using gas chromatography (GC) or high-performance
liquid chromatography (HPLC) in conjunction with a mass spectrom-
eter (MS) detector. Other methods such as ion chromatography and
capillary electrophoresis have also been attempted (Szulejko and Kim,
2014).
The goal of this project was to establish and validate a reliable and
cost-effective method that the Environmental Protection Agency could
use to perform the large-scale monitoring of amine contamination.
This method can also serve as a tool for assessing chemical exposure
in strategies for reducing occupational health risks (Ng and Hassim,
2015). A list of seven amines has been compiled by the local EPA based
on frequent usage in chemical and electronic industries. In the present
work, we used temperature tuning ion chromatography to achieve suf-
Fig. 1 (A) Schematic diagram of the calibration system, (B)
cient separation for selected target amines. The sample recovery and
preservation time when using a Teon impinger with deionized water
conguration of the impinger sampler.
as the sampling media were evaluated. Field tests of this method in the
from the previous impingers. The sampling ow rate was
environment surrounding a chemical plant and inside a printed circuit
board plant are discussed. set at 1.0 L/min using a pump (SKC AirCheck 2000) and was
calibrated via a mass ow meter (SKC 717) before and after
every sample was taken. A sample volume of 30 L was used
2. Material and methods throughout all tests in this study.

2.1. Chemicals 2.3. Amine analysis using an ion-chromatograph

The seven target amines for this study were methyl amine The ion chromatograph used for this study was an ICS-5000
(MA), ethyl amine (EA), dimethyl amine (DMA), isopropyl (Thermo Scientic Dionex, USA) equipped with a conductivity
amine (IPA), propyl amine (PA), diethyl amine (DEA), and detector. This ion chromatograph also employs a thermo-
trimethyl amine (TMA). All amines were obtained from either stat system to test the effect of temperature on separation.
Aldrich (USA) or Acros (USA) with a purity >99% or higher. The columns used for this experiment included an Ion Pac
Methyl sulfonic acid (MSA) that was used for the eluent and CS19 guard column (4.0 m packing particle diameter, 2 mm
standard dilution was obtained from Dionex (USA). Deionized i.d., 5 cm in length) and an Ion Pac CS19 separation column
water with 18.2 M cm1 resistance was prepared using the (4.0 m packing particle diameter, 2 mm i.d., 25 cm in length).
Milli-Q system (Merck Millipore, Germany). A current-controlled type suppressor (CSRS 300, Thermo Sci-
entic Dionex, USA) was used with this ion chromatograph.
2.2. In-lab calibration and sampling apparatus The volume of the sample injection loop was 100 L. The
eluent was an MSA solution with a controlled concentration
Fig. 1A shows the setup for in-lab calibration experiments. gradient. The elution ow rate was 0.25 mL/min.
Standard amine solutions were injected into a heated glass
T-union using a micro syringe. The glass T-union was placed 3. Results and discussion
inside a small oven that was maintained at 150 C. A makeup
gas at 1.0 L/min N2 from gas cylinder ow through the heated 3.1. The temperature effect on ion chromatographic
area carried the evaporated amines into the impinger. The separation
equivalent mass of an amine can be calculated according to
the concentration and volume of injected amine standard Fig. 2 shows the chromatograms of seven amines at temper-
solutions. The equivalent concentration in air was calculated atures ranging from 45 to 13 C. Following a few initial trials,
according to the injection mass of amines and the air ow- we found that analytes will elute too fast and co-elute if the
through volume (i.e., 30 L). concentration of MSA is too high. Therefore, we kept the elu-
Three Teon midget impingers were used in series in ent strength at low levels during the separation of amines.
our sampling apparatus (Fig. 1B). The rst impinger was There was only a limited range for eluent strength adjust-
lled with 25 mL deionized water as a primary sampler. The ment. The blue lines in revised Fig. 2 are eluent programs that
second impinger was also lled with 25 mL deionized water correspond to the MSA concentration at the 2nd y-axis. The
to check for breakthrough from the rst impinger. The third MSA concentration started at a low level (i.e., 2.0 mM) during
impinger was empty and was used only to remove mist the separation and rose to a high concentration (815 mM) to
330 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335

Fig. 2 Ion chromatograms of column temperature at (A) 13 C, (B) 17.5 C, (C) 25 C, (D) 35 C, (E) 45 C. The blue lines stand
for the eluent programs (i.e., MSA concentrations corresponding to 2nd y-axis). (For interpretation of the references to color
in this gure legend, the reader is referred to the web version of this article.)

purge all remaining ions after the analytes had been eluted. would be rare. The species of amines presented in a given envi-
As Fig. 2A shows, these target amines did not separate well at ronment are related to a nearby source or process. Therefore,
low temperature. DMA and IPA were completely overlapped at we could use a 17.5 C column temperature if either IPA or DMA
13 C. PA and DEA were only partially separated at 13 C, but were the only compounds likely to be present in the eld. Like-
these two amines were completely resolved when the temper- wise, if the likely compounds were either DEA or TMA while
ature was raised above 17.5 C. When the column temperature IPA and DMA both existed in the air, a column temperature of
reached 25 C, the TMA retention time was signicantly short- 35 C would be sufcient for monitoring. In the eld applica-
ened, which caused it to be overlapped by DEA (Fig. 2C). Also, tion of an unknown environment, we can split the collected
DMA and IPA showed incomplete separation at 25 C. The sample into two compartments and test whether the above
separation of these two compounds was improved by contin- amines are present. Once the species of amines is conrmed,
uously raising the column temperature. As shown in Fig. 2D, the environmental agents can then apply a column tempera-
DMA and IPA were effectively separated when the column ture of either 17.5 or 35 C for long-term periodic sampling.
temperature reached 35 C. Unfortunately, the temperature
effect of a reduction in the retention of TMA was more dras- 3.2. Interference of other ions
tic than for other amines. Therefore, the elution time of DEA
caused an overlapping of TMA at 35 C. There are some possible interference ions that could co-exist
Although the seven amines that were selected for the in the samples with targeted amines. The possible interfer-
present study are common species in the environment, the ence ions tested in this study were as follows: K+ , Mg2+ , Ca2+ ,
detection of seven amines altogether at one sampling site mono-ethanol amine (MEA), and tetramethyl ammonium
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335 331

Fig. 3 IC chromatograms at 17.5 C for (A) six targets, (B) MEA interference, (C) K+ interference, (D) TMAH interference, (E)
Mg2+ interference, (F) Ca2+ interference.

hydroxide (TMAH). Fig. 3 shows the ion chromatogram of gure shows, all the amine calibration lines were non-linear.
amines at a column temperature of 17.5 C and the corre- We have repeatedly tested the responses at all concentrations.
sponding chromatograms of each interference ion. As these These results are highly reproducible. Non-linear calibration
gures show, MEA elutes earlier than the rst target amine lines reportedly occur if the analyte concentration is very low
(MA) under our separation conditions. The retention time and high eluent strength (i.e., >20 mM) is used. This is due to
of K+ lies between the peaks of (DMA + IPA) and PA. The the leakage of a small fraction of conductive ions back to the
remaining interference ions (e.g., Mg2+ , Ca2+ and TMAH) elution ow. When the conductivity of the analyte is low, the
have much longer retention times compared with our target deviation from linearity at low concentration often causes a
compounds. Therefore, the interference of these ions can be negative interception (SeQuant AB, 2007).
ignored under our chromatographic condition settings. The These curves can be tted by second-order equations and
tests of the possible interference of these ions at 35 C are forced to zero. The liquid concentrations of LOD were cal-
shown in the supporting information (Fig. S1), and there was culated using a calibration equation and an equivalent peak
no signicant interference at this column temperature. area that was three times the standard deviation of the seven
replicates at the lowest concentration tested. The LODs for air
3.3. Calibration and detection limits concentration were calculated assuming a 100% amine recov-
ery of the 30 L air sample using 25 mL DI water in the impinger.
Fig. 4 shows the calibration curves of the seven target amines. In comparison with recent work reported by Verriele et al.
The x-axis represents the concentration of amines in the sam- (2012), the absolute masses of amines tested are different. As
ple liquid (i.e., DI water). The corresponding peak areas were in the work of Verriele et al., we used a 25 mL impinger lled
obtained by using a 100 L sample loop for IC injection. As this with D.I. water as the sampling media. Verriele et al. sampled
332 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335

(A) 0.025
Peak area (S*Min) PA
0.020 DMA
EA
0.015

0.010

0.005

0.000
0 20 40 60 80
Concentration (ng/mL)
(B) 0.040
Peak area (S*Min)

MA Fig. 5 Sample preservation time test for methyl amine.

0.030

0.020
IPA introduce an uncertainty in the nal analytical results that
DEA
could reach almost 20%.
0.010
TMA
0.000 3.5. Sample preservation duration tests
0 20 40 60 80
Concentration (ng/mL) When a large-scale eld investigation is conducted, imme-
diate analysis is often difcult due to the quantities of eld
Fig. 4 Calibration curves of seven amines using ion
samples and to lab schedules. Thus, aqueous amine samples
chromatograph with conductivity detector.
often must be preserved for certain periods of time before
72 L air volume in 2 h. We sampled only 30 L air volume. Ver- they can be scheduled for ion chromatography analysis. In
riele et al. used a 500 L sample loop for ion chromatography order to test the sample stability, we prepared the standard
and we used only a 100 L sample loop. It would be a mistake to amine samples at three different concentration levels and
assume that both studies used a similar concentration range. maintained them in a 4 C refrigerator. These samples were
In fact, the absolute masses of amines injected in our method analyzed on days 1, 2, 3, 7, and 14 after preparation to see
were 12-fold lower than the previous research (Table 1). if there was any sign of decay. Fig. 5 gives the example data
from the preservation test on MA. The recoveries of MA during
3.4. Breakthrough and sampling efciency of Teon the 14 days varied from 91.9 to 102.3%. There was no con-
impingers sistent trend of decay. Similar results were found in all other
amines as well (supporting information, Fig. S2). Therefore,
In order to test the sample validity, two impingers lled with these amine samples were reliably analyzed within the 14
25 mL DI water were connected in series and a sampling ow days of eld sampling. Longer periods of preservation were not
was bubbled through both impingers. The recoveries of the tested, and, therefore, we recommend that the task of analysis
rst impinger were estimated by dividing the measured amine be completed within 14 days after eld samples are collected.
concentration with the injected concentration. The second
impinger served as a monitor for amine breakthrough from 3.6. Field studies for industrial environments
the rst impinger. The gas-phase amine samples were gen-
erated using the apparatus shown in Fig. 1A. Both impingers There were two eld studies conducted in this work. The
were immersed in an ice-water bath to improve the solubility rst eld study was performed inside the production area
of the amines in DI water. As shown in Table 2, the break- of a printed circuit board (PCB) manufacturing company.
through did not occur at the rst impinger because there was Organic amines are important agents for reducing copper as
no detectable amine in the solution of the second impinger. a conduction layer for PCBs. A very strong odor was found in
Although the average recoveries of all seven amines were the manufacturing area. One example chromatogram for the
above 93%, some of the sampling results showed quite large eld samples is shown in Fig. 6. We found MA, EA, DMA, IPA,
variations. The lowest recovery appeared during the second PA, and TMA in this area. The peak of TMA was much higher
test of TMA (79.6%) and the highest recovery was seen in the than all the other amines found. In an initial analysis, TMA
rst trial of EA (118.1%). The sampling process appeared to was above the concentration range of the calibration line.

Table 1 The detection limit of the targets for the calibration curves.
Compound Abbreviation Odor threshold (ppb) Detection limits

Liquid (ng/mL) Vapora (ppb)

Methyl amine MA 18.2 0.72 0.30

Ethyl amine EA 27.0 1.17 0.48
Dimethyl amine DMA 24.1 0.86 0.36
Isopropyl amine IPA 191.0 0.64 0.20
Propyl amine PA 61.0 0.33 0.11
Diethyl amine DEA 20.0 0.55 0.14
Trimethyl amine TMA 0.3 1.02 0.32

a
Calculations based on 30 L air sample volume.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335 333

Table 2 Sample recovery and breakthrough tests.

Amine Conc. (ng/mL) First test (%) Second test (%) Third test (%) Average (%)

1st impinger 2nd impinger 1st impinger 2nd impinger 1st impinger 2nd impinger

MA 21.6 105.1 N.D. 98.7 N.D. 103.9 N.D. 102.6

EA 21.6 118.1 N.D. 89.6 N.D. 98.1 N.D. 102.0
IPA 16.7 89.2 N.D. 115.6 N.D. 98.9 N.D. 101.2
PA 25.9 108.8 N.D. 107.5 N.D. 93.9 N.D. 103.4
DEA 25.6 92.3 N.D. 111.9 N.D. 103.5 N.D. 102.6
DMA 21.6 95.0 N.D. 96.4 N.D. 90.5 N.D. 93.9
TMA 25.6 99.9 N.D. 79.6 N.D. 99.9 N.D. 93.2

Fig. 6 Ion chromatogram of a eld sample in PCB production area.

Fig. 7 Ion chromatograph of a eld sample outside an electronic chemical plant.

The second eld study site was a chemical plant that

Table 3 Field tests of amines inside a PCB plant (unit:
ppb). produces chemicals such as dimethyl amine borane (DMAB),
which is widely used in the manufacturing of semiconductors
Tests # 1st 2nd 3rd
and power transistors. In this process, dimethyl amine was
MA 10.18 9.39 used as one of the raw materials. The same chemical plant
DMA 8.62 10.49 12.93 also produces a series of agrochemicals such as formetanate,
IPA 3.47 6.43 13.18 methomyl, propoxur, etc. Various organic amines are also used
PA 5.62 10.79 19.60
to produce these chemicals. The samples were taken outside
TMA 29.36 148.03 178.15
the fence of the plant to see if amines could be detected in
the nearby environment. Fig. 7 shows one of the ion chro-
matographs of a eld sample at this site. Three amines, DMA,
Therefore, secondary analyses of diluted eld samples were IPA and TMA, were found in the environment outside of this
used to reduce the TMA concentration down to the calibration plant. Five impinger samples were collected at different times
range. The analysis results of three eld samples collected during the day of the eld study. The quantitative analysis
at the same location are summarized in Table 3. MA, DMA, results of environmental amines near this chemical plant are
IPA, and PA were all below 10 ppb. The concentrations of TMA summarized in Table 4. As shown in this table, DMA and
found in the three samples were 29.36, 148.03, and 178.15 ppb. TMA appear to permanently exist in this environment and
The unusually high concentrations of TMA detected in the often exceed the odor threshold. IPA and PA were both found
production area indicated the need for improving local in relatively low concentrations. These two amines were not
ventilation and the process related to this chemical. detected in some of the eld samples, which may have been
334 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 328335

Table 4 Field tests of amines outside a chemical plant Appendix A. Supplementary data
(unit: ppb).
Tests # 1st 2nd 3rd 4th 5th Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.psep.
DMA 8.00 10.25 9.29 9.05 18.95
2016.04.005.
IPA 1.63 0.40 1.43
PA 2.02 2.37
TMA 2.10 17.38 26.67 3.31 20.73
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