Zhang Asu 0010E 15975
Zhang Asu 0010E 15975
Zhang Asu 0010E 15975
by
Jinwei Zhang
May 2016
ABSTRACT
found in clouds and fogs at concentration up to 500 ng/L and in drinking water as
disinfection by-product. NDMA exposure to the general public is not well understood
because of knowledge gaps in terms of occurrence, formation and fate both in air and
water. The goal of this dissertation was to contribute to closing these knowledge gaps
Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas
sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to
have more impact than inorganic species on NDMA photolysis by competing with
NDMA for photons and therefore could substantially increase the NDMA lifetime in
aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a
higher mass absorption efficiency (MAE) than organic matter in fog and cloud water,
resulting from a different composition, especially in regards of volatile species, that are
samples including wastewater, surface water and ground water, at two monochloramine
concentrations. A simple second order NDMA formation model was developed using
i
measured NDMA and monochloramine concentrations at select reaction times. The
model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed
model was then optimized and applied to fit the data of NDMA formation from natural
organic matter (NOM) and model precursors in previously studies. By determining the
rate constants, the model was able to describe the effect of water conditions such as
ii
ACKNOWLEDGMENTS
First and foremost, I would like to thank my advisors, Dr Pierre Herckes and
Dr Paul Westerhoff, for their support and guidance on my science projects as well as
life. Without their help I would not have been able to accomplish and achieve my
goals. I really appreciate their encouragement, criticism and inspiration. I would also
Everett Shock as well as Dr Hilairy Hartnett and Dr Timothy Steimle for all of their
Westerhoff Groups at ASU: David Hanigan, Youliang Wang, Jershon Eagar, Aurelie
Marcotte, Sarah Frey, Denise Napolitono, Christy Rose, Taka Nosaka, Samantha
Donovan, Jun Wang and Fariya Sharif. I would like to thank all of the Arizona State
University School of Molecular Science staff for their hard work and help. I would like
to thank all my other friends in Arizona and other states in United States
At last, I want to say thank you to my parents and sister, who have provided
Chengyu, for her support and love in the past ten years.
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TABLE OF CONTENTS
Page
CHAPTER
iv
CHAPTER Page
.................................................................................................82
vi
CHAPTER Page
REFERENCES .........................................................................................................111
APPENDIX
vii
LIST OF TABLES
Table Page
Method ............................................................................................................28
Concentrations ...............................................................................................40
4.1 Water Quality, Treatment and NDMA Formed in Source Waters .................65
5.3 Optimized Rate Constant kapp for Model Compounds under Various Reaction
5.4 Optimized Rate Constant kapp for Model Compounds in Different Water
Matrices with Varied TOC. (NDMA Data from Shen and Andrews, 2011b)
.........................................................................................................................89
viii
LIST OF FIGURES
Figure Page
1.3 NDMA Formation Pathway of DMA and (a) Monochloramine (Choi and
Valentine, 2002; Mitch and Sedlak, 2002a) and (b) Dichloramine (Schreiber
.........................................................................................................................24
3.1 Image of Irradiation Setup with the Water Chiller, Irradiation Flask, Lamp,
3.2 UV-Vis Absorbance of WSOC with 1 mg/L Nitrate and 1.4 mgC/L Dissolved
Organic Carbon (a), 1 mg/L Nitrate (b) and the Dissolved Organic
Components (a-b)............................................................................................41
3.3 AAE for WSOC from Aerosol and Fog/Cloud Samples ...............................42
3.4 Correlation of Absorbance at 365 nm vs. WSOC for Aerosol Extracts and
ix
Figure Page
4.1 (A) Monochloramine (NH2Cl) Decay Kinetics in WW1 for Two Initial
Fitted by Equation 2&3 (lines). Error Bars Represent One Standard Deviation
4.2 NDMA Formation Observed (symbols) and Fitted by Equation 2&3 (line) in
Standard Deviation (n = 3) for Select Time Points. (pH = 8.0, 23 ± 1 °C) ....60
4.3 NDMA Formation Observed (symbols) and Fitted by Equations 2&3 (line) in
Concentrations in all Waters. Data from all Reaction Time Periods are
Included ..........................................................................................................66
4.5 Plots of P/P0 versus Monochloramine Exposure for Water Samples (a) WW1,
(b) WW4, (c) GW1, (d) SW1. L = Lower, H = Higher, Represent Samples
5.1 NDMA Formation Pathways as Proposed in the Literature: (1) Choi and
Valentine, 2002; Mitch and Sedlak, 2002a. (2) Schreiber and Mitch, 2006b. (3)
x
Figure Page
Observation Data, Lines: Model Predictions, pH=7. Data from Chen and
5.4 NDMA Formation from Model Precursor Compound Data (Symbols), Model
0.04mM, pH=7.5) and SDS Conditions with Excess Ammonia. (NDMA Data
(Symbols) and Model Fitting (Lines) (NDMA Data from Shen and Andrews,
2011b) .............................................................................................................90
6.2 Distribution Diagram for Chloramines with pH (Palin, 1950; USEPA, 1999)
.........................................................................................................................93
6.3 NDMA Formation Kinetics of Wastewater Effluents with and without Excess
6.4 NHCl2/NH2Cl Ratio with and without Excess NH4+ in Nano Pure Water at
pH=7 ...............................................................................................................99
xi
Figure Page
Deviation (n=3) for Select Time Points. (pH = 8.0, 23 ± 1°C ) ....................100
6.7 (a) NDMA Formation from Model Precursors (pH=8); (b) NDMA Formation
.......................................................................................................................103
xii
CHAPTER 1
family, since it is the most widely detected nitrosamine in water with high toxicity
(Krasner et al., 2013). NDMA has been detected in all environmental compartments
including air, soil and water (ATSDR, 1999). It was initially recognized as
industry (Brubaker et al., 1985; Lunn et al., 1991; Lunn and Sansone 1994). It can also
rubber, pesticide and other amine related chemical plants (Fajen et al. 1979;
Spiegelhalder and Preussmann, 1981, 1983; Stefan and Bolton, 2002). NDMA is also
found in a variety of foodstuffs such as cured meat (e.g. sausage, bacon), fish products,
dairy and cheese products, and alcoholic beverages (Tricker and Preussmann, 1991). It
originates from reactions of nitrosating agents (e.g. nitrite, nitrogen oxide) and amines
contained in the food products. NDMA was also identified in indoor environments with
active tobacco smoking (Brunnemann and Hoffmann, 1978; Ruhl et al., 1980).
especially NDMA (IARC 1987; Afonso Perera 2006). Although there is no direct
from food, environment and in-vivo formation in human body have been associated
with higher risk of cancer (Fajen et al. 1979; Bartsch and Spiegelhalder 1996; Mirvish
1995; Straif et al, 2000; WHO, 2002b). NDMA can enter the human body by ingestion,
inhalation and through dermal exposure. Ingestion occurs when people eat and drink
food and water that contains NDMA. Inhalation exposure is mainly related to polluted
air and particulate matter in the atmosphere. Dermal exposure could happen when skin
gets in contact with rubber-made things, detergent or water that contains NDMA.
However, it was calculated that daily dermal exposure during shower from water is
only 0.04% of ingestion of same water (OEHHA, 2006). While NDMA may be avoided
in foodstuffs by choosing not to eat certain foods, it is not possible to avoid air
regulatory determinations of NDMA and other nitrosamines in water and air. Currently
(UCMR 2) (USEPA, 2005) and the Contaminant Candidate List 3 (CCL3) (USEPA,
2009). For NDMA in the air, the USEPA has calculated a residential air screening level
of 0.07 ng/m3 (exposure of 24 h/day in 26 years) and an industrial air screening level
of 0.88 ng/m3 (exposure of 1h/day in 25 years) at a target cancer risk (TR) of one in
one million (10-6) (USEPA, 2015). USEPA’s Integrated Risk Information System
2
(IRIS) database indicates that a drinking water concentration of 0.7 ng/L is associated
with 10-6 lifetime cancer risk. Local government has taken actions to regulate NDMA
Assessment (OEHHA) set a public health goal at 3 ng/L for NDMA and California’s
Department of Public Health (CDPH) has set 10 ng/L notification for nitrosamines
Since the 1970s, NDMA has been reported in the air in industrial and urban
associated with industrial processes. The highest gas phase NDMA concentrations (130
µg/m3) ever reported were found in indoor work places in the rubber industry
(Spiegelhalder and Preussmann, 1981). Fine et al. (1976) reported 36 µg/m3 near the
closed office with smokers (Stehlik et al., 1982; Mahanama and Daisey, 1996). All the
NDMA concentrations reported before were orders of magnitude higher than the
USEPA suggested screening level of NDMA, mostly because they were measured in
highly polluted /industrial areas or indoor environments. Due to its low vapor pressure
(2.7mm Hg at 20 °C) NDMA, is more likely to exist in gas phase than to absorb to
Nitrosamines up to 161.4 ng/m3 in PM2.5 and 53.90 ng/m3 in PM2.5-10 were monitored
alkylamines. In the dark, nitrosating agents such as nitrous acid (HONO) formed from
reaction of nitrous oxides (e.g. NOx) and water vapor react with gas phase alkylamines
(Tuazon et al., 1984). The UV-Vis absorption spectrum of NDMA shows two
respectively (Figure 1.2) (Plumlee and Reinhard, 2007). Absorption at 230 nm is not in
the range of natural sunlight in the atmosphere, but NDMA absorption around 330nm
overlaps with sunlight and is responsible for the direct photolysis of NDMA. In the gas
phase, NDMA gets photolyzed quickly with a half-life of 5min (Tuazon et al., 1984).
NDMA in pure deionized water undergoes a similarly fast photolysis with half-lives of
3-18 min depending on irradiation intensity (Stefan and Bolton, 2002; Plumlee and
Reinhard, 2007; Hutchings et al., 2010; Chen et al., 2010). The short half-lives of
NDMA in air and water suggest that it is not persistent in the environment.
4
Figure 1.2: UV-Vis absorbance of nitrosamines in water and solar simulator spectra
(Plumlee and Reinhard, 2007)
atmospheric droplets (clouds and fogs) (Herckes et al., 2007; Hutchings et al., 2010).
In the Hutchings et al. (2010) study, it was suggested from model calculations that the
NDMA in droplets was not from the in-cloud nitrosating reaction between DMA and
nitrite due to the low formation yields (~1%). The source of NDMA in clouds and fogs
is probably from gas phase formation of NDMA and partitioning of gas phase NDMA
into aqueous phase because of the high water solubility of NDMA. In lab experiments
the NDMA photolysis rate was significantly reduced in the presence of organic carbon
(DOC = 2.0 mgC/L) and nitrite (1 mg/L). The lack of NDMA photolysis was attributed
to light-shielding by nitrite as it competes with NDMA for sunlight photons near 330
nm (Stefan and Bolton, 2002). The WSOC may also affect photolysis of NDMA since
DOC in surface water matrices (Stefan and Bolton, 2002; Plumlee and Reinhard, 2007;
Chen et al., 2010). Due to such possible light-shielding effect in droplets, the high
5
concentrations of NDMA in fogs may result from NDMA formation in gas phase,
accumulation in the droplets in the dark and persistence with little photolysis in droplets
Most recently NDMA and other nitrosamines have been of growing concern
capture pilot plant in Maasvlakte, Netherlands (da Silva et al., 2013). In post
combustion CO2 capture (PCCC) plants, amines are used as solvents to capture and
store CO2 to decrease the CO2 emissions. Nitrosamines can be formed as amine
degradation products though reactions with NOx in the flue gas (Masuda et al., 2000;
Reynolds et al., 2012). The amines in emission gas could also react with nitrosating
agents (e.g. NOx) present in atmosphere from various combustion sources to form
nitrosamines. Such reactions will generally follow mechanisms similar to the pathway
in Equations 1-1&1-2. The NDMA formed in the air would probably partition into
cloud droplets and end up in soil or surface water by precipitation if not photolyzed.
NDMA was found in drinking water wells near a rocket engine testing facility
County, CA in 1998 (Mitch et al., 2003). In 2002, two drinking water production wells
al., 2013). Ozonation of DMA has been reported to only form NDMA at low yields
6
(<0.02%) at acidic or basic pH (Andrzejewski et al., 2008; Yang et al., 2009).
sulfamide functional groups, forms NDMA with more than 50% yield, resulting in more
than 10 ng/L NDMA formation in drinking water (Schmidt and Bruch, 2008; Von
precursors.
NDMA formation. Choi and Valentine (2003) reported such formation starting with the
intermediate then forms NO* which will nitrosate the amine precursor (e.g. DMA). The
pathway is of little importance in drinking water due to the low formation yields and
low concentrations of nitrite in drinking water (Shah et al., 2012). However, NDMA
Activated carbon can catalyze the formation of NDMA from secondary amines.
Reactive nitrogen species formed on surface of activated carbon react with a secondary
amine like DMA and form NDMA at low yields (<0.3%) (Padhye et al., 2011). With
the low concentrations of DMA in drinking water, the pathway is considered unlikely
Compared to chlorination or ozonation, most studies have found that NDMA formation
is mainly associated with chloramination (Choi and Valentine, 2002; Mitch and Sedlak,
drinking water systems and the population using drinking water containing chloramines
has increased from 17% in 2007 to 22% in 2010 in United States (Li, 2011). NDMA
detections in high concentrations in treated drinking water (67 ng/L) and in higher
from water systems using chloramine and only 3% of samples from those using chlorine
presented detectable levels of NDMA. All samples that had NDMA concentrations
higher than 50 ng/L, were from systems with the highest fraction of chloramine use
(Russel et al., 2012). Plants using chloramine with longer hydraulic contact times in
plant and distribution system (e.g., 12–18 hr) tend to form more NDMA in the water
system than plants using chloramine for shorter (e.g., 0.5–2 hr) contact times (Krasner
et al., 2012).
The precursors of NDMA are from three main sources: wastewater treatment
effluent, natural organic matter (NOM) and in-plant treatment chemicals. Wastewater
has been identified as the most important precursor source producing 300-1300 ng/L
NDMA in chloramination (Mitch and Sedlak, 2004). NOM can be precursor for NDMA
when nitrogen in organic matter reacts with chloramines. Water treatment chemicals
also showed the potential for NDMA formation. For example, coagulation polymers
leading to higher NDMA formation potential (FP) (Najm and Trussell, 2001; Kohut
formed from primary amines decay quickly and are not stable (Ridd, 1961). DMA, the
secondary amine precursor of NDMA, has been studied a lot as the model precursor of
NDMA (Mitch and Sedlak, 2002a; Choi and Valentine, 2003; Andrzejewski et al.,
2008) due to its occurrence in natural waters. Mitch and Sedlak (2002a) and Choi and
1.3a). It was later found that NDMA formation yield in chloramination of UDMH is at
least two orders of magnitude lower than that in chloramination of DMA; and the
formation rate was also much slower in chloramination of UDMH (Schreiber and
dissolved oxygen was then discovered. It was observed that dichloramine which forms
9
Figure 1.3: NDMA formation pathway of DMA and (a) monochloramine (Choi and
Valentine, 2002; Mitch and Sedlak, 2002a) and (b) dichloramine (Schreiber and Mitch,
2006b)
In this pathway dichloramine reacts to form NDMA via the formation of a Cl-
UDMH intermediate and the intermediate is then oxidized by dissolved oxygen in water
to produce NDMA (Figure 1.3b). Some tertiary amines, such as trimethylamine (TMA),
can also act as a significant NDMA precursor in chloramination (Mitch and Schreiber,
release DMA that forms NDMA in chloramination via the reaction in Figure 1.3b.
However, with the low NDMA yield and low alkylamine (DMA or TMA)
pharmaceuticals and personal care products, in wastewater. Some other tertiary amines
with NDMA yields higher than DMA were found. For example, ranitidine, the active
at yields between 60-90% (Le Roux, 2011; Shen and Andrews, 2011a, b). In a more
10
NDMA yields from methadone ranged from 23%-70% depending on chloramine dose.
methadone. These high formation yields indicate that such tertiary amines do not form
amines (10 aliphatic and 11 aromatic) and they suggested that the NDMA formation
mechanism starts with a nucleophilic attack of the DMA functional group on the
nitrogen in chloramines (Figure 1.4). Through this pathway amines with electron
monochloramine while amines with electron donating groups react preferentially with
dichloramine. The NDMA formation yields are associated with the structure of the
leaving group in the amine precursors. Most amine precursors could react with both
Figure 1.4: NDMA formation pathway of amine precursors and chloramines (Selbes,
et al., 2013).
besides the precursor amines structure and stability. Chloramine speciation may be the
most important factor. Reactions between chlorine and ammonia form chloramines.
11
monochloramine formation is dominant at pH higher than 8 with 5:1 or less Cl2:N mass
start to form as pH decrease and Cl2:N increase. The pH also has an impact on the amine
precursor. For example, the maximum NDMA formation from precursors such as DMA
or ranitidine were observed between 7 and 8 (Mitch and Sedlak, 2002b; Kim and
Clevenger, 2007; Shen and Andrews, 2013a). It was suggested that at pH lower than 7
chloramines; and at higher pH, there is lower dichloramine formation resulting in lower
NDMA production. However, due to the fact that NDMA formation is not limited to
only one chloramine species, the pH effect on NDMA would vary with precursors and
their reactivity to chloramines. Chloramine dose and contact times are important
factors. Experiments have shown higher NDMA concentrations with higher chloramine
doses (Sacher et al., 2008) or longer contact times in drinking water distribution
Schreiber and Mitch (2006) suggested the rate of NDMA formation from DMA and
chloramination follows a first order kinetics and a second-order reaction kinetics was
assumed for NDMA formation from ranitidine and monochloramine. However, the
NDMA formation was not found related to decomposition of ranitidine. Shen and
formation kinetics. The developed model fitted NDMA formation from four
pharmaceuticals (e.g. ranitidine) in surface water very well, but it did not provide
in wastewater due to the complexity of precursor types and various NDMA formation
mechanisms.
NDMA toxicity, occurrence and formation have been widely studied over
several decades now, in food, air and water. Despite all this work, NDMA exposure of
the general public is still not well understood because of knowledge gaps in terms of
occurrence, formation and fate, both in air and water. This work aims to contribute to
carbon sequestration efforts, novel, sensitive but cheap methods of measuring gas phase
Extraction (SPE) and Solid Phase Microextraction (SPME) coupled with Gas
Chapter 2 of this thesis. Typical analytical methods in previous studies were not able
logistically challenging to perform. We have therefore developed SPE and SPME based
water or foodstuffs to the determination of NDMA in air. The SPE method was then
applied in field sampling and NDMA were measured in ambient air. The new methods
will provide us with more easy and economical ways to measure NDMA at in gas phase
and help to investigate NDMA formation, transportation and health risk in the
atmosphere.
13
The fate of atmospheric NDMA is strongly linked to its photolysis, which is the
main atmospheric sink of the compound together with cloud processing. The fate of
NDMA in fogs and clouds remains not well understood because of the potential
“screening effect” resulting from the competition of photons from other cloud
constituents like ions and organic matter. Any such screening effect will delay
inorganic ions and dissolved organic carbon in atmosphere relevant concentrations. The
compounds. An extensive characterization of the water soluble organic carbon was then
performed to show that the optical properties like mass absorption coefficient (MAE)
(aerosol, fog, cloud) and by location or particle size. The results suggest that the
absorptivity of water soluble organic matters in aerosol more than that in atmospheric
Besides the air we were also interested in the aqueous formation during water
treatment, in particular chloramination. Until now very little research has been
and simulated distribution system (SDS) conditions. A second order reaction model of
chloramination. The model fits NDMA formation well (R2 > 0.88) in all source waters;
and rate constants were in a narrow range (0.01–0.09 M-1s-1) for different waters.
14
In Chapter 5 the NDMA formation kinetics model developed in Chapter 4 was
applied to NDMA formation data from the literature including different water sources
and model compounds. The kinetic model parameters were optimized and the resulting
model performances are discussed. The model fitted NDMA formation from model
compounds and surface water under a variety of reaction conditions. The rate constants
were able to describe how water conditions such as DOC and pH affect the NDMA
formation kinetics.
takes monochloramine into account as the oxidant while dichloramine have shown
influence on the NDMA formation kinetics. In Chapter 6 some more experiments were
designed and conducted to further develop the kinetic model of NDMA formation.
Parameters such as dissolved oxygen, chloramine speciation and buffer solution were
15
CHAPTER 2
2.1 Introduction
has been of great concern since it was discovered at up to 130 µg/m3 and 36 µg/m3in
industrial and ambient air respectively in the 1970s (Fine et al., 1976a, b; Walker et al.,
(such as rubber, leather and rocket fuel production) and around sources of nitrosamine
environments with active tobacco smoking (Brunnemann et al., 1977; Stehlik et al.,
1982; Mahanama and Daisey, 1996). At that time substantial research on occurrence in
In recent years NDMA in ambient has received renewed interest for several
reasons. First, recent studies have detected NDMA in concentrations up to 500 ng/L in
fogs and clouds (Herckes et al., 2007; Hutchings et al., 2010), due to the high water
droplets. Although NDMA is very easily photolyzed in the gas phase (Tuazon et al.,
1984), it can be formed in nighttime air as the result of the atmospheric reaction of
dimethylamine with nitrogen oxides (Hanst et al., 1977) and the subsequent partitioning
into the cloud droplets appears to contribute most of the NDMA in fogs and clouds
(Hutchings et al., 2010). In addition, model calculations have shown that NDMA may
remain in air for more than 4 hours even past sunrise. This led to an emerging concern
for the development of carbon sequestration and storage. In fact, in the process of
nitrosamines in air (Strazisar et al., 2003; Nielsen et al., 2012). NDMA was also
reported in particulate matter PM2.5 and PM10 at ng/m3 level (Akyüz and Ata, 2013;
Farren et al., 2015). U.S.EPA has calculated a residential air screening level of 0.07
ng/m3 (exposure of 24 h/day in 25 years) and an industrial air screening level of 0.88
ng/m3 (exposure of 1h/day in 25 years) at target cancer risk of 10-6 (U.S.EPA 2015).
Hence, monitoring NDMA in air is crucial with the reemerging concern about NDMA
in the air.
air have been developed over the past few decades. Among them are wet sampling
techniques using cold traps and wet traps such as KOH (Spiegelhalder and Preussmann,
1983; Mahanama and Daisey, 1996) ; however, these labor intensive wet trap
techniques had sample recovery problems (Mahanama and Daisey, 1996) and the
preparation of aqueous traps was challenging in field settings. Then sampling cartridges
containing various dry sorbents (e.g. silica gel) were developed to collect NDMA from
the gas phase (Rounbehler et al., 1980; Spiegelhalder and Preussmann, 1983). Still
some limitations persisted such as the need for a nitrosation inhibitor to prevent
found to be the only sorbent free of artifact formation (Rounbehler et al., 1980).
standard nitrosamines monitoring methods such as those by the Occupational Safety &
Health Administration (OSHA) or the National Institute for Occupational Safety and
Health (NIOSH) with a detection limit at µg/m3 levels (OSHA, 1981; NIOSH, 1994).
17
In the recent studies the detection limit of nitrosamine was reported less than 0.1ng/m3
by using thermosorb/N and GC-TEA (Tønnesen et al., 2011). The low detection limit
was achieved using a specifically constructed multi-line sampling device and very large
volume (>100 m3) air sample which is substantially larger than the validated sample
concentration.
(Karl et al., 2013) and selected ion flow tube mass spectrometry (SIFT-MS) (Langford
injection, these methods are quite limited because of their high detection limits,
aqueous samples. Solid phase extraction (SPE) coupled with GC-MS was one of the
most widely used method determining NDMA in wastewater and drinking water
(Munch and Bassett, 2004; Hanigan et al., 2012; Selbes et al., 2013). Solid phase
microextraction (SPME) with GC-MS or GC-TEA were also employed for measuring
nitrosamines in aqueous and food matrices (Andrade et al., 2005; Grebel et al., 2006;
In the present work we are evaluating the use of commercial SPME or SPE
of gas phase NDMA. Positive and negative artifact formation was investigated for the
more sensitive SPE method and the optimized method was applied to determine NDMA
NDMA (solution in methanol, 5000 mg/L), EPA 8270 nitrosamine mix (solution
in methanol, 2000 μg/L) and dimethylamine (DMA) (solution in methanol, 2.0 M) were
d6) (1 g/L in methylene chloride (DCM)) was purchased from Cambridge Isotopes
(Andover, MA). All the above stock solutions were then diluted to desired
concentrations using DCM (Optima Grade, Fisher Scientific, Waltham, MA). All
standards were stored in a freezer prior to use. Aqueous NDMA solutions were prepared
Louis, MO). Nitric oxide gas (>99.5%) was purchased from Praxair (Bethlehem, PA)
used as detailed in Figure 2-1. Continuous airflow containing gas phase NDMA was
in a 250 mL gas washing bottle. In the SPE sampling tests, a continuous gas flow went
through two successive coconut charcoal SPE cartridges (2 g/6 mL, Supelco, Bellefonte,
PA). The second cartridge was used to test for possible breakthrough. During the entire
19
sampling, SPE cartridges were wrapped with Aluminum foil to prevent photolysis of
collected NDMA.
A similar set-up was used for SPME testing. The air containing NDMA passed
through an SPME gas sampling bulb (Sigma-Aldrich, St. Louis, MO) at a constant
flowrate as shown in Figure 2.1. A manual SPME holder was employed in extraction
One potential artifact during NDMA collection onto SPE cartridges is NDMA
formation through reactions between dimethylamine (DMA) already sorbed onto the
cartridge and nitric oxides (NOx). To test the potential impact of this artifact, SPE
cartridges were loaded with DMA passing a DMA solution over the cartridge followed
by drying the cartridge with nitrogen gas for 30 minutes. Then laboratory air mixed
with NOx at concentrations ranging from 0 to 30 ppb was passed through the pretreated
20
SPE cartridges. For each sample, NOx containing air was passed through cartridges for
0.5-8 h at 3.7 L/min. Control experiments without preload DMA and /or NO x were
A negative artifact could occur if NDMA sorbed to the SPE cartridges degrades
during sampling, e.g. is oxidized or photolyzed. This negative artifact was evaluated by
passing ambient dry air with high oxidant concentrations through SPE cartridges which
were preloaded with NDMA. Sampling times ranged from 5 minutes to 1 hour. All
these negative artifact tests were performed on the roof of Life Science Building in
Arizona State University Tempe campus and in sunny afternoons between 2 PM and 4
PM in summer when oxidants such as ozone and OH radical were at their highest
Ambient air samples were collected at the Tempe campus of Arizona State
sampling was clear with no rain or fogs. Air samples were acquired using a laboratory-
built gas sampler consisting of an air pump that was operated at 5- 8 L/min drawing
ambient air through a coconut charcoal SPE cartridge. The flowrates were monitored
at the beginning and the end of the sampling period. The cartridges were wrapped in
aluminum foil during the collection and then kept frozen after collection until analysis.
Prior to extraction, all SPE cartridges were spiked with 100 μL NDMA-d6 at
1ppm as internal standard. Nitrosamines and NDMA-d6 were then eluted from SPE
cartridges with 30 mL of DCM. After extraction, the DCM extracts were treated with
anhydrous sodium sulfate to remove water residual and then concentrated under stream
21
of Ultra High Purity (UHP) nitrogen gas to 250 μL. The final extracts were stored in
The sample extracts were analyzed using an Agilent 6890N/5973 inert GC/MS
operated in positive chemical ionization mode with ammonia as the reagent gas
(Charrois et al., 2004). In brief, the chromatographic column used was an Agilent DB-
1701P (30 m × 0.250 mm × 0.25 μm)( Santa Clara, CA) and followed a pulsed splitless
injection (initial pulse 15 psi for 45 s and then 10 psi) set at 250°C with a reduced
diameter SPME inlet linear (Sigma Aldrich, St. Louis, MO). The helium carrier gas
was initially pulsed at 1.9 mL/min for 45 s and then reduced to 1.3 mL/min for the rest
of the run. The oven temperature was initially 40°C for 3 min followed by an increase
to 80 at 4°C /min, and a final temperature increase to 120 at 20°C/min when NDMA
were tested. The column interface temperature was set at 200°C. The mass selective
detector was set to analyze for mass-to-charge 92 (NDMA + NH4+) and 98 (NDMA-d6
+ NH4+). The GCMS was calibrated with a series of authentic standards and
In SPME tests, each fiber was conditioned in the GC inlet at 250°C to remove
any contaminants for 5 minutes and cooled down to room temperature prior to sampling.
SPME fibers were exposed in a gas sampling bulb where laboratory air containing
NDMA passed through. After a defined amount of exposure the fiber was retracted into
the needle and immediately injected into the heated injection port at 250°C for 5
minutes using the same GC-MS method described above. Blank air samples were also
22
2.3 Results and Discussion
were examined for gas phase NDMA measurements. A variety of SPME fibers were
developed and applied to measure N-nitosamines in water and food matrices in previous
studies (Andrade et al., 2005; Grebel et al., 2006). These two fibers were selected
because they were more widely used with more N-nitrosamines extraction compared to
(CW/DVB).
equilibration times were tested from 30 minutes to 9 hours for both SPME fiber coatings
at different NDMA concentrations. Figure 2.2a and 2.2b show the effect of time on the
NDMA recoveries on two SPME fibers respectively. For the CAR/PDMS fiber, the
response area of NDMA kept increasing with time even after 9 hours (Figure 2.2a)
suggesting that equilibrium was not yet reached. Previous studies reported shorter
fiber (Figure 2.2b). Previous studies measuring NDMA in beer reported 200h as
equilibrium time for the same SPME fiber. It is possibly because of the competition or
and Henry’s constant derived from our measurements. For the same NDMA
concentration in air (9 μg/m3) for all extraction time periods the NDMA signals and
23
hence adsorbed NDMA in the CAR/PDMS fiber were more than one order of
magnitude higher than that in the PDMS/DVB fiber. It agreed with previous findings
that CAR/PDMS fiber outperformed the PDMS/DVB fiber in terms of NDMA recovery
(Grebel et al., 2006; Ventanas and Ruiz, 2006). CAR and DVB are both porous solids
which enhance the sorption. Pore size distribution is different. CAR had a higher
proportion of micropores (<20 Å) than the DVB (Lestremau et al., 2001), making it
more efficient to extract low molecular weight polar compounds such as NDMA.
a
5
18µg/m3 NDMA
4 9 µg/m3 NDMA
GCMS response *10 6
0
0 2 4 6 8 10
Time (hour)
b
7
6
GCMS response *10 4
3
1 9 µg/m NDMA
3
4.5 µg/m NDMA
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time (hour)
Figure 2.2: GC-MS responses of NDMA absorbed on SPME fibers at different
sampling times, a: CAR/PDMS fiber coating, b: PDMS/DVB fiber coating
24
Linear regression analysis of adsorbed NDMA at three concentration levels was
performed for both SPME fiber coatings by plotting the calibration curves of obtained
mass spectrum response area versus the gas phase concentration of NDMA. Extraction
time of 30 minutes was chosen for both SPME fibers. Though the CAR/PDMS had
longer equilibrium time, it still could be used in NDMA analysis by using non-
equilibrium extraction at a selected extraction time (Grebel et al., 2006). The correlation
coefficients were 0.97 and 0.81 for PDMS/DVB and CAR/PDMS fibers respectively,
reproducibility caused by CAR coating (Popp and Paschke, 1997) and non-equilibrium
regime. The influence of the air flowrate was also tested by varying the sampling flow
through the gas sampling bulb from 0.1 L/min to 1L/min (PDMS/DVB fiber) in 30mins
sampling intervals. The amounts of NDMA detected were very stable with a low
signal-to-noise (S/N) ratio equals 3, were 8 ng/m3 and 0.5 ng/m3 for PDMS/DVB fiber
and CAR/PDMS fiber, respectively. The detection limit was not sensitive enough to
detected NDMA at levels lower than 1 ng/m3. However the SPME sampling method
In a first stage, the sampling efficiency of commercial SPE cartridges was tested.
No NDMA was detected in the third cartridge when three cartridges were used in series,
even at high gas phase NDMA concentrations (16 µg/m3) and/or high flowrates (6
L/min). Two consecutive cartridges were used in tests to quantify breakthrough and
25
physical losses by re-volatilization of sorbed material. The collection efficiency was
defined as the amount of NDMA collected in the first cartridge divided by the amount
evaluated in two ways. First is to pump the air containing NDMA through the cartridges.
Flowrate ranged from 0.3 L/min to 5.8 L/min. The NDMA concentration were changed
from 16 µg/m3 to 3 ng/m3. Laboratory air only was also tested with NDMA
concentration of 0.8 ng/m3. As shown in Table 2-1, the SPE cartridge had collection
efficiencies higher than 90% in most tests. NDMA concentrations and flowrates
showed no effect on the collection efficiency. Second is pumping the air through the
two cartridges after spiking 100 ng NDMA on the upstream cartridges. The cartridges
were dried with laboratory air for 30 minutes at 5.8L/min. After 30 minutes drying, the
downstream cartridge was connected to collect the breakthrough or the physical losses
from the first cartridge. No detectable NDMA was found in the second cartridges after
the calculated gas and aqueous phases concentrations of NDMA was 5.3 ± 0.4 × 10-7
26
atm×m3/mol at 22°C. With huge variance of flowrates (0.1-6 L/min) and NDMA
concentrations (3-16000 ng/m3) the calculated Henry's law constant only change with
a small variance (< 10%). Previous studies reported several different Henry’s law
constant at different temperatures (Mirvish et al., 1976; Haruta et al., 2011). At 22°C,
Henry’s law constant determined in our experiments was twice of the reported Henry's
constant (2.63 × 10-7 atm×m3/mol at 20°C) which was estimated by using vapor
pressure and water solubility data (Mirvish et al., 1976). The difference was not
substantial considering the fact that the tests in this work were in a dynamic aqueous-
gas system and were at a higher temperature. The Henry's law constant in our dynamic
experiment conditions can be used to determine NDMA gas phase concentrations when
NDMA water phase concentrations are known. For NDMA, the sensitivity of the
analytical detection method, which was estimated as 3 times of the background noise,
was 0.04 pg/injection. For an air sample of 0.1 m3 (~30 min at 3L/min), the detection
limit of the overall method was 0.06ng/m3. With larger sampling volumes e.g. 2 m3
obtained by extending sampling time or increasing flowrate the detection limit can be
as low as 0.003 ng/m3. With such a low detection limit, small sample volume and simple
set-up sampling instrument, the SPE sampling method with the following GCMS
analysis presented in this work is more applicable than all previous methods in NDMA
27
Table 2.2: Sampling parameters in this work compared to Thermosorb/N sorbent
method.
SPME GCMS SPE Thermosorb/N
CAR/PDMS PDMS/DVB (activated UHPLC1
carbon)
GCMS
Sample time (h) >0.5 0.5 0.5-8 167
Sample Volume (m ) 3 - - 0.1-2 20
3
Detection limit (ng/m ) ~1 8 0.003 0.01
Sample breakthrough - - <10% unknown
Flowrate (L/min) - 0.1-1 0.3-6 2
1.
Nielsen et al., 2012
The sources of atmospheric NDMA are not only direct emissions of NDMA by
industrial processes but also nitrosation of atmospheric amines (Hanst et al., 1977).
These nitrosating reactions could possibly occur on the surface of the collection
cartridges during sampling if sorbed amines react with a nitrosating reagent (i.e. NOx),
leading to a positive artifact formation. The latter was a concern as it was reported that
commercial activated carbon could catalyze the formation of reactive nitrogen specious
(e.g. NO) from oxygen and nitrogen in the reactive sites on the activated carbon
surfaces (Padhye et al., 2011). Therefore the possible formation of NDMA from the
reactions between Dimethylamine (DMA) and such NOx during the sampling process
was explored. One nanomole DMA in DCM solution was spiked onto the cartridges,
simulating maximum DMA in 0.1 m3 ambient air (Ge et al., 2011). Pure NO was diluted
in lab air to 30 ppbv which was similar to the upper limit of NOx concentrations in
ambient conditions. After pumping the NOx/air mixture through the cartridges, the
substantially higher DMA (1µM) loadings, NDMA was detected. The overall NDMA
28
formation yield (NDMA formed/DMA spiked) was 0.15% when lab air with no NO x
passed the cartridges. The formation yield increases to 0.24% in the presence of air
containing 30 ppbv NOx. Previous studies reported the similar NDMA formation yields
0.05% -0.29% in air-dried activated carbon particles from preloaded DMA (Padhye et
al., 2011). In actual ambient air (~pmol/m3) the DMA concentrations are orders of
magnitudes lower than those in our experiments (nmol/m3) (Ge et al., 2011). While
NDMA can and will form by nitrosation of amines on the cartridge during sampling,
even more true as the DMA collected in real air samples would be much less than we
used in lab test due to the fact that sampling was a continuous process but total amount
during sampling. While physical losses and hence breakthrough, were discussed above
(section 2.3.2), chemical loss mechanisms are also possible. In particular direct
photolysis of NDMA is possible and is the major loss mechanism for NDMA in the gas
phase (Hutchings et al., 2010). However during SPE sampling, photolysis could be
such as ozone or hydroxyl radicals could possibly lead to NDMA sampling losses
(Tuazon et al., 1984). Therefore, the possible oxidation of NDMA was investigated by
loading NDMA on a cartridge and passing ambient air through the cartridge. No
significant loss of the preloaded 2 ng NDMA was observed after 2 hours of sampling
at 6 L/min. This is not unexpected as reported gas phase reaction rates of NDMA
reaction with O3 and OH· (< 1.0 × 10-20 and 3.0× 10-12 cm3/molecule/s) and the upper
29
limits of O3 and OH· concentration (2× 1012 cm-3 and 1× 106 cm-3) the half-life of
NDMA was more than 3 months and 2.5 days in presence of O 3 and OH· respectively.
Therefor the effect of such oxidation processes on NDMA sampling appears negligible.
With a lower detection limit, the SPE sampling method was applied to determine
NDMA in ambient air samples. NDMA concentrations observed at different sites are
summarized in Table 2.3. All NDMA concentrations in our observations were orders
of magnitude lower than in previous studies in 1970s & 1980s (40-36,000 ng/m3) which
mostly focused on the heavily polluted industrial indoor environments and urban areas
clearly impacted by or adjacent to such industries (Fine et al., 1976b; Spiegelhalder and
are higher than the 0.07 ng/m3 residential air screening concentration at 10 -6 lifetime
In Tempe (AZ) NDMA was detected in relatively low concentrations, ranging from
0.4-0.7 ng/m3. There are no nitrosamine or amine related industries in the vicinity. The
low humidity in Tempe can be another reason for low concentrations of NDMA since
NDMA formation in air from nitrosation is preferable during nighttime when the air is
humid (Hanst et al., 1977). Air samples from Norway showed a similar but lower
similar locations no NDMA or nitrosamine was found (Nielsen et al., 2012). However,
NDMA found in this work agreed with the expected NDMA concentration range (0.02-
0.1 ng/m3) based on DMA concentrations monitored (0- 31 ng/m3) and potential
30
The highest NDMA concentrations (5.9 -13.0 ng/m3) in our studies were found in
Bakersfield, CA. There are several possible explanations. Bakersfield is located in the
Central Valley in California where NOx and humidity are relatively high and there is
It is noteworthy that in the air samples from Bakersfield, CA, other nitrosamines
detected. Both NDBA and NDEA had similar concentrations to NDMA in all air
since laboratory tests, such as collection efficiency or artifact formation has not been
conducted.
2.4 Conclusions
In this work, SPME and SPE techniques with following GCMS analysis were
evaluated as sampling method measuring gas phase NDMA in ambient air. SPME-
GCMS method was tested using PDMS/DVB and CAR/PDMS fibers. SPME sampling
is not a favorable method to determine NDMA air concentrations due to the high
31
detection limits (> 1 ng/m3). However, SPME method had its own advantages over
other methods. It is solvent free, environmentally friendly and labor efficient. SPME
technique could still be used to monitor high NDMA concentration especially for high
shown to be favorable for the analysis of NDMA in air in many aspects. The simple
set-up and small sample volume needed in this method make it easy and economical
for outside ambient sampling. The high collection efficiency and small
The detection limit for NDMA with this method was less than 0.003 ng/m3, lower than
rather small range (0.1-13.0 ng/m3) among different locations. Presence of other
nitrosamines was also detected. Further evaluation will be needed on SPE or SPME
32
CHAPTER 3
3.1 Introduction
They have been widely found not only in drinking water (Mitch et al., 2003) but also
in the atmospheric waters like fogs and clouds (Herckes et al., 2007). A recent study
discussed the enrichment of nitrosamines in fogs and clouds and emphasized on the fact
that while nitrosamine photolyze readily, they will concentrate in fog and cloud droplets
especially at night time (Hutchings et al., 2010) and might persist into the daytime. Post
combustion CO2 capture (PCCC) plants are currently using amines (e.g.
of amines and their degradation products (Rochelle, 2009; da Silva et al., 2013a; da
Silva and Booth, 2013). Nitrosamines are of concern for PCCC because they can form
from their corresponding amines and NOx which are in flue gas or in ambient air
(Veltman et al., 2010; Reynolds et al., 2012; da Silva et al., 2013b). Several
ng/m3 in emission from a PCCC pilot plant (da Silva et al., 2013b).
It was reported that the main source of NDMA in fogs and clouds is not in cloud
nitrosation of amines to NDMA (Hutchings et al., 2010). With a low Henry’s constant
(2.63 × 10-7 atm m3/mol) (Mitch et al., 2003), NDMA formed in the gas phase will
partition into the atmospheric aqueous phase and accumulate. However, it does not
33
explain by itself NDMA’s occurrence in clouds and fogs at high concentrations since
NDMA has been reported to be highly photoreactive in aqueous solution with half-lives
ranging from 3-18 min depending on experimental conditions (e.g. irradiation intensity)
(Stefan and Bolton, 2002; Plumlee and Reinhard, 2007; Hutchings et al., 2010). The
organic matter in a wastewater matrix was found to have limited impact on NDMA
or the organic matter in the atmosphere could have stronger impact on NDMA
photolysis than waste water organic matter and substantially change NDMA lifetime in
the atmosphere.
carbonaceous material can be divided into elemental or black carbon (EC or BC) and
organic carbon (OC). It was thought that EC mainly absorb light whereas OC scatters
radiation in the atmosphere (Hallquist et al., 2009). Several recent studies found organic
species also absorb solar radiation effectively (Andreae and Gelencser, 2006), and
organic species can contribute up to 50% of the light absorption (Kirchstetter et al.,
organic carbon (WSOC) (Jeffrezo et al., 2005; Feng et al., 2006; Park and Cho, 2011).
Light-absorbing aerosol organic carbon is often referred to as brown carbon (BrC) and
mostly soluble as part of the WSOC. WSOC is important because it influences the
ability of aerosols to act as cloud condensation nuclei (CCN) and the dissolution of
WSOC into clouds and fogs affects cloud chemistry. Since the absorption of WSOC is
significant in the UV-vis range (hence “brown” carbon), WSOC is expected to impact
photons.
biomass burning or fuel combustion and secondary formation from gas and particle
phase precursors (Sullivan et al., 2006; Miyazaki et al., 2006; Weber et al., 2007; Yan
et al., 2009). Many studies have investigated the light absorbing or optical properties
(AAE), Å, exhibits distinct variations between BC and OC and in WSOC from different
sources, locations and seasons (Kirchstetter et al., 2004; Cheng et al., 2011; Du et al.,
2014; Kirillova et al., 2014; Kim et al., 2016). The mass absorption efficiency (MAE)
of WSOC is another optical property that varies by location, season and origin
(Hecobian et al., 2010; Cheng et al., 2011; Zhang et al., 2011). However, limited
The present work investigates the effect of WSOC and inorganic ions on
NDMA photolysis in the atmospheric aqueous phase. The optical properties of WSOC
were then investigated in atmospheric aerosol, fog and cloud droplets from different
locations and from a variety of sources including urban, rural, biomass burning and
vehicle emission. Two representative optical parameters, AAE and MAE, were
compared between aerosol and fog/cloud sample as well as among aerosol from
different sources, providing information on how the optical properties and hence the
35
3.2 Experimental and Analytical Methods
number of field studies in the US, Mexico and Canada for ambient aerosol samples and
from controlled burn experiments for biomass burning source samples. Details are
provided in Appendix A.
Cloud samples were obtained from field studies in Arizona (Hutchings et al.,
2009) and Whistler, Canada (Lee et al., 2012). Fog samples were obtained from studies
collected in Fresno (CA) during an earlier study (Ehrenhauser et al., 2012) and on the
Tempe campus of Arizona State University (ASU). More detailed site descriptions are
provided in Appendix A.
The water soluble organic carbon (WSOC) fraction was determined as follows.
One section of a quartz fiber for each aerosol sample (PM2.5 and PM>2.5) was extracted
under ultrasonication with 15mL deionized (DI) water (>18MΩ cm) for 30 minutes.
All water extracts of aerosol samples as well as fog and cloud water samples were
filtered through a 0.22 µm pre-fired QFF filter (Whatman, UK) using syringe filtration
150 mL water soluble extracts from two aerosol samples collected in Fresno (CA) and
Tempe (AZ). Nitrate and nitrite were added into aliquots to simulate the occurrence of
36
NO3- and NO2- at environmentally relevant concentrations. NaOH or H2SO4 were used
Nitrate and nitrite were determined by ion chromatography (Dionex IC20) using
All photolysis tests were performed using 500 ppt NDMA solutions in batch
experiments. Each experiment used 150 mL of solution which were extracted using a
method similar to EPA method 521 and analyzed using gas chromatography- mass
spectrometry (GC/MS) after the experiment. NDMA extraction and analysis details can
hydrogen phthalate standards. The light absorption spectra of WSOC extracts or fog
and cloud samples were recorded over a wavelength range from 200 to 700 nm with
characterized using the absorption angstrom exponents (AAE) and the mass absorption
calculated based on the linear regression fit of A λ between 300 and 600 nm on log-log
plots.
water extracts or fog/cloud samples. It was calculated using the following Equation 3-
All irradiation experiments are carried out within a solar simulator set up
a 300W ozone free Xe lamp, a water filter, an air mass 1.5 global (AM 1.5G) filter, a
manual shutter, a recirculating water chiller, and a 200mL jacketed flask. The jacketed
flask can be sealed with an O-ring and a Teflon lid which has a Suprasil quartz window
with an opening diameter of 3.2 cm. This solar simulator utilizes the AM1.5G filter to
simulate solar irradiation at a 48.2o solar zenith angle which corresponds to the solar
irradiation in the 48 contiguous states of the United States. The combination of the
300W ozone-free Xe lamp, the water filter, and the AM1.5G filter produces typically
an actinic flux of 1.07×1016 photons cm-2s-1 for this solar simulator. The actinic flux
the procedures of Allen et al (2000) and the actinic flux will be re-verified regularly.
This actinic flux is comparable to the actinic flux at the Earth’s surface in Phoenix,
Arizona at noon during winter which is 1.31×1016 photons cm-2s-1 (Finlayson-Pitts and
Pitts, 1999).
38
Figure 3.1: Image of irradiation setup with the water chiller, irradiation flask, lamp,
filters, and power source
NDMA photolysis rates have been characterized in select matrices like surface
water (Chen et al., 2010) in which organic matter could potentially decrease the
photolysis rates of NDMA. Due to limited sample of fog and clouds, water extracts
investigated the impact of WSOC from ambient aerosol samples described in section
3.2.2. WSOC showed dramatic effects on the photolysis rates. Even at moderate
WSOC concentrations of 7-9 mgC/L, well within the range of many cloud and fog
observations (Herckes et al., 2013), the photolysis rates are decreased by a factor of
2-3 resulting in double to triple lifetimes (Table 3.1). At the higher end of the WSOC
39
Table 3.1: Half-lives of NDMA in various matrices and at different WSOC
concentrations
DOC
WSOC Half-life t1/2 (min)
(mgC/L)
pH from 1.2 to 6.8 which covers a wide range of cloud and fog pH observations
(Herckes et al., 2013). These observations are contrary to previous studies which saw a
Nitrite and nitrate are common components of fogs and clouds. It was suggested
that both species could affect NDMA photolysis since they have similar absorbance
around 300nm as NDMA which mainly absorbs at 330nm (e.g. Plumlee and Reinhard,
2007; Hutchings et al., 2010). Our results show that at high end of environmentally
relevant concentrations (2000 µeq/L and 100 µeq/L for nitrate and nitrite respectively)
concentration range for nitrate and nitrite, as in clean to moderately polluted clouds and
fogs, the effect would only be in the 10-20% range. Therefore WSOC likely has the
40
3.3.2 Wavelength Dependence of Light Absorption
The absorption spectra of aerosol extracts and fog/cloud filtered samples were
measured between 200nm and 700nm. Figure 3.2 shows the UV-Vis spectra of aerosol
extracts which have 1 mg/L nitrate and nitrate standards at 1 mg/L. Nitrate has strong
absorbance at wavelength < 250 nm and contributes up to 50% of the total absorbance
nm in the presence of WSOC. The majority of the absorbance was from the organic
components in WSOC.
0.35
0.20
0.15
0.10
0.05
0.00
200 300 400 500 600
Wavelength nm
Figure 3.2: UV-Vis absorbance of WSOC with 1 mg/L nitrate and 1.4 mgC/L dissolved
organic carbon (a), 1 mg/L nitrate (b) and the dissolved organic components (a-b).
The wavelength dependence of light absorption was investigated using the AAE
calculated between 300 nm to 600 nm. In most samples, signals below 300 nm had
interference of inorganic species and therefore were not included. The AAE of aerosol,
41
Aerosol
Fog and Cloud, 300-600nm
Fog and Cloud, 300-400nm
ASU, AZ
Higley,AZ
Davis, CA
Monterrey, Mexico
Bakersfield, CA
Whislter, BC
Biomass burning
Prescribed burn
Port O'Connor, TX
Big Bend, TX
South Padre Island, TX
Galveston, TX
Tunnel JQ, Brazil
Tunnel RA, Brazil
Parking Lot
Parking Lot unfiltered
0 2 4 6 8 10 12
AAE
Figure 3.3: AAE for WSOC from aerosol and fog/cloud samples
The AAE of unfiltered and filtered aerosol water extracts from the emission
impacted aerosols were compared (Parking Lot & Parking Lot unfiltered in Figure 3-
3). AAE in unfiltered extracts (1.64 ± 0.22) were substantially lower than filtered
extracts (3.57 ± 0.44). It was reported the AAE for BC is close to 1, while AAE of
organic matter is larger than 1 (Bond, 2001; Kirchstetter et al., 2004). The soot in
unfiltered extracts might have lowered the AAE of the light-absorbing organic matter.
In addition, absorption in unfiltered extract does not follow the Equation 3-1 well with
lower log-log regression R2 (0.81) than filtered extracts (0.99). In this work, the AAE
42
of all WSOC extracts varied between 2.52 and 6.45 with average of 3.78 ± 0.84. The
linear fit of the log(λ) and logA(λ) showed good correlations, with R2 > 0.92 except the
samples from Bakersfield, CA. For the fog and cloud sample, AAE were between 2.02
and 5.12 with an average 3.69 ± 1.04. This is the first attempt ever characterizing the
The cloud and fogs samples show a wider range of AAE compared to aerosol
WSOC although there are fewer samples and lower R2 values (0.22-0.98) were
aerosol and fog/cloud and among fog/clouds samples from different locations as well.
Additionally, it was found for fog/cloud that the AAE calculated between 300 nm and
400 nm (7.46 ± 2.13) are substantially different from above AAEs above 400 nm. The
AAE suggests that chromophores absorb mainly below 400 nm in fog/cloud water.
The AAE observed in aerosol extracts were lower than what was reported using
similar extraction methods in previous studies. For example, the AAE was calculated
to be 7.23 ± 1.58 and 7.2-7.5 for WSOC in aerosol from Seoul and Beijing respectively
(Cheng et al., 2011; Du et al., 2014; Kim et al., 2016). AAE values close to 7 were
reported for water extracts collected in Los Angeles and the southeastern United States
(Hecobian et al., 2010; Zhang et al., 2013). It was suggested based on AAE values in
previous studies that BrC are mainly from biomass burning and SOA formed from
SOA have similar AAE (~ 7) (Hoffer et al., 2006; Bones et al., 2010; Kim et al., 2016).
However, in our study, the biomass burning aerosols showed a much lower AAE than
(3.81 ± 0.62) than previous studies (Figure 3.3). Auto emission impacted aerosol
samples, parking structure (3.21 ± 0.10), Tunnel JQ (4.05) and Tunnel RA (3.07) have
43
similar AAE values with other samples collected in urban (e.g. ASU or Monterrey) or
values in summer compared to other seasons which was mainly attributed to the
enhanced formation of SOA and strong photochemistry during summer time (Du et al.,
2014; Kim et al., 2016). A similar seasonal pattern of AAE was not observed in our
study in Arizona. AAE of aerosols in warmer months (Apr-Sep, 3.77 ± 0.47, n = 9) are
in similar to those during the other months (Oct-Mar, 3.31 ± 0.93, n = 10). Despite the
small difference of aerosol extracts AAE from varied sources such as biomass burning
or vehicle emission, the narrow range of AAE values suggested that the composition of
absorptivity and screening effect of WSOC. Strong correlations were observed between
A365 and WSOC for all aerosols extracts (r = 0.81, p < 0.01, Figure 3.4), indicating the
In fog and cloud samples, A365 did not correlate with WSOC as well as in aerosol
extracts (r = 0.72, p < 0.01, Figure 3.4), suggesting a larger variation of WSOC
fog and clouds had lower absorption than WSOC extracts. This is consistent with what
is known about the composition of fog and clouds organic matter in previous studies.
In fog and cloud a substantial fraction (~24%) of organic matter are small molecular
weight acids such as formic and acetic acids (Herckes et al., 2013). These small volatile
organics (e.g. formic and acetic acids) have very low absorptivity at 365 nm. While
44
they are abundant in fogs and clouds, they are not commonly found in aerosol WSOC
due to their high volatility. Hence we observe a kind of ‘dilution’ effect where a strong
contribution of weakly absorbing species lowers the A365 of WSOC in fogs and clouds.
Thus the screening effect on photolysis of NDMA in fog and clouds caused by WSOC
25
20
Aerosol
Fog/Cloud
Absorbance m-1
15
y = 0.9315x - 0.2845
R² = 0.6519
10
5
y = 0.2197x - 0.0016
R² = 0.4819
0
0 5 10 15 20
DOC (mgC/L)
Figure 3.4: Correlation of Absorbance at 365 nm vs. WSOC for aerosol extracts and
fog/cloud samples
and the MAE at 365nm was calculated by Equation 3-2. Figure 3.5 summarizes MAE
values for WSOC from aerosol and fog/cloud samples collected in various
45
Figure 3.5: MAE values of WSOC and fog/cloud samples
WSOC from locations except Whistler, BC exhibit higher MAE than cloud/fog
samples. The lower MAE in cloud/fog samples were possibly due to the presence of
small volatile organics in cloud/fog as discussed in section 3.3.3. For WSOC, MAE in
Whistler aerosol samples was substantially lower than all the other aerosol samples
Mountain where SOA formation from biogenic VOCs is dominant and organics in those
Previous studies reported a higher MAE of WSOC during summer in Los Angeles
where SOA formation is dominant by anthropogenic VOCs than Atlanta where SOA
are mainly from biogenic VOCs (Brown et al., 2007; Muller et al., 2008; Zhang et al.,
2011). It was also confirmed by chamber experiments that SOA produced from
46
biogenic VOCs were less light-absorbing than that produced from anthropogenic VOCs
(Nakayama et al., 2010; Zhong and Jan., 2011). This was consistent with the observed
differences in MAE between fogs and clouds. The MAE values in fog samples (0.32 ±
0.10 m2/gC) were higher than those in cloud samples (0.17 ± 0.14 m2/gC). It may be
because the fog samples were collected in lower altitude locations that were more
samples were all sampled at mountain sites which were more remote and which
experienced a stronger impact of biogenic sources, showing lower MAE than fog
For the other aerosol samples, MAE values also varied by sample locations and
sources. WSOC in aerosol collected in Galveston showed highest MAE (4.86 ± 0.75
m2/gC) (Figure 3.5). The high absorbing OC could come from the heavy polluted
emission from many refinery and petrochemical plants in Galveston. High MAE values
of WSOC were also found in samples associated with vehicle emissions. The MAE of
samples collected in Tunnel JQ, Brazil and Tunnel RA, Brazil are 2.31 m2/gC and 3.06
m2/gC (Figure 3.5), respectively. Although there is only one sample from each location,
the two tunnel samples exhibited highest MAE values amongst all samples. The Tunnel
JQ sample were more associated with gasohol or ethanol fueled light duty vehicles
emission while the Tunnel RA sample were more related to diesel-fueled heavy duty
vehicles emission. The difference of MAE between these two samples might suggest
the different absorptivity of chromophores from the two emission types. WSOC of
parking lot samples have a lower MAE (1.36 ± 0.30 m2/gC) than the tunnel samples,
possibly due to the less intensive traffic activity in parking lot. However, parking lot
aerosol samples still have higher MAE than urban or rural samples (e.g. ASU or
Higley). The high MAE values of WSOC from mobile emission were consistent with
47
previous studies. For example, it was reported by Hecobian et al. (2010) that the
absorptivity of WSOC was substantially higher in morning rush hour than the rest of
the day, suggesting high absorptivity might be associated with primary vehicles
emission. Du et al. (2014) also reported high MAE (2.89 m2/gC) of WSOC from
For urban or rural aerosol samples including ASU, Higley, Davis and Monterrey
in this study, WSOC exhibited MAE values similar to that of biomass burning and
prescribed burning samples. It was reported that the biomass burning is one of the major
sources of the WSOC in aerosols (Hecobian et al., 2010; Cheng et al., 2011; Du et al.,
2014).
A seasonal pattern of MAE values was observed in many studies in East Asia
and the United States. MAE in Seoul were 1.02 and 0.28 m2/gC for winter and summer,
respectively (Kim et al., 2016). Observations in Beijing (Cheng et al., 2011; Du et al.,
2014) and southeastern United States (Hecobian et al., 2010) showed similar seasonal
variations. It was suggested that the higher MAE was linked to more biomass burning
in winter than in summer. However, in our study no such seasonal pattern was observed
in aerosol samples collected on ASU’s campus. The reasons could be that there is less
of a difference between SOA in the summer than in the winter month which is
Some studies suggest that haze or cloud processing cloud lead to the formation
of more light absorbing carbon (Ervens et al., 2011). This hypothesis was investigated
high RH period. MAE values were calculated in 330 nm where NDMA got photolyzed.
It is known that water vapor plays important role in formation organic aerosols.
48
Previous study reported that the ratio of WSOC between particle phase and gas phase
increased with RH when RH was above ~60% (Hennigan et al., 2009). The uptake of
liquid water by particles probably would enhance the partitioning of small volatile
with the absorptivity of WSOC change in Bakersfield sample. As shown in Figure 3.6,
MAE changes seem to track the RH change during our sampling. The MAE values
increased following the decrease of the average RH and they decreases when RH was
high.
100 RH 2
90 MAE 1.8
80 1.6
Relative Humidity (%)
70 1.4
60 1.2
MAE330
50 1
40 0.8
30 0.6
20 0.4
10 0.2
0 0
Figure 3.6: Temporal variations of WSOC MAE and RH in aerosol extracts from
Bakersfield, CA
3.4 Conclusions
and optical properties of WSOC from aerosol extracts and atmospheric aqueous phases
(cloud/fog) were investigated. It was found that WSOC had more effect than inorganic
species on NDMA photolysis. The organic matter screening effect observed was
49
substantial and even under moderate DOC concentrations for fogs and clouds, the
It was also found that WSOC from aerosol has a higher mass absorption
efficiency than organic matter from fog and cloud waters. Combining AAE and MAE
between aerosol WSOC and fog/cloud samples. AAE values were similar for aerosol
samples from various sources and locations, whereas MAE values were different by
their sources. Anthropogenic activities such as vehicle emission were associated with
high absorbing organic matters while the organic matter from biogenic sources appears
found in our study. However, the MAE seem related to RH as the composition of
provide more knowledge on the composition of WSOC from different samples and the
50
CHAPTER 4
4.1 Introduction
drinking water are leading the United States Environmental Protection Agency
(USEPA) and some Canadian Provinces to set health standards and regulatory
determinations for individual or groups of NAs. Over the past decades, NAs have
emerged as a large scale concern because water utilities have increasingly relied upon
acid (HAA) regulations (Krasner et al., 2013). Six NAs were included in Unregulated
Contaminant Monitoring Rule 2 (UCMR2), and five of those were then included on the
drinking waters) with detections of four other NAs being rare (<1% of samples) and
typically occurring in samples with high NDMA concentration (Russell et al., 2012).
NAs, including NDMA, are classified as probable human carcinogens in water at low
ng/L levels associated with a 10-6 lifetime cancer risk (USEPA, 2015). Based on this
(OEHHA) set a public health goal at 3 ng/L for NDMA (OEHHA, 2006) and
California’s Department of Public Health (CDPH) has set 10 ng/L notification for three
nitrosamines (CDPH, 2013). Because of their potential to cause cancer, the USEPA
A recent review indicates that most studies have found that NDMA formation
is more associated with chloramination than with chlorination (Krasner et al., 2013).
51
Systems using chloramines as the primary, rather than secondary, disinfectant have
high NDMA Formation Potential (FP) (i.e., >50 ng/L) in plant effluent, indicating the
nitrosamine formation is a kinetically slow process, plants using chloramine with long
hydraulic contact times in plant plus distribution system (e.g., 12–18 hr) tend to have
more NDMA in the effluent than those using chloramine for short (e.g., 0.5–2 hr)
contact times (Krasner et al., 2012). NDMA concentrations tend to increase throughout
plus an oxidant (e.g., inorganic chloramine, ozone) (Choi and Valentine, 2002; Lee et
al., 2007). Oxidation chemistry, including inorganic reactions with bromide and
ammonia (Schreiber and Mitch, 2005; Le Roux et al., 2012), is important; however,
little information is available regarding which organic precursors control the rate and
NDMA from chloramination of most secondary and tertiary model amines are ~0–2%
but can be >80% for certain tertiary amines with -aryl functional groups (Shen and
precursors have not been characterized outside of a select few (Hanigan et al., 2015) in
2006a; Schreiber and Mitch, 2006b; Mitch and Schreiber, 2008; Shen and Andrews,
2011b), less information exists related to the kinetics of NDMA formation in surface
and wastewaters. Many studies rely upon NDMA FP measurements which are akin to
THM-FP measurements and, while useful, lack information suitable for managing DBP
methods for NA’s have been developed, but often include a short free chlorine period
(before NH3 addition) to mimic common drinking water treatment plant (DWTP)
The aim of this paper is to investigate NDMA formation kinetics in waters with
lower (surface waters) and higher (treated wastewater effluents) levels of NDMA
monochloramine and formation of NDMA were monitored. Experimental data were fit
second order apparent rate constant for NDMA formation across a range of water
sources, suggesting the model represented a possible common rate limiting step that
wastewater effluents, one surface water, and one groundwater. Secondary wastewater
effluents were collected at local wastewater treatment plants (WWTP) in the Metro
Phoenix and Nogales regions of Arizona. The surface water was collected from central
AZ surface water supplies and the groundwater was pumped from a canal in a heavily
53
industrial/agricultural impacted area. All water samples were filtered immediately after
sampling (10 μm, CLR 1-10 Pall Corporation, Port Washington, NY) and stored in the
4.2.2 Reagents
All reagent water was >18.2 MΩ-cm and of laboratory grade (Milli-Q Millipore,
Billerica, MA). Sodium hypochlorite (5.65−6%), sodium borate, and sodium sulfite
were purchased from Fisher Scientific (Fairlawn, NJ). Ammonium chloride and
anhydrous sodium sulfate were obtained from Sigma Aldrich (St. Louis, MO).
(Gibbstown, NJ). NDMA was purchased through Sigma-Aldrich (St. Louis, MO).
mL sample aliquots using 1 L amber bottles. A borate buffer stock solution was
prepared by dissolving sodium borate and boric acid in water. Aliquots were buffered
borate buffered (10 mM, pH = 8.0 ± 0.1) ammonium chloride solution to produce a
N:Cl2 molar ratio of 1.2:1. For samples from each water source, experiments were
conducted using two monochloramine doses, a higher dose at 15–20 mg/L and a lower
dose at 5–7 mg/L to simulate FP test and SDS test conditions. After adding
monochloramine, samples were allowed to react in the dark at room temperature (23 ±
1 °C). Reaction times ranged from 0 minutes to longer than 720 hours. Residual
54
monochloramine was measured before quenching the residual using 5 mL of 0.5 M
ascorbic acid. All samples were spiked with 1 mL of 100 μg/L NDMA-d6 and kept in
NDMA extraction and concentration procedures used in this work have been
described previously (Hanigan et al., 2012). Briefly, activated coconut charcoal solid
phase extraction (SPE) cartridges (Restek, Bellefonte, PA) were first conditioned with
DCM, methanol, and HPLC grade water. Then, 500 mL water samples with isotope
(NDMA-d6) were passed through SPE cartridges. After loading, the cartridges were
dried using ultra high purity (UHP) nitrogen gas, and 5 mL DCM was used to elute
NDMA. After being dried with anhydrous sodium sulfate powder, the extract of NDMA
GC/MS operated in positive chemical ionization mode with ammonia as the reagent
gas (Charrois et al., 2004). In brief, the chromatographic column used was an Agilent
DB-1701P (30 m × 0.250 mm × 0.25 μm) (Santa Clara, CA) and followed a pulsed
splitless injection (initial pulse 15 psi for 45 s and then 10 psi) set at 250 °C with a
reduced diameter SPME inlet liner (Sigma Aldrich, St. Louis, MO). The helium carrier
gas was initially pulsed at 1.9 mL/min for 45 s and then reduced to 1.3 mL/min for the
rest of the run. 4 μL of sample was injected into GC through the inlet, with oven
120 °C at 20 °C/min. The column interface temperature was set at 200 °C. The mass
selective detector was set to analyze for mass-to-charge 92 (NDMA + NH4+) and 98
(NDMA-d6 + NH4+). The GC/MS was calibrated using a series of NDMA standards
ranging from 1 µg/L to 1 mg/L and NDMA-d6 (100 µg/L) as internal standard.
55
4.2.5 Other Analyses
carbon (DOC) was measured using a Shimadzu Total Organic Carbon (TOC)-VCSH
Beckman Counter Inc., Brea, CA). Dissolved oxygen was measured by a portable meter
secondary treated wastewater with two different monochloramine doses. The pH values
remained unchanged during the reaction. Monochloramine decayed slowly over the
level of ~460 ng/L (~6 nM) within 120 hours at the higher monochloramine dose and
more slowly approached a lower maximum NDMA concentration ~300 ng/L (~4 nM)
NDMA formation increased faster and reached its maximum in less time. Thus, the
thermodynamically and kinetically. Data collected for the other wastewater effluents
showed a similar impact of monochloramine on the rate and yields of NDMA formation
(see Appendix B Figure A1-4). The maximum NDMA formation in each experiment
56
will be referred to as NDMAmax, and equals the molar concentrations of NDMA
precursors (P0) in the water under the specific experimental conditions before
chloramination.
Table 4.1 summarizes NDMAmax values for each experiment. In the wastewater
effluent samples, NDMAmax ranged from 4 to 12 nM. There was no correlation found
elsewhere (Chen and Westerhoff, 2010; Uzun et al., 2015). In all cases, higher
monochloramine doses led to 30% to >50% higher NDMA max values. This was
unexpected because even at very long reaction times there was adequate oxidant
dominant chloramine species in our test (pH = 8, N:Cl2 molar ratio 1.2:1), dichloramine,
the disproportionation product from monochloramine, was still present according to the
equilibrium:
formation from NDMA precursors such as DMA (Shen and Andrews, 2011b; Schreiber
and Mitch, 2006b). Additionally, NDMA precursors were found to react preferably
with either monochloramine or dichloramine (Selbes et al., 2013; Le Roux et al., 2011).
Thus, in our experiment, even trace levels of dichloramine formed could affect the
formation.
57
A
20
NH2Cl =18mgCl 2/L
18
NH2Cl =6mgCl 2/L
16
NH2 Cl (mgCl2 /L)
14
12
10
8
6
4
2
0
0 100 200 300 400 500 600
Time (hour)
B
600
500
400
NDMA (ng/L)
300
200
NH2Cl=18mgCl 2/L model
NH2Cl=18mgCl 2/L observation
100 NH2Cl=6mgCl 2/L model
NH2Cl=6mgCl 2/L observation
0
0 100 200 300 400 500 600
Time (hour)
Figure 4.1: (A) Monochloramine (NH2Cl) decay kinetics in WW1 for two initial
monochloramine doses. (B) NDMA formation observed (symbols) and fitted by
equation 2&3 (lines). Error bars represent one standard deviation (n = 3) for select
time points. (pH = 8.2, Temperature = 23 ± 1 °C)
58
4.3.2 NDMA Formation Kinetics in Surface Waters.
values in the surface water (3.9 mgC/L) were approximately an order of magnitude
lower than in wastewater (DOC 4.6-6.2 mgC/L) (Table 1). Figure 4.2 shows that the
concentration. NDMA formation was less and slower in surface water samples than in
wastewater. Monochloramine residual slowly decayed during the experiments and was
present throughout the duration of the experiments. In our test in surface water at two
monochloramine doses (Figure 4.2), the quick NDMA increase within hours possibly
indicated the fast reaction part of NDMA and the slow NDMA increase thereafter
showed a slow and rate limiting step of NDMA formation. Similar NDMA formation
kinetics tests from natural organic matter (NOM) in surface water were made by Chen
and Valentine (Chen and Valentine, 2006). These authors separated NDMA precursors
in NOM into two groups and postulated that the fast-reacting group reacts with
monochloramine within hours while the slow-reacting group reacts with HOCl over
days respectively. However, the fast-reacting group forming NDMA was not monitored
in their work due to the low time resolution. Such fractionation of NDMA precursors
remains controversial. The two kinetic parts (fast vs. slow) were not observed in the
wastewater samples (Figure 4.1, Appendix B) in similar conditions (e.g. DOC and
NH2Cl), possibly due to the difference in amine precursors between wastewater and
59
60
50
40
NDMA (ng/L)
30
20
NH2Cl=36mgCl 2/L model
NH2Cl=36mgCl 2/L observation
10 NH2Cl=12mgCl 2/L model
NH2Cl=12mgCl 2/L observation
0
0 100 200 300 400 500
Time (hour)
Figure 4.2: NDMA formation observed (symbols) and fitted by equation 2&3 (line) in
SW at two initial monochloramine doses. Error bars represent one standard deviation
(n = 3) for select time points. (pH = 8.0, 23 ± 1 °C)
The groundwater had NDMAmax (15-20 ng/L) on the same order of magnitude
with, but lower than the surface water (30-50 ng/L). It is possibly because it contained
less DOC (1.78 mg/L) in groundwater. No two kinetic parts (fast vs. slow) were
observed and NDMA formation reached maximum in less than 100 hours (Figure 4.3)
60
25
20
NDMA (ng/L)
15
10
0
0 200 400 600 800
Time (hour)
Figure 4.3: NDMA formation observed (symbols) and fitted by Equations 2&3 (line)
in GW at two initial monochloramine doses. (pH = 8.0, 23 ± 1 °C)
showed higher NDMA formation (200-950 ng/L) than surface waters (30-50 ng/L) and
groundwater (15-20 ng/L). The reaction times for NDMA formation reaching its
maximum were shorter when higher monochloramine doses were applied in wastewater
and groundwater. No significant difference of such reaction times was found between
the two doses of chloramine in surface water. The differences in NDMA formation
potential are due to the various types and concentrations of precursors in the different
source waters. Precursors such as DMA, which is more reactive with dichloramine,
may explain the higher and faster NDMA formation at higher doses of
methadone, which was found in wastewater effluents has high yields of NDMA and
61
could contribute to large fractions of total NDMA formed. It is possible that such high
yield precursors are also more reactive to chloramines making the NDMA formation in
wastewater relatively faster. So higher amine concentrations and higher levels of these
known high yield NDMA precursors may be responsible for a higher overall NDMA
NDMA yields in source waters, the differences in kinetics or rates were rather small.
precursors are needed to improve our understanding of NDMA formation in real waters.
Three main pathways for NDMA formation have been proposed and are
performed in this work, fractions of NDMA precursors with different rates were not
evident in surface water and were not observed in wastewater effluents. In addition, it
was not practical to classify NDMA precursors (nM quantities) as either having higher
or lower yields and presumably different reaction rates as they are water source specific.
experiments, NDMA formation was fit to Equation 4-2: for the reaction of NDMA
d[P]
= −k app [P]m [NH2 Cl]n Equation 4-2
dt
62
P is the NDMA precursor concentration and kapp is a best fit rate constant. Here
we only count the ‘active’ compounds that form NDMA as NDMA precursors. So we
assume a 1:1 relationship between the disappearance of the precursor (P) and NDMA
formation (m = 1). The rate order with respect to NH2Cl (n) was calculated ~1 (n = 1.20
± 0.41) by plotting log [NDMA formation rate] vs. log [NH2Cl] in the same time period
for the same water at two NH2Cl doses. Therefore we used the second order expression
where [P]t is calculated from Equation 4-2. It is noteworthy that NDMA is only one of
Equation 4-3 refers to the precursors that would form NDMA under certain conditions
hydrolysis and reactions with inorganic or organic species (e.g. NDMA precursors).
time points with a first order model in which the decomposition rate of monochloramine
the model did not use dichloramine as a reactant variable. One reason is that the
63
conditions (pH = 8.0) the NHCl2/NH2Cl ratio would be constant because the system is
in equilibrium during the reaction time (Ozekin et al., 1996; Zhang et al., 2015). Thus
also be fit with our model empirically, leading to an apparent rate constant kapp.
surface waters was well fit with correlation coefficients (R2) greater than 0.9 in most
tests. Optimized data fits were achieved using Kintecus (Ianni, 2002). Model fits of
experimental data are shown in Figure 4.1-4.3. In wastewater effluents tests, the model
overestimated the NDMA in the beginning of the test (<50 h) at low doses of
surface waters. In work conducted by Shen and Andrews, the lag and a subsequent
modeled with a dose-response curve (Shen and Andrews, 2011a). The lag and the rate
constants were found correlated to TOC and SUVA values for certain pharmaceuticals.
It was suggested that there was NOM-pharmaceutical binding that inhibited the initial
NDMA formation (Shen and Andrews, 2011a). A similar lag-period was interpreted as
organics. A similar dose-response curve model was applied to our kinetics data. The
NDMA formation was well represented with a similar correlation coefficient than in
our kinetic model (R2 > 0.9) (Table A2 in APPENDIX B). The wastewater effluent
samples with the ‘lag-period’ were better fit with the dose-response curve model than
our proposed model. However, the rate constant k (h-1) derived from the dose-response
64
model showed broad variations, ranging from 0.007 h -1 to 0.175 h-1 for surface water
and wastewater respectively. No correlation was found between water quality (e.g.
TOC and SUVA) and model parameters (e.g. lag and rate constant k). The dose-
response model also did not take into account the role of monochloramine dose, which
in our kinetic experiments, impacted NDMA FP and the reaction kinetics. Finally the
dose-response model is purely descriptive and does not provide insight into the
Table 4.1 Water quality, treatment and NDMA formed in source waters
† Data of NDMA formation and monochloramine were from Chen and Valentine,
2006
Table 4.1 summarizes fitted kapp and R2 values for all experiments. The
magnitude of kapp values fall within a relatively narrow range of less than one order of
Equation 2 and 3, was evaluated by comparing observed NDMA formation data and
65
model prediction in Fig 4-4. The small 95% confidence intervals suggested significant
and Valentine’s 2006 work on NDMA formation from NOM was also fit with our
model and the kapp (0.09 M-1s-1) was similar to that of our wastewater and surface
waters. A narrow range in kapp values was surprising given the very different precursors
expected in varying source waters and the order of magnitude differences in NDMA max
between sources.
1200
NDMA model prediction (ng/L)
y=0.96x+13
2
1000 R =0.98
800
600
95% confidence interval
400
0
0 200 400 600 800 1000 1200
NDMA observation (ng/L)
Figure 4.4: Linear correlation between model predictions and observations of NDMA
concentrations in all waters. Data from all reaction time periods are included.
conducted with secondary amines such as DMA (Schreiber and Mitch, 2006b). It has
been suggested that during chlorination some tertiary amines could decay to secondary
66
amines forming NDMA upon subsequent chloramination (Mitch and Schreiber, 2008).
It was still unclear if such transformation reaction between amines or NDMA formation
from amines was a rate limiting step. The small variance of rate constants suggests that
there any were present, are rapid compared to NDMA formation. This is in agreement
secondary amines and tertiary amines with either low or high yields, probably have a
monochloramine dose. The intermediates then function as the precursors (P) and the
reaction kinetics (Gunten, 2003, Ramseier et al., 2011). In this work NDMA formation
was modeled as second order reaction in Equation 4-2, which can be integrated
67
[𝑃]
𝑙𝑛 = −𝑘𝑎𝑝𝑝 ∫[𝑁𝐻2 𝐶𝑙]𝑑𝑡 Equation 4-4
[𝑃]0
Equation 4-4 offers another way of quantifying the apparent second order rate
precursor, is related to the NH2Cl exposure. Figure 5 shows the plots of [P]/[P0] against
NH2Cl exposure for water samples at low and high NH2Cl doses. In different water
samples, the reaction required different NH2Cl exposure for the same conversion of
precursors. The rate constants varied by water sources, possibly due to the varying
precursor groups and their different reactivity with NH2Cl or NHCl2. From the previous
discussion in this work NH2Cl dose determines the NDMAmax even in the same water
sample, but does not affect the rate constants in wastewater and groundwater. The
relative change of precursors (or increase of NDMA formation) had the same kinetics
for the same water at different NH2Cl doses (Figure 4.5a-4.5c, Figure A5-7 in Appendix
B). Surface water represents an exception (Figure 4.5d). The surface water had a lower
kapp than all other waters tested. The relative change of precursors in surface water
differed with low and high dose NH2Cl, especially when NH2Cl exposure is less than
5×106 mgCl2 × min/L, possibly due to the ‘fast and slow’ reaction mechanism in surface
water.
68
a b
1.0 1.0
WW1-L WW4-L
WW1-H WW4-H
0.8 0.8
0.6 0.6
P/P 0
P/P 0
0.4 0.4
0.2 0.2
0.0 0.0
0.0 5.0e+4 1.0e+5 1.5e+5 2.0e+5 2.5e+5 3.0e+5 0.0 5.0e+4 1.0e+5 1.5e+5 2.0e+5 2.5e+5 3.0e+5
NH2Cl exposure (mgCl2*min/L) NH2Cl exposure (mgCl2*min/L)
c d
1.0 GW1-L 1.0 SW1-L
GW1-H SW1-H
0.8 0.8
0.6 0.6
P/P 0
P/P 0
0.4 0.4
0.2 0.2
0.0 0.0
0.0 5.0e+4 1.0e+5 1.5e+5 2.0e+5 2.5e+5 3.0e+5 0.0 5.0e+4 1.0e+5 1.5e+5 2.0e+5 2.5e+5 3.0e+5
NH2Cl exposure (mgCl2*min/L) NH2Cl exposure (mgCl2*min/L)
Figure 4.5: Plots of P/P0 versus monochloramine exposure for water samples (a)
WW1, (b) WW4, (c) GW1, (d) SW1. L = lower, H = higher, represent samples with
lower or higher NH2Cl concentrations.
lower than those used in our test (0.09-0.51 mM). From our results, NDMA formation
reaction kinetics are dependent upon NH2Cl exposure, not NH2Cl concentrations. The
rate constants could be applied to waters with lower NH2Cl concentration and longer
contact time ranges. NH2Cl exposure and the rate constants are the key parameters for
the prediction of the transformation efficiency of NDMA precursors into NDMA. With
proposed model provides a practical way to predict NDMA formation in drinking water
influenced by wastewater effluents and surface waters in water plants and drinking
69
4.5 Conclusions
investigated in wastewater and surface water samples. Under reaction conditions in our
experiments (pH = 8.0, NH2Cl = 0.09-0.51 mM) NDMA formation increased to its
predicted by the model with correlation coefficients higher than 0.9 in most cases. The
modeled rate constants for different water samples were found surprisingly within a
narrow range (0.01–0.09 M-1s-1), indicating a possible rate limiting step of NDMA
formation for different amine precursor groups. With only two simple measurements
0.09 mM to 0.51 mM with wastewater effluents and surface water samples. It would be
of value to extend the work further in a larger variety of water matrices and reaction
conditions such as pH, N:Cl2 ratio and dissolved oxygen level, to simulate a larger
model precursors are needed to better understand different pools of precursors and how
70
4.5 Acknowledgements
This research was supported by the Water Research Foundation (Project 4499,
Fellowship, Water Environment Federation Canham scholarship, and the Arizona State
71
CHAPTER 5
WASTEWATER DISCHARGES
5.2 Introduction
(Krasner et al., 2013). NAs were included in the Unregulated Contaminant Monitoring
Rule 2 (UCMR2) and then listed on the third Contaminant Candidate List (CCL3)
drinking water at low ng/L levels associated with a 10-6 lifetime cancer risk.
notification level of 10ng/L for NDMA (OEHHA, 2006). Because of their high
carcinogenic potential, the USEPA may soon make a regulatory determination for NAs.
nitrosamine. Most studies have found that NDMA is rather associated with
chloramination than with chlorination (Mitch et al., 2009; Boyd et al., 2011; Russell et
al., 2012). Systems with high plant effluent NDMA (i.e., >50 ng/L) typically use
chloramines as the primary rather than secondary disinfectant (Russell et al., 2012),
chlorine. Due to the long time-scale for nitrosamine formation, plants with long in-plant
chloramine contact times (e.g., 12–18 hr) tend to have higher NDMA concentrations in
72
the plant effluent than those with short (e.g., 0.5–2 hr) contact times (Krasner et al.,
systems (Krasner et al., 2012; Valentine et al., 2005; Krasner et al., 2009; Liang et al.,
Primary amines can be nitrosated to yield primary NAs, however the latter are
unstable and decay nearly instantaneously (Ridd, 1961). Secondary amines can be
formation from dimethylamine (DMA) (Mitch and Sedlak, 2002; Choi and Valentine,
2002; Schreiber and Mitch, 2006a; Schreiber and Mitch, 2006b; Shah and Mitch, 2012).
However, some studies indicated that the presence of DMA was not sufficient to
explain the NDMA formed in surface water and wastewaters (Gerecke and Sedlak,
2003; Mitch and Sedlak, 2004). Tertiary amines may also serve as nitrosamine
(Mitch and Schreiber, 2008). Mechanistic studies indicate that yields of NDMA from
chloramination of most secondary and tertiary amines are very low (~0–3%) but
recently a subset of tertiary amines were found to have substantially higher NDMA
yields (up to 90%) compared to previously studied precursors (Le Roux et al., 2011;
Shen and Andrews., 2011a; Shen and Andrews., 2011b). In particular, ranitidine, a
widely found amine-based pharmaceutical, forms NDMA at yields higher than 80%
(Le Roux et al., 2011; Shen and Andrews, 2011b). It was suggested that the electron
donating group (furan ring) in ranitidine favors the reaction with chloramine leading to
higher NDMA yields. The differences of NDMA formation yields among tertiary
amines revealed the importance of tertiary amine structures (N bond leaving group) on
the NDMA formation. The higher yields also suggest that tertiary amines can form
73
nitrosamines without proceeding through a secondary amine intermediate (Selbes et al.,
2013).
proposed (Figure 5-1). Mechanistic studies using DMA as the model precursor found
then oxidized by monochloramine to NDMA (Choi and Valentine, 2002; Mitch and
oxygen was later discovered and a second mechanism proposed ((2) in Figure 5-1).
Here, dichloramine reacts to yield NDMA via the formation of the chlorinated UDMH
NDMA (Schreiber and Mitch, 2006). Based upon competition reaction kinetics, it has
dichloramine (2) pathway. As the molar yield of NDMA from DMA is low (i.e., <5%)
compared to that from other compounds (e.g., ranitidine), it was suspected that a third
pathway, other than through DMA, exists. Compounds such as ranitidine may follow a
chloramines ((3) in Figure 5.1) (Le Roux et al., 2012). Through this pathway, NDMA
formed from ranitidine was more sensitive to monochloramine (Le Roux et al., 2011).
react with monochloramine while compounds with electron donating groups react
preferentially with dichloramine (Selbes et al., 2013; Liu et al., 2014). Many suspected
precursors could react with both monochloramine and dichloramine. Therefore, NDMA
chloramine species.
74
Figure 5.1: NDMA formation pathways as proposed in the literature: (1) Choi and
Valentine, 2002; Mitch and Sedlak, 2002. (2) Schreiber and Mitch, 2006. (3) Selbes et
al. 2013.
surface water or wastewater (Mitch and Sedlak, 2004; Mitch and Schreiber, 2008; Shen
and Andrews, 2011b), less information exists related to NDMA formation kinetics in
the latter water sources. NDMA formation from DMA has been initially modeled
through UDMH and Cl-UDMH pathways ((1) and (2) in Figure 5.1) and the latter
Mitch, 2006). A statistical model was proposed to predict NDMA formation kinetics
from pharmaceutical compounds such as ranitidine in various water matrices (Shen and
Andrews, 2011b). In addition, natural organic matter (NOM) was also investigated as
attempt has been ever made to model NDMA formation in wastewater or wastewater-
75
impacted waters. The challenge for a model development lies in the multitude of
precursors and precursor types present and hence the possibility of having various
The aim of this work is to formulate and evaluate a NDMA formation kinetics
model that is applicable to different water sources and model compounds. A simple
second-order kinetic reaction model was developed for NDMA formation. In this
formed during chloramination under specific water conditions, and chloramine decay
parameterized using NDMA formation data from literature data on NOM and model
precursor compounds (i.e. ranitidine). The optimization of the kinetic model parameters
have been proposed (Figure 6.1). The original concept of the model was that different
types of precursors may proceed along different mechanistic pathways with different
chloramine species and the reactions may potentially involve oxygen to produce
NDMA. Such a model would classify NDMA precursors (nM quantities) as having
either higher or lower yields and presumably different reaction rates with different
chloramine species. In a first step, using data obtained from our research of NDMA
dichloramine
Table 5.1 shows the decomposition reactions for chloramines in water (Ozekin
et al., 1996). The relationship between monochloramine and dichloramine derives from
reactions 3, 4 and 5. Dichloramine forms via an acid catalyzed reaction from two
NDMA as a combination of both chloramines reactions. kmono and kdi were the rate
constants for mono- and di-chloramine reactions respectively. A new apparent rate
constant kapp was then used in Equation 1c as the best fit second-order rate constant (M-
1s-1) in terms of monochloramine and NDMA precursor. Measured monochloramine
was used in the model to represent all chloramines since it is the dominant source of
dichloramine.
77
Table 5.1: Chloramine Decomposition Kinetics and Associated Rate Constants (Ozekin
et al., 1996)
Reaction Rate Constant
1 HOCl + NH3→ NH2Cl + H2O k1= 1.0×1010M-1h-1
2 NH2Cl + H2O → HOCl + NH3 k2=0.1h-1
3 HOCl + NH2Cl → NHCl2 + H2O k3=1.26×106 M-1h-1
4 NHCl2 + H2O→HOCl + NH2Cl k4=2.3×10-3 h-1
5 NH2Cl + NH2Cl → NHCl2 + NH3 kd*
6 NHCl2 + NH3 → NH2Cl + NH2Cl k6=2.0×108 M-1h-1
7 NH2Cl + NHCl2 →N2 + 3H+ + 3Cl- k7=55.0 M-1h-1
8 NHCl2 + H2O → NOH + 2HCl k8=6.0×105 M-1h-1
9 NOH + NHCl2 → N2 + H2O + HCl k9=1.0×108 M-1h-1
10 NOH + NH2Cl → N2 + H2O +HCl k10=3.0×107 M-1h-1
11 NH4+ → NH3 + H+ pKa=9.3
12 H2CO3 →HCO3 + H- + pKa=6.3
13 HCO3- → CO3 + H
2- + pKa=10.3
+
*kd= kH[H ] +kH2CO3[H2CO3] + KHCO3[HCO3 ];-
kH=2.5×107 M-2h-1
kHCO3= 800 M-2h-1
kH2CO3=40000 M-2h-1
despite there being various reactions pathways of chloramines and probably multiple
groups of precursor species with highly variable yields (0.017% for TMA, 90% for
water. Currently there is no method to predict NDMA formation kinetics, and most
research has relied upon simulated distributed system (SDS) tests (NH 2Cl~2.5mg/L))
DMA showed variable NDMA yields (Le Roux et al., 2011; Mitch et al., 2009).
formation from NOM. However, there was no correlation between NDMA formation
78
measurable in NDMA kinetic tests. Together with the measurement of
= [NDMAmax] ) as follows:
Vikesland et al., 2001). NDMA formation data at different time points were fitted to
the model using Kintecus (Ianni, 2002) and the rate constant, kapp, was optimized with
the highest correlation coefficient between experimental values and model fitting.
Monochloramine decays over time due to hydrolysis and reaction with organic
oxidants such as free chlorine or dichloramine, which would react with DOC. Another
pathway is, in the presence of NOM, monochloramine reacting directly with organic
matter. The rate of monochloramine loss in both pathways was found to be dependent
parameters (i.e. fast and slow reactive fractions of NOM) need to be reoptimized since
they are specific to reaction conditions. A simple first order degradation model with
79
presence of NDMA precursors (Equation 5-3). The rate constant is specific to
𝑑[𝑁𝐻2 𝐶𝑙]
= −𝑘𝑑𝑒𝑐𝑎𝑦 [𝑁𝐻2 𝐶𝑙] Equation 5-3
𝑑𝑡
Chen et al. modeled NDMA formation from reactions between NOM and
monochloramine (Chen and Valentine, 2006). They suggested that NOM in surface
waters could be oxidized involving two types of reactive sites of monochloramine loss.
A portion of the dissolved organic carbon (DOC) could react with monochloramine
rapidly within hours and the other part had a much slower reaction with free chlorine
(over days). However, their model had five parameters (i.e. fast and slow reactive
fractions of NOM) to be optimized which would vary between water sources. Here we
fitted their experimental data with our model. The monochloramine decay was modeled
as a first order reaction in Equation 5-2 and the monochloramine decay rate constants
are shown in Table 5.2. The decay rate of monochloramine increased when pH was
Then the NDMA formation data was fitted with our second order model (Figure
5.2). NDMA concentration at 120 h was used as NDMAmax (P0) although NDMA
formation had not reached its maximum at this time. The model fits NDMA formation
chloramine species, the model was not able to simulate the NDMA formation because
80
6. NDMA formation yields appear to increase with decreasing pH from 9 to 7 due to
presence of more dichloramine at lower pH. The optimized rate constant kapp varied
81
Figure 5.3: Model prediction of NDMA formation and monochloramine decay at
various ammonia concentrations (Cl/N ratio) in surface water. (Symbols: observation
data, lines: model predictions, pH=7. Data from Chen and Valentine, 2006)
The NDMA formation data in surface waters with various Cl/N ratios in Chen’s
work was also fitted with our model. Both monochloramine decay and NDMA
formation were well predicted (Figure 5.3). Results showed that a decreasing Cl/N ratio
reduced monochloramine decay rates, NDMA formation rates and NDMA yields. This
was the result of dichloramine formation being favored at high Cl/N ratios (low
(Chen and Valentine, 2006), the model successfully predicted NDMA formation over
time in surface waters from pH 7 to 9 and in conditions of Cl/N ratio from 0.1 to 0.7.
In addition to NOM, model compounds such as DMA and ranitidine were also
from various amine precursors (Selbes, 2014). However, NDMA formation kinetics
were not discussed. Here we apply our model to the NDMA kinetics data of five
precursor compounds from Selbes’ work (Selbes, 2014). DMA and four tertiary amines
(DMBzA) and ranitidine) were selected. These five precursors were chloraminated by
82
Selbes in three reaction conditions: in distilled deionized water at pH 7.5, a formation
potential (FP) test condition with 1.4mM monochloramine, and simulated distribution
system (SDS) with 0.04mM monochloramine, and SDS condition with 100 mg/L
monochloramine model simulation in NOM in Chen’s work showed that pH has a more
monochloramine decay rate of 0.007 h-1, between the rate constants at pH 7 (0.01 h -1)
decomposition in the deionized water. Figure 5.4 shows NDMA formation data
obtained from Selbes’ work and model fitting for precursors under various conditions
and the resulting rate constants are shown in the figure and listed in Table 5.3. The
model successfully fitted the NDMA formation kinetics for all five chemicals in most
tests. However, in SDS condition with excess ammonia, our model overestimates
NDMA formation in the first half reaction time and underestimates NDMA in the
second half period for ranitidine and DMBzA. It was the same with DMiPA in the SDS
condition test. In previous studies it was found that ranitidine and DMBzA were more
al., 2014). In NDMA formation from tertiary amines such as ranitidine, an intermediate
Roux et al., 2012; Liu et al., 2014). A possible explanation could be, in conditions with
form NDMA. Therefore, the presence of intermediates could ‘delay’ the NDMA
83
84
85
Figure 5.4: NDMA formation from model precursor compound data (Symbols), model
fitting (Lines) in FP tests (NH2Cl 1.4mM, pH=7.5), SDS conditions (NH2Cl 0.04mM,
pH=7.5) and SDS conditions with excess ammonia. (NDMA data from Selbes, 2014)
Although kapp× [NH2Cl] was greater in the FP tests, indicating a faster NDMA
formation in FP conditions than in SDS conditions, the optimized rate constants (k app)
in the FP tests were less than under SDS conditions, by an order of magnitude for model
the monochloramine concentrations (1.4 mM) were more than 5000 times the precursor
monochloramine present that reduced the rate constant. Rate constants kapp of ranitidine,
DMBzA and DMA are similar and that of DMiPA is much smaller. The similar k app
between ranitidine and DMA was unexpected since DMA and ranitidine have very
different yields (<3% and 80% respectively) and different proposed NDMA formation
mechanisms. In SDS conditions with excess ammonia, optimized kapp for both
ranitidine and DMBzA are less than those under SDS conditions, suggesting
Table 5.3: Optimized rate constant kapp for model compounds under various reaction
conditions. (NDMA data from Selbes, 2014)
Presence of NOM
Our model was also applied to NDMA formation by amine precursors in the
presence of NOM in natural waters. Shen et al. investigated the NDMA formation
decomposition. Model fitting and optimized rate constants are shown in Figure 5.5 and
Table 5.4. The model in equation 1c simulates NDMA formation from ranitidine in MQ
water with a high correlation coefficient (R2>0.93) and yields an optimized rate
constant of 1.3 M-1s-1. This is similar to the rate constant (1.2 M-1s-1) in Selbes’ work
87
under similar reaction conditions (DDW water, SDS, NH2Cl=0.04mM) and
demonstrates that our model is applicable to predict NDMA formation from ranitidine
However, for all four pharmaceutical precursors, the model overestimates the
NDMA formation in the first half experiment time and underestimated NDMA in the
second half. This is possibly due to the formation of an intermediate that delays the
Figure 5.5: NDMA formation from pharmaceutical compounds under SDS condition
(MQ water, NH2Cl=0.035mM, pH=7), data (symbols) and model fitting (lines).
(NDMA data from Shen and Andrews, 2011b).
88
Table 5.4: Optimized rate constant kapp for model compounds in different water
matrices with varied TOC. (NDMA Data from Shen and Andrews, 2011b)
Compounds NDMA kapp M-1s-1 (R2)
Yields in
SDS MQ % SDS 2mg/L TOC 6mg/L TOC
ranitidine ~90 1.3 (0.93) 0.82 0.25
sumatriptan ~2 0.28 (0.86) 0.24 0.08
chlorphenamine 3 0.73 (0.90) - 0.22
doxylamine 10 0.28 (0.84) - 0.13
natural waters, there was an initial lag-time when NDMA formation did not increase
for all four pharmaceutical compounds in lake and river waters. The lag-time was
longer at higher TOC concentrations. However, the lag-time could not be simulated
with our proposed model. In Shen’s work it was suggested that there was NOM-
pharmaceutical binding that inhibited the initial NDMA formation (Shen and Andrews,
2011b). In addition, dichloramine has a lower electron density on nitrogen due to two
charged NOM. Thus in the presence of NOM, dichloramine could more easily react
To better understand how NOM affects NDMA formation rates, our proposed
model was adjusted to fit the kinetics data. As there is no NDMA formed during the
lag-time, we start the model simulation at the end of the NDMA formation lag. The lag
time was removed and the kinetics data was refitted with our model. The model fits the
experimental data better for all four pharmaceutical compounds (Figure 5.6) and the
optimized rate constants were listed in Table 5.3. The optimized second-order rate
constants kapp were found to decrease with increasing TOC concentrations. This can be
89
explained by a competition between NOM and model compounds to react with mono-
and/or di- chloramine. In the river water samples (TOC = 6mg/L), the optimized rate
constants kapp for the pharmaceutical model compounds were in the range of 0.08 to
0.25 M-1s-1 (Table 4) and were comparable to the rate constants (0.02 to 0.09 M-1s-1) of
NDMA formation from NOM in surface waters with similar TOC concentration (TOC
=3.4 mg/L) in Chen’s work we discussed previously. By using the lag model, we were
able to compare the rate constant of NDMA formation at different DOC concentrations
and reveal how the DOC impacted the NDMA formation kinetics.
Figure 5.6: NDMA formation of amine precursors in river water (SDS, pH=7,
TOC=6mg/L) and modeling of NDMA formation without lag-time, data (symbols) and
model fitting (lines) (NDMA data from Shen and Andrews, 2011b)
90
5.4 Summary and Conclusions
observed in the literature. Results show that a second-order kinetic rate model simulates
NDMA formation from NOM and model precursors over a range of reaction conditions.
A narrow range of rate constants were obtained and appear to indicate a similar rate-
limiting reaction step among different precursors and water sources. Though the model
was not intended to reveal the relative importance of mono- or di- chloramine reactions
DOC and pH affect NDMA formation kinetics. In real water utilities, the model could
be used to predict NDMA formation by measuring the NDMA max and monochloramine.
different amines such as DMA and ranitidine. NDMA kinetics test could be performed
characterization of more precursors and their kinetics studies could help better
understand NDMA formation in different water sources and a more precise model could
be developed.
5.5 Acknowledgements
This research was supported by the Water Research Foundation (Project 4499,
Fellowship, Water Environment Federation Canham Scholarship, and the Arizona State
91
CHAPTER 6
6.1 Introduction
water matrices based on a simple second order reaction model (Equation 6-1):
d[NDMA]
= 𝑘𝑎𝑝𝑝 [Precursor][NH2 Cl] Equation 6-1
dt
This model worked very well when applied to our experiments as well as to
literature data with correlation coefficients more than 0.9 (Chapters 4 & 5). However
this model does not take into account some of our observations as well as issues
(Schreiber and Mitch, 2006b), the potential impact of dissolved oxygen (Schreiber and
Mitch, 2006b; Le Roux et al., 2011) as well as an impact of the nature of the buffer in
In our experimental design and in the model monochloramine was used as the
only oxidant that chloraminates the NDMA precursors to form NDMA. This
92
Figure 6.1: Theoretical Breakpoint Curve (USEPA, 1999)
Figure 6.2: Distribution Diagram for Chloramines with pH (Palin, 1950; USEPA, 1999)
our experimental conditions (pH = 8, Cl2:N = 4.2) and the dichloramine formation from
monochloramine is negligible.
93
Monochloramine is a of great advantage when aiming to develop an operational
colorimetry, is used to measure total chlorine, free chlorine and monochloramine. The
chlorine- and monochloramine plus free chlorine. The detection limit of this method is
both equations using the respective molar extinction coefficients at 245nm and 295 nm
(Schreiber and Mitch, 2005).The detection limit of the second method is ~ 0.2 mgCl2/L.
Both of these methods are hence endowed with substantial uncertainties and high
detection limits.
kinetics experiments in Chapter 4, showed that dichloramine does likely affect NDMA
formation even at pH 8 and a Cl2:N ratio of 4.2. Specifically, the final NDMA
conversion in samples with more monochloramine (18-20 mgCl2/L) is higher than that
with less monochloramine (6~7 mgCl2/L). Both monochloramine doses are in large
more NDMA formation. Our model using only monochloramine worked even the
trace levels. However, the model can most likely not be extended to other reaction
Cl2:N ratio. Therefore, it is necessary to investigate the NDMA formation kinetics from
will improve the NDMA kinetics model and make it more applicable to predict NDMA
d[NDMA]
= 𝑘𝑚𝑜𝑛𝑜 [Precursor][NH2 Cl] + 𝑘𝑑𝑖 [Precursor][NHCl2 ] Equation 6-2
dt
is the potential role of dissolved oxygen in NDMA formation. In fact, it has been shown
that dissolved oxygen concentrations affect the NDMA formation from model
precursors such as DMA and ranitidine (Schreiber and Mitch, 2006b; Le Roux et al.,
2011). However, no experimental data has been reported on complex real samples like
wastewater or surface water and hence it is unknown if the amount of oxygen matters
the pH itself. A variety of buffer systems has been applied to maintain constant pH
addressed the impact of the nature of the buffer species as it is not expected to affect
NDMA formation. However in the literature there are many instances of disagreement
in terms of NDMA formation reported for the same amine precursors (Selbes et al.,
2013) and one of the differences between studies is the nature of the buffer system.
95
Therefore it might be necessary to exclude the possible effect of buffer species on
NDMA formation.
buffer effects.
prepared by adding sodium hypochlorite into buffered (10 mM, Borate pH = 8.0 or
Phosphate pH =7) ammonium chloride solution to produce a Cl2:N mass ratio of 6:1.
Chloramine stock solution was then spiked into DI water at ~5 mgCl2/L. Since
Loveland, CO). The method in our test to quantify monochloramine and dichloramine
and 245 nm and solving for their concentration from their extinction coefficients at both
wavelengths.
with varying dissolved oxygen levels in one wastewater secondary effluent (WW5 in
Chapter 4). Dissolved oxygen concentrations were reduced from ~8 mg/L to below 0.1
mg/L by bubbling high purity argon gas into each sample for 5 minutes. Dissolved
oxygen was measured by a portable meter (Thermo Scientific Inc., Waltham, MA).
solutions, borate, phosphate, and carbonate buffer solutions were made and were added
into water samples and chloramine stock solutions (pH=8, 10 mM). Water samples of
solutions into DI water. Wastewater effluent samples and surface water were sampled
precursor solutions, wastewater and surface water at 18 mgCl2/L. Samples for NDMA
formation were kept in dark at room temperature (23 ± 2 °C) for 72 hours until
quenching and extraction. Quenching, extraction and NDMA analysis were the same
as described in Chapter 4.
include it in the model, the dichloramine contribution needs to be isolated from the
To increase the dichloramine concentration, the Cl2 to N2 ratio was changed and
a Cl2:N ratio = 6:1 was chosen based on Figure 6.1. However, at pH 8 only 10% of
dichloramine at maximum can be obtained. After 1 day aging, the ratio between
(USEPA, 1999). However under these conditions the observed pH was around 2 and
Experiments were conducted several times and showed similar results. The
dichloramine and hence isolate out the sole contribution of monochloramine. Therefore
ammonium was first used to inhibit the formation of dichloramine in order to shift the
equilibrium distribution.
NH4+ (mass ratio NH3: NH2Cl = 100:4, NH2Cl = 2000mgCl2/L) was added in
preformed chloramine stock solution. The excess NH4+ lowered the pH in stock solution
from 8 to less than 7. Chloramine solutions with and without addition of NH 4+ were
35
30
25
NDMA ng/L
20
15
10 NH4+ added
5 No Excess NH4+
0
0 50 100 150 200 250
Time h
Figure 6.3: NDMA formation kinetics of wastewater effluents with and without excess
NH4+ in chloramine stock solution
98
NDMA formation was lower with an excess NH4+ than without excess NH4+
(Figure 6.3). However, as the pH could not be well controlled in this method, the lower
NDMA formation was possibly due to the decomposition of chloramine at the lower
NH4+ in stock solution was not a good way to inhibit dichloramine formation.
We then added NH4+ (mass ratio NH3: NH2Cl = 100:4) directly into buffered
water solution in which pH did not change in presence of NH 4+ during test. First at pH
8 an excess NH4+ was added in the water solution prior to 5 mgCl2/L chloramine. No
detectable dichloramine was found within 90 hours in both water samples with and
without excess NH4+, probably due the high detection limit of the measurement. Then
monochloramine in all water samples. As shown in Figure 6.4, excess NH 4+ does not
50 50
NH2Cl = 4mg/L NH2Cl = 20mg/L
40 40
add NH4+
add NH4+
NHCl2 %
NHCl2 %
30 30
No excess No excess
NH4+ NH4+
20 20
10 10
0 0
24h 72h 24h 72h
Figure 6-4: NHCl2/NH2Cl ratio with and without excess NH4+ in nano pure water at
pH=7.
within 24 hours. While samples without ammonia had about 15% of dichloramine.
However, 10mM phosphate buffer solution we used was not strong enough to buffer
99
the excess ammonia. The pH of water went up to 9 after ammonia was added. In
addition, after 24 hours, about 5% dichloramine was found in the water with ammonia.
Ammonia could only inhibit formation of dichloramine in limited time and the pH
The role of the dissolved oxygen on NDMA formation kinetics was studied in
chloramination tests in wastewater (WW5 in Chapter 4). Figure 6-5 shows the impact
700
600
500
NDMA (ng/L)
400
300
0
0 20 40 60 80 100 120 140
Time (hour)
concentrations were achieved over a similar time period (~50 hours). But similar to
monochloramine, NDMAmax (~8.4 nM) at the higher dissolved oxygen level (8.2 ± 0.1
mg O2/L) was more than that (3.8 nM NDMAmax) formed in the presence of lower
dissolved oxygen level (less than 2.3 mg O2/L). Previous work showed a dependence
100
of NDMA yields on dissolved oxygen in the NDMA formation from DMA and
ranitidine although their mechanisms were thought to be different (Schreiber and Mitch,
2006b; Le Roux et al., 2011). For both precursors, NDMA formation could be
sensitive to dichloramine and monochloramine respectively, and our results could not
tell if monochloramine or dichloramine was the responsible species for NDMA formed.
Monochloramine degradation was observed to be much slower in the sample with low
dissolved oxygen (Figure 6.6), indicating the interactions between chloramines and
25
20
NH2Cl (mgCl2/L)
15
10
High O2 level
5
Low O2 level
0
0 50 100 150
Time (hour)
formation kinetics. Dissolved oxygen could possibly be included in the kinetics model,
formation potential was investigated using commonly used buffer systems such as
101
borate (Hanigan et al., 2012), phosphate (Selbes et al., 2013) and bicarbonate (Schreiber
and Mitch, 2006b). As shown in Figure 6.7, no effect of buffer species on NDMA
formation from the four model precursors as well as in wastewater and surface water
was observed. In addition, no effect of buffer concentration was observed. In the borate
buffer at 100 mM NDMA formation was reduced, however this was the result of a
102
Figure 6.7: (a) NDMA formation from model precursors (pH=8); (b) NDMA formation
in buffered (pH=8) wastewater and surface water; (c) NDMA formation in buffered
wastewater with buffer concentration from 0.1 mM to 100 mM.
103
6.4 Conclusions
In the first part of this work, experiments were designed to explore the NDMA
solution (2000 mgCl2/L) but the chloramine concentration was reduced to less than 250
enhanced at pH lower than 7 (Figure 6.2), but the problem is that the low pH does not
apply to the real waters such as surface water or wastewater effluents. The suppression
of dichloramine formation also turned out unsuccessful. In our experiments we did not
observe that the excess ammonium (NH4+) could inhibit the formation of dichloramine
in either chloramine stock solution and in water sample. Large excess of ammonium
(mass ratio NH3: NH2Cl = 100:4) in the stock solution will however affect the pH of
the chloramine stock solution. Ammonia was found to be able to inhibit the
addition, but the dichloramine formation happened after 24 hours. Therefore, in our
preliminary tests neither ammonium nor ammonia was able to suppress the
dichloramine measurements. The current two methods as described in section 6.1, due
to their high detection limits, are not able to quantify the dichloramine concentration or
monitor the change of dichloramine concentrations over time in water samples where
dichloramine could be interfered by species in water samples. In the Hach method, the
104
ammonium could affect the chloramine measurement. Organic matter would
In the last part of this chapter, we found that NDMA formation was not
is higher in the presence of more dissolved oxygen. Future experiments are needed to
reveal the role of dissolved oxygen in the NDMA formation yields and kinetics.
105
CHAPTER 7
This chapter will summarize the main findings of this thesis and provide suggestions
7.1 Summary
Analytical methods based on SPME and SPE coupled with GC-MS were
PDMS/DVB and CAR/PDMS fibers were tested for the SPME method.
fiber could not reach equilibrium even after 9 hours. SPME sampling is possible
but leads to high detection limits (~ 1 ng/m3 and 8 ng/m3 for CAR/PDMS and
PDMS/DVB, respectively) which might allow for high exposure monitoring but
cartridges allows for low detections limit of 0.003ng/m3 for a 2 m3 air sample.
The collection efficiency of SPE cartridges is more than 90% with negligible
The SPE method was applied to ambient sampling in various environments and
NDMA was found in all field samples at concentrations between 0.1 and 13.0
ng/m3, higher than EPA’s suggested screening level of NDMA in ambient air
of 0.07 ng/m3.
106
Chapter 3- Optical Properties of Water Soluble Organic Carbon (WSOC) in
WSOC has a stronger impact on NDMA photolysis than inorganic species such
as nitrate or nitrite. The screening effect from organic matter can increase the
(MAE) than organic matter in fog and cloud water, resulting from a different
Waters
maximum formations were observed in the range of 100 -1000 ng/L and 15-50
was well predicted by the model with correlation coefficients higher than 0.9.
107
The model fitted rate constants were in range of 0.01-0.09 M-1s-1 for different
NDMA formation data from the literature, including natural organic matter
(NOM) and model precursors, were successfully fitted with the second order
NDMA formation rate constants were able to describe how water conditions
Precursors with different NDMA formation yields were found to have similar
the dichloramine formation for a limited time (less than 24h), but ammonia will
formation.
For NDMA measurement in air, the SPME method has not been used in ambient
sampling due to its high detection limit. However, the SPME with GC-MS could still
be applied to measure NDMA in locations such as indoor area, especially with tobacco
Not only NDMA but also other nitrosamines are present in air. Therefore,
matter.
WSOC from particulate matter has shown to impact NDMA photolysis and it is
found to have different absorptivity from organic matter in fog and cloud. It will be
interesting to explore what other species could be impacted by such ‘screening’ effect
of organic matter and the extent of this effect. Additionally, it remains unknown how
radicals which will react with the species we are interested, such as nitrosamines.
Although in this work the developed second order reaction model fitted NDMA
formation data well in our experiments and in literature data, additional NDMA kinetics
work is needed, especially for those precursors that have been recently identified, such
109
developed as we have identified possible impacts of dichloramine and dissolved
oxygen, which might limit the conditions under which the model remains valid.
using current methods. To explore the NDMA formation from dichloramine at trace
developed.
110
REFERENCES
Allen, J.M., Allen, S.K. and Baertschi, S.W., 2000. 2-Nitrobenzaldehyde: a convenient
UV-A and UV-B chemical actinometer for drug photostability testing. Journal of
Pharmaceutical and Biomedical Analysis, 24(2), pp.167-178.
Andrade, R., Reyes, F.G. and Rath, S., 2005. A method for the determination of volatile
N-nitrosamines in food by HS-SPME-GC-TEA. Food Chemistry, 91(1), pp.173-179.
Andreae, M.O. and Gelencsér, A., 2006. Black carbon or brown carbon? The nature of
light-absorbing carbonaceous aerosols. Atmospheric Chemistry and Physics, 6(10),
pp.3131-3148.
Aragón, M., Marcé, R.M. and Borrull, F., 2013. Determination of N-nitrosamines and
nicotine in air particulate matter samples by pressurised liquid extraction and gas
chromatography-ion trap tandem mass spectrometry. Talanta, 115, pp.896-901.
Baisautova, Z., 2008. Environmental Fate Assessment of the Rocket Fuel Compound,
1, 1-dimethylhydrazine and Its By-product N-nitrosodimethylamine. ProQuest.
111
Benn, T., Herckes, P., Westerhoff, P., 2012. Fullerenes in Environmental Samples: C60
in atmospheric particulate matter, in Analysis and Risk of Nanomaterials in
Environmental and Food Samples, Edited by Damia Barcelo and Marinella Farré,
Elsevier Science, Comprehensive Analytical Chemistry Series, #59
Bolto, B., 2005. Reaction of chlorine with organic polyelectrolytes in water treatment:
a review. Journal of Water Supply: Research and Technology-Aqua, 54(8), pp.531-
544.
Bones, D.L., Henricksen, D.K., Mang, S.A., Gonsior, M., Bateman, A.P., Nguyen,
T.B., Cooper, W.J. and Nizkorodov, S.A., 2010. Appearance of strong absorbers and
fluorophores in limonene‐O3 secondary organic aerosol due to NH4+‐mediated
chemical aging over long time scales. Journal of Geophysical Research:
Atmospheres, 115(D5).
Boyd, J.M., Hrudey, S.E., Li, X.F. and Richardson, S.D., 2011. Solid-phase extraction
and high-performance liquid chromatography mass spectrometry analysis of
nitrosamines in treated drinking water and wastewater. TrAC Trends in Analytical
Chemistry, 30(9), pp.1410-1421.
Brito, J., Rizzo, L.V., Herckes, P., Vasconcellos, P.D.C., Caumo, S.E.D.S., Fornaro,
A., Ynoue, R.Y., Artaxo, P. and Andrade, M.D.F., 2013. Physical–chemical
characterisation of the particulate matter inside two road tunnels in the São Paulo
Metropolitan Area. Atmospheric Chemistry and Physics, 13(24), pp.12199-12213.
Brown, S.G., Frankel, A. and Hafner, H.R., 2007. Source apportionment of VOCs in
the Los Angeles area using positive matrix factorization. Atmospheric
Environment, 41(2), pp.227-237.
Brubaker, K.L., Stetter, J.R., Demirgian, J.C., Boparai, A. and Schneider, J.F.,
1985. Products of the neutralization of hydrazine fuels with hypochlorite (No. CONF-
8511110-4). Argonne National Lab., IL (USA).
Brunnemann, K.D., Stahnke, G. and Hoffmann, D., 1978. Chemical studies on tobacco
smoke. LXI. Volatile pyridines: Quantitative analysis in mainstream and sidestream
smoke of cigarettes and cigars. Analytical Letters, 11(7), pp.545-560.
112
Carrico, C.M., Petters, M.D., Kreidenweis, S.M., Sullivan, A.P., McMeeking, G.R.,
Levin, E.J.T., Engling, G., Malm, W.C. and Collett Jr, J.L., 2010. Water uptake and
chemical composition of fresh aerosols generated in open burning of
biomass. Atmospheric Chemistry and Physics, 10(11), pp.5165-5178.
Charrois, J.W., Arend, M.W., Froese, K.L. and Hrudey, S.E., 2004. Detecting N-
nitrosamines in drinking water at nanogram per liter levels using ammonia positive
chemical ionization. Environmental Science & Technology, 38(18), pp.4835-4841.
Charrois, J.W. and Hrudey, S.E., 2007. Breakpoint chlorination and free-chlorine
contact time: Implications for drinking water N-nitrosodimethylamine
concentrations. Water Research, 41(3), pp.674-682.
Chen, B., Lee, W., Westerhoff, P.K., Krasner, S.W. and Herckes, P., 2010. Solar
photolysis kinetics of disinfection byproducts. Water Research, 44(11), pp.3401-3409.
Cheng, Y., He, K.B., Zheng, M., Duan, F.K., Du, Z.Y., Ma, Y.L., Tan, J.H., Yang,
F.M., Liu, J.M., Zhang, X.L. and Weber, R.J., 2011. Mass absorption efficiency of
elemental carbon and water-soluble organic carbon in Beijing, China. Atmospheric
Chemistry and Physics, 11(22), pp.11497-11510.
da Silva, E.F. and Booth, A.M., 2013. Emissions from postcombustion CO2 capture
plants. Environmental Science & Technology, 47(2), pp.659-660.
da Silva, E.F., Hoff, K.A. and Booth, A., 2013a. Emissions from CO2 capture plants;
an overview. Energy Procedia, 37, pp.784-790.
da Silva, E.F., et al., 2013b. Emission studies from a CO2 capture pilot plant. Energy
Procedia 37, 778–783.
113
Du, Z., He, K., Cheng, Y., Duan, F., Ma, Y., Liu, J., Zhang, X., Zheng, M. and Weber,
R., 2014. A yearlong study of water-soluble organic carbon in Beijing II: Light
absorption properties. Atmospheric Environment, 89, pp.235-241.
Duirk, S.E., Gombert, B., Croué, J.P. and Valentine, R.L., 2005. Modeling
monochloramine loss in the presence of natural organic matter. Water
Research, 39(14), pp.3418-3431.
Ehrenhauser, F.S., Khadapkar, K., Wang, Y., Hutchings, J.W., Delhomme, O.,
Kommalapati, R.R., Herckes, P., Wornat, M.J. and Valsaraj, K.T., 2012. Processing of
atmospheric polycyclic aromatic hydrocarbons by fog in an urban environment. Journal
of Environmental Monitoring, 14(10), pp.2566-2579.
Ervens, B.T.B.W.R., Turpin, B.J. and Weber, R.J., 2011. Secondary organic aerosol
formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory,
field and model studies. Atmospheric Chemistry and Physics, 11(21), pp.11069-11102.
Fajen, J.M., Carson, G.A., Rounbehler, D.P., Fan, T.Y., Vita, R., Goff, U.E., Wolf,
M.H., Edwards, G.S., Fine, D.H., Reinhold, V. and Biemann, K., 1979. N-nitrosamines
in the rubber and tire industry. Science, 205(4412), pp.1262-1264.
Farren, N.J., Ramírez, N., Lee, J.D., Finessi, E., Lewis, A.C. and Hamilton, J.F., 2015.
Estimated Exposure Risks from Carcinogenic Nitrosamines in Urban Airborne
Particulate Matter. Environmental Science & Technology, 49(16), pp.9648-9656.
Feng, J., Hu, M., Chan, C.K., Lau, P.S., Fang, M., He, L. and Tang, X., 2006. A
comparative study of the organic matter in PM 2.5 from three Chinese megacities in
three different climatic zones. Atmospheric Environment, 40(21), pp.3983-3994.
Fine, D.H., Rounbehler, D.P. and Belcher, N.M., 1976a. N-Nitroso compounds:
Detection in ambient air. Science, 192(4246), pp.1328-1330.
Fine, D.H., Rounbehler, D.P., Pellizzari, E.D., Bunch, J.E., Berkley, R.W., McCrae, J.,
Bursey, J.T., Sawicki, E., Krost, K. and DeMarrais, G.A., 1976b. N-
nitrosodimethylamine in air. Bulletin of environmental contamination and
toxicology, 15(6), pp.739-746.
Fine, D.H., Reinhold, V. and Biemann, K., 1979. N-nitrosamines in the rubber and tire
industry. Science, 205(4412), pp.1262-1264.
Finlayson-Pitts, B.J. and Pitts Jr, J.N., 1999. Chemistry of the upper and lower
atmosphere: theory, experiments, and applications. Academic press.
Ge, X., Wexler, A.S. and Clegg, S.L., 2011. Atmospheric amines–Part I. A
review. Atmospheric Environment, 45(3), pp.524-546.
114
Gordon R. J., 1978. Survey for Airborne Nitrosamines Prepared by University of
California, School of Medicine, for the California Air Resources Board. Contract No.
A6-096-30.
Hallquist, M., Wenger, J.C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M.,
Dommen, J., Donahue, N.M., George, C., Goldstein, A.H. and Hamilton, J.F., 2009.
The formation, properties and impact of secondary organic aerosol: current and
emerging issues. Atmospheric Chemistry and Physics, 9(14), pp.5155-5236.
Hanigan, D., Zhang, J., Herckes, P., Krasner, S.W., Chen, C. and Westerhoff, P., 2012.
Adsorption of N-nitrosodimethylamine precursors by powdered and granular activated
carbon. Environmental Science & Technology, 46(22), pp.12630-12639.
Hanigan, D., Thurman, E.M., Ferrer, I., Zhao, Y., Andrews, S., Zhang, J., Herckes, P.
and Westerhoff, P., 2015. Methadone Contributes to N-Nitrosodimethylamine
Formation in Surface Waters and Wastewaters during Chloramination. Environmental
Science & Technology Letters, 2(6), pp.151-157.
Hanst, P.L., Spence, J.W. and Miller, M., 1977. Atmospheric chemistry of N-nitroso
dimethylamine. Environmental Science & Technology, 11(4), pp.403-405.
Haruta, S., Jiao, W., Chen, W., Chang, A.C. and Gan, J., 2011. Evaluating Henry's law
constant of N-nitrosodimethylamine (NDMA). Water Science & Technology, 64(8).
Hecobian, A., Zhang, X., Zheng, M., Frank, N., Edgerton, E.S. and Weber, R.J., 2010.
Water-Soluble Organic Aerosol material and the light-absorption characteristics of
aqueous extracts measured over the Southeastern United States. Atmospheric
Chemistry and Physics, 10(13), pp.5965-5977.
Hennigan, C.J., Bergin, M.H., Russell, A.G., Nenes, A. and Weber, R.J., 2009.
Gas/particle partitioning of water-soluble organic aerosol in Atlanta. Atmospheric
Chemistry and Physics, 9(11), pp.3613-3628.
Herckes, P., Leenheer, J.A. and Collett, J.L., 2007. Comprehensive characterization of
atmospheric organic matter in Fresno, California fog water. Environmental Science &
Technology, 41(2), pp.393-399.
Herckes, P., Valsaraj, K.T. and Collett, J.L., 2013. A review of observations of organic
matter in fogs and clouds: Origin, processing and fate. Atmospheric Research, 132,
pp.434-449.
Hoffer, A., Gelencsér, A., Guyon, P., Kiss, G., Schmid, O., Frank, G.P., Artaxo, P. and
Andreae, M.O., 2006. Optical properties of humic-like substances (HULIS) in biomass-
burning aerosols. Atmospheric Chemistry and Physics, 6(11), pp.3563-3570.
Hung, H.W., Lin, T.F., Chiu, C.H., Chang, Y.C. and Hsieh, T.Y., 2010. Trace analysis
of N-nitrosamines in water using solid-phase microextraction coupled with gas
chromatograph–tandem mass spectrometry. Water, Air, & Soil Pollution, 213(1-4),
pp.459-469.
115
Hutchings, J.W., Robinson, M.S., McIlwraith, H., Kingston, J.T. and Herckes, P., 2009.
The chemistry of intercepted clouds in Northern Arizona during the North American
monsoon season. Water, Air, and Soil Pollution, 199(1-4), pp.191-202.
Hutchings, J.W., Ervens, B., Straub, D. and Herckes, P., 2010. N-nitrosodimethylamine
occurrence, formation and cycling in clouds and fogs. Environmental Science &
Technology, 44(21), pp.8128-8133.
IARC, 1987. Some N-nitroso compounds. IARC Monographs on the Evaluation of the
Carcinogenic Risk of Chemicals to Humans, vol. 17. Lyon, France
Jaffrezo, J.L., Aymoz, G., Delaval, C. and Cozic, J., 2005. Seasonal variations of the
water soluble organic carbon mass fraction of aerosol in two valleys of the French
Alps. Atmospheric Chemistry and Physics, 5(10), pp.2809-2821.
Karl, M., Dye, C., Wisthaler, A., Schmidbauer, N., Mikoviny, T., Lanza, M., D'Anna,
B., Meme, A., Vázquez-Moreno, M., Muñoz, A., Garciá, M.R., Bórras, E., 2013. Photo-
oxidation of two amines for use in CO2 capture: Experimental studies in the European
Photo Reactor EUPHORE. Kjeller, NILU (NILU OR, 44/2013)
Kemper, J.M., Walse, S.S. and Mitch, W.A., 2010. Quaternary amines as nitrosamine
precursors: a role for consumer products?. Environmental Science &
Technology, 44(4), pp.1224-1231.
Kim, H., Kim, J.Y., Jin, H.C., Lee, J.Y. and Lee, S.P., 2016. Seasonal variations in the
light-absorbing properties of water-soluble and insoluble organic aerosols in Seoul,
Korea. Atmospheric Environment.
Kirchstetter, T.W., Novakov, T. and Hobbs, P.V., 2004. Evidence that the spectral
dependence of light absorption by aerosols is affected by organic carbon. Journal of
Geophysical Research: Atmospheres, 109(D21).
Kirillova, E.N., Andersson, A., Han, J., Lee, M. and Gustafsson, Ö., 2014. Sources and
light absorption of water-soluble organic carbon aerosols in the outflow from northern
China. Atmospheric Chemistry and Physics, 14(3), pp.1413-1422.
Krasner, S.W., Westerhoff, P., Chen, B., Rittmann, B.E. and Amy, G., 2009.
Occurrence of disinfection byproducts in United States wastewater treatment plant
effluents. Environmental Science & Technology, 43(21), pp.8320-8325.
116
Krasner, S.W., Westerhoff, P., Mitch, W.A. and Skadsen, J., 2012. Case studies on
nitrosamine formation and control at full-scale drinking water treatment plants. In
Proceedings of the 2012 American Water Works Association Water Quality
Technology Conference, Denver, Colo.
Krasner, S.W., Mitch, W.A., McCurry, D.L., Hanigan, D. and Westerhoff, P., 2013.
Formation, precursors, control, and occurrence of nitrosamines in drinking water: a
review. Water Research, 47(13), pp.4433-4450.
Langford, V.S., Gray, J.D., Maclagan, R.G., Milligan, D.B. and McEwan, M.J., 2015.
Real-time measurements of nitrosamines in air. International Journal of Mass
Spectrometry, 377, pp.490-495.
Le Roux, J., Gallard, H., Croué, J.P., Papot, S. and Deborde, M., 2012. NDMA
formation by chloramination of ranitidine: kinetics and mechanism. Environmental
Science & Technology, 46(20), pp.11095-11103.
Lee, A.K., Hayden, K.L., Herckes, P., Leaitch, W.R., Liggio, J., Macdonald, A.M. and
Abbatt, J.P.D., 2012. Characterization of aerosol and cloud water at a mountain site
during WACS 2010: secondary organic aerosol formation through oxidative cloud
processing. Atmospheric Chemistry and Physics, 12(15), pp.7103-7116.
Lee, C., Schmidt, C., Yoon, J. and Von Gunten, U., 2007. Oxidation of N-
nitrosodimethylamine (NDMA) precursors with ozone and chlorine dioxide: kinetics
and effect on NDMA formation potential. Environmental Science &
Technology, 41(6), pp.2056-2063.
Lestremau, F., Desauziers, V. and Fanlo, J.L., 2001. Formation of artefacts during air
analysis of volatile amines by solid-phase micro extraction. Analyst, 126(11), pp.1969-
1973.
Li, C, 2011. Trends and Effects of Chloramine in Drinking Water. Water Conditioning
& Purification, 53(10), 52-56.
Liew, D., Linge, K.L., Joll, C., Heitz, A., Trolio, R., Breckler, L., Henderson, R. and
Charrois, J.W.A., 2011. Formation of nitrogenous disinfection by-products (N-DBPs)
in raw and treated drinking water. In 2011 Oz Water Conference.
Liu, Y.D., Selbes, M., Zeng, C., Zhong, R. and Karanfil, T., 2014. Formation
Mechanism of NDMA from ranitidine, trimethylamine, and other tertiary amines
during chloramination: A computational study. Environmental Science &
Technology, 48(15), pp.8653-8663.
117
Lunn, G. and Sansone, E.B., 1994. Oxidation of 1, 1-dimethylhydrazine (UDMH) in
aqueous solution with air and hydrogen peroxide. Chemosphere, 29(7), pp.1577-1590.
Lunn, G., Sansone, E.D., Andrews, A.W. and Zeiger, E., 1991. Aerial oxidation of
hydrazines to nitrosamines. Environmental and Molecular Mutagenesis, 17(1), pp.59-
62.
Mancilla, Y., Mendoza, A., Fraser, M.P. and Herckes, P., 2015. Chemical
characterization of fine organic aerosol for source apportionment at Monterrey,
Mexico. Atmospheric Chemistry and Physics Discussions, 15(13), pp.17967-18010.
Masuda, M., Mower, H.F., Pignatelli, B., Celan, I., Friesen, M.D., Nishino, H. and
Ohshima, H., 2000. Formation of N-nitrosamines and N-nitramines by the reaction of
secondary amines with peroxynitrite and other reactive nitrogen species: comparison
with nitrotyrosine formation. Chemical Research in Toxicology, 13(4), pp.301-308.
Mirvish, S.S., Issenberg, P. and Sornson, H.C., 1976. Air—Water and Ether—Water
Distribution of N—Nitroso Compounds: Implications for Laboratory Safety, Analytic
Methodology, and Carcinogenicity for the Rat Esophagus, Nose, and Liver. Journal of
the National Cancer Institute, 56(6), pp.1125-1129.
Mirvish, S.S., 1995. Role of N-nitroso compounds (NOC) and N-nitrosation in etiology
of gastric, esophageal, nasopharyngeal and bladder cancer and contribution to cancer
of known exposures to NOC. Cancer Letters, 93(1), pp.17-48
Mitch, W., Krasner, S. W., Westerhoff, P., Dotson, A. 2009. Occurrence and Formation
of Nitrogenous Disinfection By-Products (Final Report, Project #3014);
AwwaRF/USEPA: Denver, CO, 2009; p 145.
Mitch, W.A. and Sedlak, D.L., 2002b. Factors controlling nitrosamine formation during
wastewater chlorination. Water Science and Technology: Water Supply, 2(3), pp.191-
198.
Mitch, W.A., Sharp, J.O., Trussell, R.R., Valentine, R.L., Alvarez-Cohen, L. and
Sedlak, D.L., 2003. N-nitrosodimethylamine (NDMA) as a drinking water
contaminant: a review. Environmental Engineering Science, 20(5), pp.389-404.
118
Mitch, W.A. and Schreiber, I.M., 2008. Degradation of tertiary alkylamines during
chlorination/chloramination: implications for formation of aldehydes, nitriles,
halonitroalkanes, and nitrosamines. Environmental Science & Technology, 42(13),
pp.4811-4817.
Miyazaki, Y., Kondo, Y., Takegawa, N., Komazaki, Y., Fukuda, M., Kawamura, K.,
Mochida, M., Okuzawa, K. and Weber, R.J., 2006. Time‐resolved measurements of
water‐soluble organic carbon in Tokyo. Journal of Geophysical Research:
Atmospheres, 111(D23).
Müller, J.F., Stavrakou, T., Wallens, S., Smedt, I.D., Roozendael, M.V., Potosnak,
M.J., Rinne, J., Munger, B., Goldstein, A. and Guenther, A.B., 2008. Global isoprene
emissions estimated using MEGAN, ECMWF analyses and a detailed canopy
environment model. Atmospheric Chemistry and Physics, 8(5), pp.1329-1341.
Munch, J.W. and Bassett, M.V., 2004. Method 521 determination of nitrosamines in
drinking water by solid phase extraction and capillary column gas chromatography with
large volume injection and chemical ionization tandem mass spectrometry
(MS/MS). National Exposure Research Laboratory Office of Research and
Development, US Environmental Protection Agency, Cincinnati.
Nielsen, C.J., Herrmann, H. and Weller, C., 2012. Atmospheric chemistry and
environmental impact of the use of amines in carbon capture and storage
(CCS). Chemical Society Reviews, 41(19), pp.6684-6704.
Ozekin, K., Valentine, R.L. and Vikesland, P.J., 1996. Modeling the decomposition of
disinfecting residuals of chloramine. Water Disinfection and Natural Organic
Matter, 649, pp.115-125.
Padhye, L.P., Hertzberg, B., Yushin, G. and Huang, C.H., 2011. N-nitrosamines
formation from secondary amines by nitrogen fixation on the surface of activated
carbon. Environmental Science & Technology, 45(19), pp.8368-8376.
119
Park, S.H., Wei, S., Mizaikoff, B., Taylor, A.E., Favero, C. and Huang, C.H., 2009.
Degradation of amine-based water treatment polymers during chloramination as N-
nitrosodimethylamine (NDMA) precursors. Environmental Science &
Technology, 43(5), pp.1360-1366.
Park, S.S. and Cho, S.Y., 2011. Tracking sources and behaviors of water-soluble
organic carbon in fine particulate matter measured at an urban site in
Korea. Atmospheric Environment, 45(1), pp.60-72.
Pérez, D.M., Alatorre, G.G., Álvarez, E.B., Silva, E.E. and Alvarado, J.F.J., 2008.
Solid-phase microextraction of N-nitrosodimethylamine in beer. Food
Chemistry, 107(3), pp.1348-1352.
Popp, P. and Paschke, A., 1997. Solid phase microextraction of volatile organic
compounds using carboxen-polydimethylsiloxane fibers. Chromatographia, 46(7-8),
pp.419-424.
Reynolds, A.J., Verheyen, T.V., Adeloju, S.B., Meuleman, E. and Feron, P., 2012.
Towards commercial scale postcombustion capture of CO2 with monoethanolamine
solvent: key considerations for solvent management and environmental
impacts. Environmental Science & Technology, 46(7), pp.3643-3654.
Rochelle, G.T., 2009. Amine scrubbing for CO2 capture. Science, 325(5948), pp.1652-
1654.
Rounbehler, D.P., Reisch, J.W., Coombs, J.R. and Fine, D.H., 1980. Nitrosamine air
sampling sorbents compared for quantitative collection and artifact
formation. Analytical Chemistry, 52(2), pp.273-276.
Rühl, C., Adams, J.D. and Hoffmann, D., 1980. Chemical Studies on Tobacco Smoke
LXVI. Comparative Assessment of Volatile and Tobacco-Specific N-Nitrosamines in
the Smoke of Selected Cigarettes from the USA, West Germany and France. Journal of
Analytical Toxicology, 4(5), pp.255-259.
Russell, C. G.; Blute, N. K.; Via, S.; Wu, X.; Chowdhury, Z.; More, R., 2012.
Nationwide assessment of nitrosamine occurrence and trends. Journal (American Water
Works Association), 104 (3), 57-58.
Sacher, F., Schmidt, C., Lee, C., & von Gunten, U., 2008. Strategies for minimizing
nitrosamine formation during disinfection. Water Research Foundation: Denver,
Colorado.
120
Schmidt, C.K. and Brauch, H.J., 2008. N, N-dimethylsulfamide as precursor for N-
nitrosodimethylamine (NDMA) formation upon ozonation and its fate during drinking
water treatment. Environmental Science & Technology, 42(17), pp.6340-6346.
Schreiber, I.M. and Mitch, W.A., 2006a. Occurrence and fate of nitrosamines and
nitrosamine precursors in wastewater-impacted surface waters using boron as a
conservative tracer. Environmental Science & Technology, 40(10), pp.3203-3210.
Schreiber, I.M. and Mitch, W.A., 2006b. Nitrosamine formation pathway revisited: the
importance of chloramine speciation and dissolved oxygen. Environmental Science &
Technology, 40(19), pp.6007-6014.
Schreiber, I.M. and Mitch, W.A., 2007. Enhanced nitrogenous disinfection byproduct
formation near the breakpoint: implications for nitrification control. Environmental
Science & Technology, 41(20), pp.7039-7046.
Selbes, M., 2014. The effects of amine structure, chloramine species and oxidation
strategies on the formation of N-nitrosodimethylamine.
Selbes, M., Kim, D., Ates, N. and Karanfil, T., 2013. The roles of tertiary amine
structure, background organic matter and chloramine species on NDMA
formation. Water Research, 47(2), pp.945-953.
Shah, A.D. and Mitch, W.A., 2011. Halonitroalkanes, halonitriles, haloamides, and N-
nitrosamines: a critical review of nitrogenous disinfection byproduct formation
pathways. Environmental Science & Technology, 46(1), pp.119-131.
Shen, R. and Andrews, S.A., 2011b. NDMA formation kinetics from three
pharmaceuticals in four water matrices. Water Research, 45(17), pp.5687-5694.
Shen, R. and Andrews, S.A., 2013a. Formation of NDMA from ranitidine and
sumatriptan: The role of pH. Water Research, 47(2), pp.802-810.
Sørensen, L., Zahlsen, K., Hyldbakk, A., da Silva, E.F. and Booth, A.M., 2015.
Photodegradation in natural waters of nitrosamines and nitramines derived from CO 2
capture plant operation. International Journal of Greenhouse Gas Control, 32, pp.106-
114.
Spiegelhalder, B. and Preussmann, R., 1981. Nitrosamines and rubber. IARC scientific
publications, (41), pp.231-243.
121
Spiegelhalder, B. and Preussmann, R., 1983. Occupational nitrosamine exposure. 1.
Rubber and tyre industry. Carcinogenesis, 4(9), pp.1147-1152.
Straub, D.J., Hutchings, J.W. and Herckes, P., 2012. Measurements of fog composition
at a rural site. Atmospheric Environment, 47, pp.195-205.
Straif, K., Weiland, S.K., Bungers, M., Holthenrich, D., Taeger, D., Yi, S. and Keil, U.,
2000. Exposure to high concentrations of nitrosamines and cancer mortality among a
cohort of rubber workers. Occupational and Environmental Medicine, 57(3), pp.180-
187.
Strazisar, B.R., Anderson, R.R. and White, C.M., 2003. Degradation pathways for
monoethanolamine in a CO2 capture facility. Energy & Fuels, 17(4), pp.1034-1039.
Sullivan, A.P., Peltier, R.E., Brock, C.A., De Gouw, J.A., Holloway, J.S., Warneke, C.,
Wollny, A.G. and Weber, R.J., 2006. Airborne measurements of carbonaceous aerosol
soluble in water over northeastern United States: Method development and an
investigation into water‐soluble organic carbon sources. Journal of Geophysical
Research: Atmospheres, 111(D23).
Tønnesen, D., Dye, C. and Bøhler, T., 2011. Baseline study on air and precipitation
quality for CO2 Technology Centre Mongstad. Norwegian Institute for Air Research,
NILU OR, 73.
Tricker, A.R. and Preussmann, R., 1991. Carcinogenic N-nitrosamines in the diet:
occurrence, formation, mechanisms and carcinogenic potential. Mutation
Research/Genetic Toxicology, 259(3), pp.277-289.
Tuazon, E.C., Carter, W.P., Atkinson, R., Winer, A.M. and Pitts, J.N., 1984.
Atmospheric reactions of N-nitrosodimethylamine and dimethylnitramine.
Environmental Science & Technology, 18(1), pp.49-54.
122
USEPA. Risk-Based Screening Table. 2015.
http://semspub.epa.gov/work/03/2218450.pdf (accessed September 26th, 2015)
Valentine, R. L.; Choi, J.; Chen, Z.; Barrett, S. E.; Hwang, C. J.; Guo, Y.; Wehner, M.;
Fitzsimmons, S.; Andrews, S. A.; Werker, A. G.; Brubacher, C.; Kohut, K. D., 2005.
Factors affecting the formation of NDMA in water and occurrence. AWWA Research
Foundation, Denver, CO.
Reynolds, A.J., Verheyen, T.V., Adeloju, S.B., Meuleman, E. and Feron, P., 2012.
Towards commercial scale postcombustion capture of CO2 with monoethanolamine
solvent: key considerations for solvent management and environmental
impacts. Environmental Science & Technology, 46(7), pp.3643-3654.
Ventanas, S. and Ruiz, J., 2006. On-site analysis of volatile nitrosamines in food model
systems by solid-phase microextraction coupled to a direct extraction
device. Talanta, 70(5), pp.1017-1023.
Vikesland, P.J., Ozekin, K. and Valentine, R.L., 2001. Monochloramine decay in model
and distribution system waters. Water Research, 35(7), pp.1766-1776.
Von Gunten, U., Salhi, E., Schmidt, C.K. and Arnold, W.A., 2010. Kinetics and
mechanisms of N-nitrosodimethylamine formation upon ozonation of N, N-
dimethylsulfamide-containing waters: bromide catalysis. Environmental Science &
Technology, 44(15), pp.5762-5768.
Walker, E.A., Castegnaro, M., Griciute, L. and Lyle, R.E., 1978.Environmental aspects
of N-nitroso compounds (No. 19).
Weber, R.J., Sullivan, A.P., Peltier, R.E., Russell, A., Yan, B., Zheng, M., De Gouw,
J., Warneke, C., Brock, C., Holloway, J.S. and Atlas, E.L., 2007. A study of secondary
organic aerosol formation in the anthropogenic‐influenced southeastern United
States. Journal of Geophysical Research: Atmospheres, 112(D13).
WHO, 2002b.
http://www.who.int/water_sanitation_health/dwq/chemicals/ndma2ndadd.pdf
(accessed March 26th, 2015)
Yan, B., Zheng, M., Hu, Y., Ding, X., Sullivan, A.P., Weber, R.J., Baek, J., Edgerton,
E.S. and Russell, A.G., 2009. Roadside, urban, and rural comparison of primary and
secondary organic molecular markers in ambient PM2. 5. Environmental Science &
Technology, 43(12), pp.4287-4293.
Yang, L., Chen, Z., Shen, J., Xu, Z., Liang, H., Tian, J., Ben, Y., Zhai, X., Shi, W. and
Li, G., 2009. Reinvestigation of the nitrosamine-formation mechanism during
ozonation. Environmental Science & Technology, 43(14), pp.5481-5487.
123
Zhang, J., Hanigan, D., Westerhoff, P. and Herckes, P., 2016. N-Nitrosamine formation
kinetics in wastewater effluents and surface waters. Environmental Science: Water
Research & Technology.
Zhang, X., Hecobian, A., Zheng, M., Frank, N.H. and Weber, R.J., 2010. Biomass
burning impact on PM 2.5 over the southeastern US during 2007: integrating
chemically speciated FRM filter measurements, MODIS fire counts and PMF
analysis. Atmospheric Chemistry and Physics, 10(14), pp.6839-6853.
124
APPENDIX A
125
Table A1: Sample information of aerosol and fog/cloud water
Fog
SU 092009 Selinsgrove fog Straub et
SU103107 ,PA al., 2012
DAA 011511P3 Davis, CA UC Davis Ehrenhauser
DAA 011711P1 campus et al., 2012
XL CASCC F010910P3 Fresno, CA CSU Fresno
XL CASCC F010910P2 cmapus
FILTERED
Cloud
ELDEN 080205 2 OF 2 Mt. Elden, cloud Hutchings
AZ et al., 2009
ELDEN 091207 Mt. Elden,
AZ
RN0705P1 Whistler, Raven's Nest Lee et al.,
RN0621P1 BC 2012
RN0712
RN0722
128
APPENDIX B
129
Text A1: NDMA formation pathways in chloramination. NAs could be formed
from primary amines through a nitrosation pathway, these NAs are not stable and decay
rapidly (Ridd, 1961).1 Secondary amines which form stable secondary NAs have been
studied in greater detail (Choi and Valentine, 2002; Mitch and Sedlak, 2002; Schreiber
and Mitch, 2006a; Schreiber and Mitch, 2006b; Shah and Mitch, 2012). Tertiary amines
were also found to be important precursors. Some tertiary amines (e.g. trimethylamine
release a secondary amine which forms the nitrosamine upon chloramination (Mitch
and Schreiber, 2008). Mechanistic studies found that nitrosamine yields from most
secondary amines and tertiary amines are similar (i.e., ~0-2%). Some other tertiary
those alkyl substituents containing branched alkyl groups next to the nitrogen of DMA)
have much higher yields of NDMA in chloramination (Le Roux et al., 2012; Shen and
Andrews., 2011a; Shen and Andrews., 2011b). In particular, ranitidine, a widely used
amine-based pharmaceutical, forms NDMA at yields higher than 80%. It suggests that
UDMH) (NHCl2) (Choi and Valentine, 2002; Schreiber and Mitch, 2006b). UDMH is
oxygen to produce NDMA. Based upon competition kinetics, it has been suggested that
when reacted with amine-containing model compounds (Shah and Mitch, 2012).
the molar yield of NDMA from DMA is low (i.e., <5%), it was suspected that a third
pathway, not through DMA, existed. Recently it was shown that compounds such as
amine group in organic amines. Further reaction involving dissolved O 2 allows for the
direct formation of NDMA and a resulting sister carbocation (Le Roux et al., 2012).
When the requisite -aryl tertiary amine is present on a parent compound, molar yields
compounds typically have molar conversion of <5% and therefore -aryl tertiary amine
131
700
600
500
NDMA (ng/L)
200
100
0
0 50 100 150 200 250 300
Time (hour)
Figure A1. NDMA formation observed (symbols) and fitted by Equations 2&3 (line)
in WW2 at two initial monochloramine doses. (pH=8.0, 23 ± 1°C)
1000
800
NDMA (ng/L)
600
400
NH2Cl=20mgCl 2/L model
NH2Cl=20mgCl 2/L observation
200 NH2Cl=7mgCl2/L model
NH2Cl=7mgCl2/L observation
0
0 200 400 600 800
Time (hour)
Figure A2. NDMA formation observed (symbols) and fitted by Equations 4-2&4-3
(line) in WW3 at two initial monochloramine doses. (pH=8.0, 23 ± 1°C)
132
1000
800
NDMA (ng/L)
600
400
NH2Cl=20mgCl 2/L model
NH2Cl=20mgCl 2/L observation
200 NH2Cl=7mgCl 2/L model
NH2Cl=7mgCl 2/L observation
0
0 20 40 60 80 100 120 140 160 180
Time (hour)
Figure A3. NDMA formation observed (symbols) and fitted by Equations 4-2&4-3
(line) in WW4 at two initial monochloramine doses. (pH=8.0, 23 ± 1°C)
700
600
500
NDMA (ng/L)
400
300
0
0 20 40 60 80 100 120 140
Time (hour)
Figure A4. NDMA formation observed (symbols) and fitted by Equations 4-2&4-3
(line) in WW5 at two initial monochloramine doses. (pH=8.0, 23 ± 1°C)
133
1.0
WW2-L
WW2-H
0.8
0.6
P/P 0
0.4
0.2
0.0
Figure A5: Plots of P/P0 verses monochloramine exposure for water samples WW2,
L=lower, H=higher, represent samples with lower or higher NH2Cl concentration.
1.0
WW3-L
WW3-H
0.8
0.6
P/P 0
0.4
0.2
0.0
Figure A6: Plots of P/P0 verses monochloramine exposure for water samples WW3,
L=lower, H=higher, represent samples with lower or higher NH2Cl concentration.
134
1.0
WW5-L
WW5-H
0.8
0.6
P/P 0
0.4
0.2
0.0
Figure A7: Plots of P/P0 verses monochloramine exposure for water samples WW5,
L=lower, H=higher, represent samples with lower or higher NH2Cl concentration.
135