International Journal of Greenhouse Gas Control 83 (2019) 83–90

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International Journal of Greenhouse Gas Control

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

Decomposition of N-nitrosamines formed in CO2 capture systems through T

electrochemically-mediated reduction on carbon xerogel electrode
Jesse G. Thompsona,b, Xin Gaoa, Shino Tomaa, Keemia Abada, Saloni Bhatnagara, James Landona,
⁎
Kunlei Liua,c,
a
University of Kentucky Center for Applied Energy Research, Lexington, KY, 40511, United States
b
University of Kentucky, Department of Chemistry, Lexington, KY, 40506, United States
c
University of Kentucky, Department of Mechanical Engineering, Lexington, KY, 40506, United States

A R T I C LE I N FO A B S T R A C T

Keywords: N-nitrosamines, as a class of compounds, have been reported to be mutagenic, cytotoxic, genotoxic and carci-
CO2 capture nogenic. N-nitrosamine formation and emission are a major concern for amine-based CO2 capture systems. A
N-nitrosamine process using a stationary carbon electrode inside an electrochemical cell was developed and tested in this study
Electrochemical reduction to adsorb and decompose two N-nitrosamines, N-nitrosopyrrolidine and N-nitrosodiethylamine, from an aqueous
Carbon xerogel electrode
amine solution. The carbon xerogel electrode material has a high N-nitrosamine adsorption capacity and can
Amine CCS waterwash
initiate an electrochemically-mediated reduction of N-nitrosamines to a secondary amine. A greater than 80%
reduction of N-nitrosodiethylamine and 90% of N-nitrosopyrrolidine was observed from a simulated amine-
based waterwash solution using an applied current up to 300 mA. N-nitrosamine decomposition was effective in
solutions with relatively high amine or salt concentrations.

1. Introduction mitigation strategies may make implementation on a large industrial

Significant challenges exist in controlling the emissions of ha-
zardous amine degradation products, including carcinogenic N-ni-
trosamines, from post-combustion carbon capture systems. N-ni-
trosamine compounds can form from secondary amine solvents or
degradation compounds, and accumulate in the amine solvent loop and
waterwash sections prior to being emitted into the atmosphere (Yu
et al., 2017; Dai et al., 2012). Due to the recent rapid development of
CO2 capture systems employing aqueous amine solvents, N-ni-
trosamines now represent an emerging environmental concern if their
formation and emission from CO2 capture systems cannot be better
understood and controlled. Some current wastewater treatment
methods have been assessed and applied to CCS systems with limited
success. The relative complexity and/or cost of these N-nitrosamine
scale cost prohibitive, requiring simpler and more cost effective ap-
proaches to be developed.
1.1. N-Nitrosamine formation
A recently published review article summarizes many aspects of N-
nitrosamines in CO2 capture systems, including the reported formation
pathways related to amine-based CCS systems (Yu et al., 2017). The
majority of the proposed pathways generally involve the reaction of
NOx with a secondary amine. Among these reported pathways is: (1) an
NO2-initiated radical reaction; (2) an N2O3 pathway; (3) a carbamic
acid and NO2− reaction; (4) a reaction between a secondary amine and
ONOCO2−; and (5) a formaldehyde catalyst reaction of a secondary
amine and nitrate. Stable N-nitrosamines can also be formed through

Abbreviations: BAC, biological activated carbon; Ce, equilibrium concentration (mg/L); CO2, carbon dioxide; CCS, carbon capture and storage; CX, carbon xerogel;
DEA, diethylamine; DMEL, derived minimum effect limit; EDS, energy dispersive spectroscopy; ESI, electrospray ionization; FTIR, Fourier-transform infrared; GC, gas
chromatography; HPLC, high pressure liquid chromatography; IC, ion chromatography; KL, Langmuir constant (L/g); KF, Freundlich isotherm constant; MEA,
monoethanolamine; MNPZ, mono-N-nitrosopiperazine; MOR, morpholine; MRL, minimum reporting limit; MS, mass spectrometer; NDEA, N-nitrosodiethylamine;
NDELA, N-nitrosodiethanolamine; NDMA, N-nitrosodiemthylamine; NLDFT, nonlocalized density functional theory; NMOR, N-nitrosomorpholine; NOx, nitrogen
dioxides; NPY, N-nitrosopyrrolidine; PY, pyrrolidine; PZ, piperazine; qe, equilibrium sorption capacity (mg g-1); qm, maximum sorption capacity (mg g-1); R2,
coefficient of determination; RO, reverse osmosis; ROS, reactive oxygen species; SEM, scanning electron microscopy; TOF, time-of-flight; UV, ultraviolet; X2, Person’s
Chi-square statistic
⁎
Corresponding author.
E-mail address: kunlei.liu@uky.edu (K. Liu).

https://doi.org/10.1016/j.ijggc.2019.02.003
Received 28 September 2018; Received in revised form 17 January 2019; Accepted 5 February 2019
Available online 14 February 2019
1750-5836/ © 2019 Elsevier Ltd. All rights reserved.
J.G. Thompson, et al.
the formation and decay of unstable primary and tertiary amine N-ni-
trosamine compounds.
1.2. N-Nitrosamine toxicity
N-nitrosamines are a class of compounds that have been reported to
be mutagenic, cytotoxic, genotoxic and carcinogenic (Robichova et al.,
2004). N-nitrosamines can be potent carcinogens, with two N-ni-
trosamines specifically, nitrosodiethylamine (NDEA) and ni-
trosodimethylamine (NDMA) being the most hazardous (Buist et al.,
2015; Wagner et al., 2014). N-nitrosamine can exhibit mutagenic ac-
tivity when metabolically activated to produce point mutations and
chromosome breaks (Hillebrand et al., 2016). This metabolic activa-
tion, usually by cytochrome P-450, reduces the nitroso group to DNA
reactive N-hydroxylamines which in turn mutates DNA (Robichova
et al., 2004). N-nitrosamines can also induce DNA damage at the cel-
lular level directly via formation of reactive oxygen species (ROS).
ROS’s have been observed in cells exposed to nitrosomorpholine
(NMOR) without any metabolic activation present (Robichova et al.,
2004).
N-nitrosamines are also considered to be genotoxic substances that
can induce permanent genetic changes in cells and can cause cancer
when they interact with DNA (Ravnum et al., 2014). The level of
toxicity and damage varies based on the type of N-nitrosamine. In this
experiment NDMA followed by NMOR were found to be the most mu-
tagenic N-nitrosamines when examining the induction of genomic DNA
damage in mammalian cells (Wagner et al., 2014).
Apoptosis (programmed cell death) of cells exposed to carcinogens
have an important role in cancer development. Apoptosis allows the
removal of cells with extensive DNA damage. Among N-nitrosamines,
nitrosopyrrolidine (NPY) and NDMA have been studied and shown to
induce apoptosis in the presence of metabolic activation (Morales et al.,
2010). In addition, animal studies have shown the formation of tumors
when exposed to N-nitrosamines (Ravnum et al., 2014; Buist et al.,
2015).
1.3. N-Nitrosamines observed in CCS waterwash
The gas-liquid partitioning (Henry’s volatility) coefficient of CO2-
capture relevant N-nitrosamines from amine solvents reveals that N-
nitrosamines formed in the solvent can partition to the gas phase within
the absorber column and be emitted from the system (Thompson et al.,
2018). In one study, monoethanolamine (MEA) solvent testing by
Chahen et al. (2016) at the IFPEN pilot plant showed formation of ni-
trosodiethanolamine (NDELA), NMOR and NDMA in the solvent, while
NMDA was also observed in gas phase emissions at 264 μg/m3. At the
Tarong coal fired power plant, the mono-nitrosopiperazine (MNPZ)
concentration in a piperazine (PZ) solvent ranged from around
250–3000 mg/kg, with NPZ also observed in the waterwash at a range
close to 0.02 – 0.19 mmol/kg (Cousins et al., 2015). N-nitrosamines
including NDELA, NMOR, nitrosopiperadine (NPip), NDMA, MNPZ and
dinitrosopiperazine, have been observed in the nM to μM concentration
range in pilot waterwash solutions from MEA and AMP-PZ solvent
testing (Dai et al., 2012). NMOR was likewise observed at levels as high
as 6 μM from a lab-scale waterwash during morpholine (MOR) solvent
testing (Dai and Mitch, 2015).
1.4. N-Nitrosamine mitigation strategies in wastewater
Currently, CCS waterwash systems are the last location where N-
nitrosamine can be captured prior to emission and the Henry’s volatility
coefficients of these N-nitrosamines from water suggests that water
wash systems can be effective at capturing the N-nitrosamines. These
systems circulate water in a closed loop, with occasional blowdown to
either the amine loop (to recover amine) or to an external water
treatment system within the power plant. N-nitrosamine removal from
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International Journal of Greenhouse Gas Control 83 (2019) 83–90
wastewater has been studied extensively for water recovery and
drinking water production.
The removal of disinfection byproducts in treated wastewater, in-
cluding N-nitrosamines produced through the chloramine disinfection
process, has been an area of interest as the need to recycle municipal
water has increased (Chuang and Mitch, 2017). N-nitrosamines can be
effectively removed from water through a variety of treatment options
including biological treatments, adsorption onto activated carbons
(based on the N-nitrosamine hydrophobicity), using filtration mem-
branes (micro, ultra and nanofiltration), and reverse osmosis (RO) and
ultraviolet (UV) treatments (Sgroi et al., 2018; Afzal et al., 2016;
Fujioka et al., 2013, 2014; Gerrity et al., 2015).
1.5. N-Nitrosamine mitigation in CCS
N-nitrosamines formed in CCS solvents can potentially be managed
using techniques similar to those utilized in wastewater treatment. High
dose UV photolysis and UV plus ozone were effective at decomposing 6
μM NMOR from a MOR solvent in an amine containing lab-scale wa-
terwash solution (Dai and Mitch, 2015). This type of process can be
effective at controlling N-nitrosamine level at an order of magnitude
lower than without treatment, but could not completely decompose the
N-nitrosamines in solution. The downside of an UV + ozone treatment
is the parallel decomposition of amines also collected in the waterwash.
Amine recoovery is the primary function of the waterwash to avoid
costly amine make-up.
Aqeel et al. (2017) showed that the photodegradation of NDELA in
water was effective up to pH 10, which would be the pH range expected
in amine waterwash solutions, however the photodegradation of dif-
ferent N-nitrosamines including NDEA and NMOR at pH 10 was mini-
mally effective. The presence of other organic compounds in the wa-
terwash solution may also negatively impact N-nitrosamine
decomposition (SØrensen et al., 2015).
Hydrogen reduction of N-nitrosamines in amine solvents was shown
to be effective with a variety of metal catalysts (Chandan et al., 2014,
2015). Additionally, the thermal decomposition of N-nitrosamines
formed in amine solvent can be achieved by running the CCS stripper at
high temperatures. This strategy can be effective at matching the for-
mation rate and keeping the absolute N-nitrosamine level in the solvent
at a relatively low concentration, but does not fully removal all N-ni-
trosamines from the solvent and will increase the thermal degradation
of the amine component in the solvent while also increasing the overall
energy consumption of the CCS (Fine et al., 2014; Voice et al., 2015).
1.6. N-Nitrosamine adsorption
Less energy intensive N-nitrosamine removal strategies have also
been studied. Tobacco specific nitrosamines have been adsorbed from
water using a variety of activated carbons, zeolites and zeolite modified
activated carbons (coconut and coal based) (Sun et al., 2014; Li et al.,
2013; Lin et al., 2014). The acid-base sites on the zeolite surface and
electrostatic pores make these structures suitable for adsorbing ni-
trosamines from both gases and liquids.
Carbon materials have long been used for the removal of organic
contaminants from aqueous solutions in a variety of applications. The
similar polarity of a carbon surface and the carbon-containing mole-
cules leads to favorable Van der Waals interactions and a preferential
association with the carbon surface. This interaction has been shown to
be an applicable phenomenon and effective strategy for the separation
of N-nitrosamines from water (Munch, 2005). Commercial and mod-
ified activated carbons are also effective at removing high concentra-
tions of N-nitrosamines from solutions containing up to 0.3% amine
(Widger et al., 2017). In this study, activated carbons with high surface
pKa and base sites had high capacities and removal rates between
75–90% for polar and non-polar N-nitrosamines including NPY, NDEA,
NDELA and NPZ. The only downside of this process is the need to
J.G. Thompson, et al.
periodically regenerate or replace the carbon sorbent, which adds to
operating costs.
Another removal option is to use alternative carbon materials as
sorbents. Liu et al. (2016) studied the use of a capacitive deionization
cell containing carbon electrodes to remove organic disinfection by-
products from wastewater. In this process, the organic compounds are
physically adsorbed onto the carbon electrode surface due to their re-
lative affinity (polarity). The adsorbed organic compounds were then
electrochemically oxidized from the electrode surface using an applied
potential. This type of process can decompose these hazardous com-
pounds without the need for additional steps or the production of un-
desired byproducts.
Expanding on this concept, this study discusses the development
and testing of a process using stationary carbon electrodes inside an
electrochemical cell to adsorb N-nitrosamines from an aqueous solu-
tion, followed by electrochemically-mediated reduction of N-ni-
trosamines from CCS waterwash solutions.
2. Experimental
2.1. Chemical analysis
An Agilent 1260 Infinity high performance liquid chromatography
(HPLC) coupled to a 6224 series time-of-flight (TOF) mass spectrometer
(MS) was used to measure the concentration of N-nitrosamines. An
Agilent guard column (Zorbax Eclipse Plus Phenyl-Hexyl
2.1 × 12.5 mm, 5 μm) and analytical column (Zorbax Eclipse Plus
Phenyl-Hexyl, 3 × 10 mm, 3.5 μm) were installed in the HPLC. An
isocratic mobile phase of 60:40 acetonitrile (ACN; LC/MS grade, VWR)
and 0.1% formic acid (LC/MS grade, Fisher Scientific) in water (LC/MS
grade, VWR) at a flow rate of 0.3 mL/min was used with a 10 μL in-
jection volume. The column temperature was not controlled (room
temperature) and the total run time was 6 min.
The MS was operated in dual electrospray ionization (ESI+) positive
mode with mass scan range of 50–1000 m/z. A reference mass solution
of purine (121.050873 m/z) and hexakis (1H,1H,3H-tetra- fluor-
opropoxy)phosphazine (922.009798 m/z) was used in the dual ESI+
configuration to maintain mass accuracy within the TOF-MS. Samples
were prepared and diluted in the mobile phase and analyzed in tripli-
cate. Extracted ion chromatograms of the protonated molecular weights
[M+H]+ were used for product quantification. Calibration curves were
established at the beginning of each analysis using neat N-nitrosamine
standards purchased from Sigma-Aldrich (St. Louis, MO). N-ni-
trosamine degradation products were identified by their accurate mo-
lecular weight (m/z) and confirmed by calculating the mass accuracy of
the observed mass spectral peaks and the resulting molecular formula
(Thompson et al., 2017a). The stability of the amine during electro-
chemical experiments was examined with ion chromatography (IC)
using a previously described method (Thompson et al., 2017b).
Residual N-nitrosamines were recovered from the stationary CX
electrode material by a methylene chloride extraction (2X) of the dried
carbon electrode. The carbon electrode was immersed into a closed
vessel containing 10 mL methylene chloride (HPLC grade, VWR). The
solution was agitated for 30 min at room temperature (22 ± 1 °C). The
methylene chloride was decanted and a second 10 mL aliquot was
added and repeated under the same condition. The extracts were
combined and analyzed in triplicate on an Agilent 7890 A gas chro-
matograph (GC) system with a 5975C inert mass selective detector
(MSD) using electron impact ionization (EI) with scan range 35–350 m/
z. An Agilent J&W DB-624 column (60 m × 0.320 mm ID × 1.80 μm
film thickness) was operated under the following oven temperature
program: initial temperature 50 °C was held for 2 min, raised up to
220 °C at 8 °C min−1, and then held for 4 min. The temperature of inlet,
transfer-line, and ion-source were held at 200, 250, and 230 °C, re-
spectively. The injection volume was 1 μL in the splitless mode.
Calibration curves of N-nitrosamines were built using a commercial
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International Journal of Greenhouse Gas Control 83 (2019) 83–90
Method 521 N-nitrosamine calibration mix (Restek). The concentration
of N-nitrosamines were calculated from the calibration curves using
characteristic ions fragments corresponding to each N-nitrosamine. N-
nitrosamines including nitrosodiethylamine (NDEA) and ni-
trosopyrrolidine (NPY) were purchased as pure compounds (> 99%)
from Sigma Aldrich (St. Louis, MO). Monoethanolamine (MEA) was
obtained from Alfa Aesar (Haverhill, MA).
The pH of each solution was measured before and after each ad-
sorption and decomposition experiment. The pH was generally un-
changed with an average value of 9.052 ( ± 0.17) before and 9.046
( ± 0.08) after.
2.2. Carbon xerogel (CX) preparation and characterization
The carbon xerogel (CX) electrode material was synthesized using a
previously described method (Landon et al., 2012). Scanning electron
microscopy (SEM) and energy dispersive spectroscopy (EDS) was col-
lected on a Hitachi S-4800 field-emission scanning electron microscope
with a voltage of 15 kV and a current of 20 μA. N2 adsorption and
desorption isotherms were measured using an ASAP2020 surface area
and porosity analyzer (Micromeritics) with 50 mg of sample degassed at
160 °C for 12 h. Cumulative pore volume was calculated via the non-
localized density functional theory (NLDFT) provided by Micromeritics.
A Fourier-transform infrared (FTIR) spectrometer (Nicolet 6700,
Thermo Scientific) was used to identify surface species. The FTIR
sample was prepared with 0.07 g of a mixture of CX/KBr at a ratio of
0.3 wt% (SC vs. KBr). The FTIR spectra was collected by co-adding 256
scans at a resolution of 4 cm−1.
2.3. N-Nitrosamine adsorption onto CX electrode
Adsorption behavior of N-nitrosamines on the carbon CX electrode
material was evaluated in a closed vessel at 22 °C containing a stock
solution with variable concentrations of N-nitrosamines in water for a
minimum of 12 h. A sample of the solution was collected at the be-
ginning and end of each experiment to measure the baseline and final
N-nitrosamine concentrations, with total N-nitrosamine adsorption de-
termined by difference. The adsorption behavior was modeled by cal-
culating and plotting the amount of N-nitrosamine adsorbed on the
carbon per mass of carbon (qe) versus the final equilibrium concentra-
tion of N-nitrosamine in the solution (mg/L) (Widger et al., 2017). The
nonlinear Langumir and Freundlich models, which are widely used,
were applied to the adsorption isotherm data. These equations are given
in Section 3.2. The constants for the Langumir (qm and kL) and Freun-
dlich (n, kF) isotherm models were calculated using SigmaPlot® version
12.3 (Systat Software Inc., California USA) and IGOR Pro software
version 6.34 A (WaveMetrics, Inc., Oregon USA). The coefficients of
determination (R2) from a linear regression (from SigmaPlot) and Per-
son’s Chi-square statistic (χ2) from a non-linear regression (from IGOR
Pro) were used to evaluate the goodness-of-fit with the two isotherm
models in this study.
2.4. Electrochemical cell with carbon xerogel electrode
The CX material served as the working electrode (1.2 cm × 2.5 cm),
with titanium serving as the counter electrode in the two electrode
electrochemical cell containing a solution of N-nitrosamines (Fig. 1).
Solutions of nitrosodiethylamine (NDEA) and nitrosopyrrolidine (NPY)
at a concentration of 100 mg/L (each), with 0.3% or 1% mono-
ethanolamine was prepared and sparged with CO2 to simulate possible
waterwash solutions containing both amines and N-nitrosamines
(Widger et al., 2017). Separately, a solution of N-nitrosamines with 1 M
sodium chloride was prepared to examine N-nitrosamine decomposi-
tion in a high electrolyte concentration solution.
Experiments were performed in the following sequence: (1) wetting
the CX electrode in an agitated solution for a minimum of 12 h, (2)
J.G. Thompson, et al. International Journal of Greenhouse Gas Control 83 (2019) 83–90

Fig. 1. Simple lab-scale electrochemical cell with carbon xerogel (CX) elec-
trode, titanium counter electrode, and stir bar for agitating the N-nitrosamine
solution.

collecting an initial liquid sample to measure equilibrium N-ni-

trosamine adsorption onto the CX material prior to applying a charge,
(3) charging the cell at a set constant current (mA) for a measured time
period, and (4) collecting a final liquid sample to measure the re-
maining N-nitrosamine concentration in the solution. The voltage was
measured using a DC power supply (Agilent E3632 A) while performing
each experiment. The measured voltage in the cell was between 6–9 V,
with the high voltage mainly due to the low solution conductivity and
relatively large distance between the working and counter electrodes.
N-nitrosamine decomposition was determined by difference be-
tween the initial and final concentration in solution after accounting for
the amount of N-nitrosamine removed for analysis and any residual
nitrosamine recovered from the CX surface.

2.5. N-Nitrosamine handling concerns

Due to the hazard associated with the handling of N-nitrosamine

solutions, repeat experiments were minimized when possible. Previous
studies have shown that N-nitrosamine adsorption generally has a de-
viation of ≤ 2% (Widger et al., 2017), allowing a minimal number of
experiments to be considered as representative.

3. Results and discussion

3.1. Carbon xerogel characterization

Carbon xerogel (CX) is a type of mesoporous material with different

porosities and relatively high surface areas, excellent chemical stability,
conductivity, native ion-adsorption capability, and solvent wettability
(Landon et al., 2012; Gao et al., 2014). More practically, the CX ma-
terial is very stable which should allow for an extended operational
Fig. 2. a) SEM image of CX electrode material (1 μm scale); b) CX electrode
lifetime in wastewater treatment applications.
cumulative pore volume; c) FTIR spectrum of CX electrode.
The surface morphology of CX exhibits a uniform carbon matrix
with external pore size of ˜50 nm (Fig. 2a). The cumulative pore volume
(Fig. 2b) first exhibits an increase at 0.4–1.5 nm and second an increase
at 4–40 nm, resulting in a micropore volume of 0.08 mL g−1 and a total
pore volume of 0.55 mL g−1. The FTIR spectrum (Fig. 2c) depicts the
chemical species at the CX surface. Bands at ˜3400, ˜1630, and

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J.G. Thompson, et al. International Journal of Greenhouse Gas Control 83 (2019) 83–90

Fig. 3. Adsorption behavior and maximum capacity of NDEA (● black circle) and NPY (gray triangle) on the CX electrode material. Langmuir and Freundlich fits are
included with the calculated model fit values given in Table 1.

˜1100 cm−1 correspond to OeH stretching, C]C stretching, and C–O
stretching, respectively.
3.2. N-Nitrosamine adsorption on CX electrode
Two commercially available N-nitrosamines were selected for initial
testing, NDEA a non-polar N-nitrosamine and NPY a slightly polar
cyclic N-nitrosamine. A series of adsorption experiments were con-
ducted with variable N-nitrosamine concentrations and the CX ad-
sorption capacity in mg N-nitrosamine per gram CX electrode was de-
termined. The isotherm data (Fig. 3) was fitted to Langmuir and
Freundlich adsorption models using Eqs. (1) and (2) respectively, where
qe is the equilibrium adsorption capacity on the sorbent CX electrode;
qm (mg/g) is the maximum adsorption capacity of the sorbent CX
electrode; kL and kF are the Langmuir and Freundlich constants, re-
spectively; 1/n is an experimentally determined unitless exponent; and
Ce (mg/L) is the equilibrium N-nitrosamine concentration in the solu-
tion. The calculated Langmuir and Freundlich constants, as well as the
maximum N-nitrosamine capacity (qm) and uncertainty associated with
the model fits are given in Table 1.
qm kL Ce
qe = Langmuir isotherm
1 + kL Ce
q e = kFC1/n
e Freundlich isotherm
2
The Pearson’s Chi-square (χ ) test is generally thought to provide a
better method than the coefficient of determination (R2) to evaluate
goodness-of-fit during the non-linear fitting of observed data and ex-
pected data with isotherm models (Ho et al., 2005). The χ2 is given as;
(qe − qe, m)2
x2 = ∑ trosamines with both models.
qe, m
where qe is the equilibrium adsorption capacity (mg/g) from the
experimental data and qe,m is the expected equilibrium adsorption ca-
pacity. A small χ2 value indicates that the expected data from the model
matches the experimental data well. In this statistical test, the null
hypothesis, Ho, was that the experimental values equal the model va-
lues. The probability of significance level (α) was set to 5% or [0.05]
(small calculated probability (p-value) indicates a very unlikely event
and the Ho will be rejected if the p-value is less than α [0.05]). The
critical value of χ2 is obtained based on the significance level (0.05 in
this test) and the degrees of freedom (df = k-1, k is the number of
different N-nitrosamine concentration levels). The calculated χ2 should
be smaller than the critical value to accept Ho. The critical values of χ2
for NPY and NDEA were 7.815 and 9.488, respectively.
The calculated χ2, with corresponding p-value and R2 from Fig. 3,
are shown in Table 1. Since all calculated χ2 values were smaller than
the critical values of χ2,and all p-value were larger than 0.05, the Ho
was accepted. This means that all expected data from the models sta-
tistically agreed with the experimental data. A small χ2, around 0.4 was
obtained from NPY with both Langmuir and Freundlich models, and
from NDEA with Freundlich model. This shows that the experimental
data had a strong agreement with the model fits used in this study
(Fig. 3).
As mentioned earlier, the evaluation of the R2 to χ2 values shows a
(1) different level of agreement between the experimental and model va-
lues. This type of behavior has been previously reported by Ho et al.
(2)
(2005) with similar sorption isotherms. The R2 values in Table 1 gen-
erally only show goodness-of-fit of NDEA with the Freundlich model
(R2 > 0.95), with seemingly lesser agreement with the Langmuir model
of NDEA and the Langmuir and Freundlich models of NPY (R2 > 0.80).
However, the more suitable non-linear χ2 assessment shows good non-
linear fitting of observed data and expected data for both N-ni-
(3) The CX electrode was estimated to have a maximum adsorption
capacity of around 46 mg/g for NDEA and 9 mg/g for NPY (Fig. 3) using

Table 1
Calculated N-nitrosamine adsorption fitting parameters from Langmuir and Freundlich models (with standard error).
Langmuir Freundlich

N-Nitrosamine qm (mg/g) kL (L/g) χ2 R2 n kF χ2 R2

NPY 9.32 ± 1.41 0.0368 ± 0.0221 0.374 (p = 0.946) 0.801 3.70 ± 1.24 1.95 ± 0.88 0.382 (p = 0.944) 0.835
NDEA 45.62 ± 4.04 0.0304 ± 0.0136 3.452 (p = 0.485) 0.876 4.14 ± 0.47 9.66 ± 1.56 0.405 (p = 0.982) 0.973

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the Langmuir model equation (qm) in Table 1. The adsorption capacity

of NDEA is several times higher than for NPY and this may be related to
the relative differences in polarity of these N-nitrosamines, log Kow for
NDEA is 0.48 and -0.19 for NPY, and their different relative affinity for
the carbon CX material (Ventanas and Ruiz, 2006).

3.3. Electrochemically-mediated N-nitrosamine decomposition

Two N-nitrosamines were selected for initial electrochemical

testing, NDEA and NPY. Prior to each electrochemical experiment, the
CX material was placed in the N-nitrosamine solution until it became
fully saturated with N-nitrosamines. A sample of the solution (initial)
was removed to verify N-nitrosamine saturation on the CX electrode.
The amount of each N-nitrosamine (NDEA and NPY) adsorbed initially Fig. 5. Total N-nitrosamine removed (NDEA + NPY) as function of total charge
passed through the CX electrode.
by the CX matched the calculated maximum capacity (Section 3.2),
thereby confirming equilibrium before passing charge through the
electrode.
Simultaneous decomposition of the two N-nitrosamines in a solution
with 1% MEA (simulated CCS waterwash) was tested using the elec-
trochemical cell. Charge was passed through the CX electrode for 1 h at
set amperages (5–300 mA). After each experiment, a second sample of
the solution (final) was collected to measure the final N-nitrosamine
concentration remaining in solution. Additionally, the CX electrode was
dried and any residual N-nitrosamines remaining on the surface were
recovered through a methylene chloride extraction followed by GC/MS
analysis. Total N-nitrosamine decomposition was calculated by sub-
tracting the mass of N-nitrosamines remaining in solution, the mass of
N-nitrosamine recovered from the CX electrode and the mass removed
for analysis after saturating the CX electrode (initial) from the mass of
N-nitrosamines in the starting stock solution.
N-nitrosamine decomposition from the simulated CCS waterwash
solution showed considerable removal in N-nitrosamines of up to 92%
for NPY and 82% for NDEA at 300 mA for 1 h (Fig. 4). Only a marginal
difference in removal was observed with these two N-nitrosamines with
the exception of the 5 mA test. The removal was generally linear and
can be correlated to the amount of charge passed. The percentage of Fig. 6. Simple diagram of adsorption and electrochemically-mediated reduc-
total N-nitrosamine (NDEA + NPY) decomposition as a function of the tion process.
total amount of charge passed (Coulombs) was plotted in Fig. 5.
The final solutions from each experiment were analyzed for N-ni- electrodes were used to reduce N-nitrosamines in wastewater solutions
trosamine decomposition products to determine the possible decom- (Su et al., 2017).
position pathway. Two secondary amine compounds were identified, The production of DEA and PY measured did not close the mass
diethylamine (DEA) and pyrrolidine (PY), with increasing concentra- balance around the nitrosamine losses. Several factors may be con-
tion as the total charge passed increased. This suggests that the ap- tributing to this discrepancy. First, the analytical methods used for this
parent mechanism for decomposition is through electrochemically- initial screening have not been optimized for small molecule amines
mediated reduction of the N-nitrosamine to a secondary amine (Fig. 6). compounds, but were instead designed for nitrosamines. Second, it is
This type of decomposition reaction has been previously observed in a very likely that DEA and PY may also absorb onto the CX carbon and
similar electrochemical cell where functionalized carbon nanotube would not be readily observed in the remaining solution. Lastly, and
more importantly, the decomposition pathway may be more compli-
cated than expected with many intermediate products formed in addi-
tion to the amines, requiring additional studies, which are currently
ongoing.
The calculated Coulombic (Faradaic) efficiency of total nitrosamines
(NDEA + NPY) degradation was generally low, i.e., 0.8–6.9% at the
tested range of 5–300 mA. Low Faradaic efficiencies can be tied to side
reactions, e.g. dissolved oxygen reduction, carbon oxidation in aqueous
solutions, and gas evolution. In addition, the voltages associated with
these degradation processes (6–9 V) suggest that we need to improve
the electrochemical cell design, including reducing the distance be-
tween working and counter electrodes. Additional efforts will be also
need to look at the underlying mechanisms of NDEA and NPY de-
gradations using other techniques such as cyclic voltammetry and
electrochemical impedance spectroscopy.
N-nitrosamines have been identified in a variety of water sources
Fig. 4. N-nitrosamine decomposition with different applied current for 1 h (in beyond CCS, including in municipal and industrial wastewater (Hladik
1% MEA simulated waterwash solution). et al., 2014; Parker et al., 2014). N-nitrosamine removal processes that

88
J.G. Thompson, et al.
Fig. 7. N-Nitrosamine (NDEA) decomposition with constant applied current
(100 mA for 1 h) in three different matrices.
Fig. 8. Schematic of an electrochemical cell installed on a waterwash system
used to remove N-nitrosamines from a circulating waterwash solution.
can work in a variety of different solution matrices are also desirable.
To examine this, the decomposition of NDEA was examined in several
different solution matrices for CCS and wastewater applications. In this
case, solutions of 100 mg/L NDEA in 1 M NaCl, 0.3% MEA and 1% MEA
were tested and compared (Fig. 7). For each solution, a current of
100 mA was applied for 1 h. The final N-nitrosamine decomposition,
between 52–60%, was nearly identical in each matrix.
4. Future applications in CCS
As noted in the introduction section, the primary purpose of a CCS
waterwash is to reduce amine solvent emissions and return the capture
amine back to the solvent loop. During these experiments, the amine
(MEA) concentration in solution remained unchanged (< 1% loss by
mass and within the analytical error), confirming that it is unaffected
by the electrochemical treatment. This shows the specificity of the
proposed process to target N-nitrosamine in CCS waterwash solutions
while leaving the amine unaffected. This strengthens the case to use this
type of process on a CCS waterwash where N-nitrosamine can be se-
lectively removed while allowing the intact amine to be returned to the
solvent loop. Fig. 8 illustrates how the developed electrochemical cell
can installed to treat the circulating water wash solution.
Electrode materials can show deteriorating performance over time
due to oxidation on the surface or general deterioration from high ap-
plied voltages. This will also be an area of concern with this application.
Generally, the CX material is stable during multiple cycling experiments
(Xin et al., 2014, Electrochemistry Communications 39, 22-25.),
89
International Journal of Greenhouse Gas Control 83 (2019) 83–90
however the relative high applied voltages used in these experiments,
especially above 25 mA, will limited the usable lifetime of this material.
Improving the cell design to increase the lifetime of the CX electrode
material will be a key component of future development of this process.
Additional optimization of this process can come of an under-
standing the nitrosamine adsorption kinetics onto the CX as a function
of time, in addition to the decomposition kinetics. This will add addi-
tional information and may help develop other nitrosamine mitigation
strategies.
5. Conclusions
Waterwash columns are common in amine-based CO2 capture sys-
tems to help control volatile and aerosol solvent emissions to reduce
solvent makeup costs and environmental emissions. Adding a sub-
system to the waterwash to adsorb and decompose N-nitrosamines will
be beneficial if it does not decompose the amine, is robust, and can
control N-nitrosamines to very low levels. This preliminary study shows
the effectiveness of electrochemically-mediated reduction process using
carbon xerogel (CX) electrode material to decompose hazardous N-ni-
trosamine compounds from CCS waterwash solutions. The carbon xer-
ogel material has a high N-nitrosamine adsorption capacity and can
initiate an electrochemically mediated reduction of N-nitrosamines
from water containing high amine or salt concentrations. This electro-
chemical strategy can be further optimized as an effective method for
the removal of N-nitrosamines from wastewater and amine−CO2 cap-
ture waterwash streams. Future testing is planned with higher amounts
of charge passed through the cell, alternative CX materials, testing with
different N-nitrosamines, different water wash solution compositions,
and real solutions from bench and pilot-scale waterwash systems.
Acknowledgements
The authors acknowledge the Carbon Management Research Group
(CMRG) members, including Duke Energy, Electric Power Research
Institute (EPRI), Louisville Gas & Electric (LG&E) and Kentucky Utilities
(KU) for their financial support.
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