Environmental Pollution 222 (2017) 242e250

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Novel pollutants in the Moscow atmosphere in winter period: Gas

chromatography-high resolution time-of-flight mass spectrometry
study*
D.M. Mazur a, O.V. Polyakova a, V.B. Artaev b, A.T. Lebedev a, *
a
Lomonosov Moscow State University, Organic Chemistry Department, 119991 Moscow, Russia
b
LECO Corporation, 3000 Lakeview Avenue, St. Joseph, MI, USA

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

Article history: The most common mass spectrometry approach analyzing contamination of the environment deals with
Received 7 October 2016 targeted analysis, i.e. detection and quantification of the selected (priority) pollutants. However non-
Received in revised form targeted analysis is becoming more often the method of choice for environmental chemists. It in-
17 December 2016
volves implementation of modern analytical instrumentation allowing for comprehensive detection and
Accepted 18 December 2016
Available online 28 December 2016
identification of the wide variety of compounds of the environmental interest present in the sample,
such as pharmaceuticals and their metabolites, musks, nanomaterials, perfluorinated compounds, hor-
mones, disinfection by-products, flame retardants, personal care products, and many others emerging
contaminants. The paper presents the results of detection and identification of previously unreported
organic compounds in snow samples collected in Moscow in March 2016. The snow analysis allows
evaluation of long-term air pollution in the winter period. Gas chromatography coupled to a high res-
olution time-of-flight mass spectrometer has enabled us with capability to detect and identify such novel
analytes as iodinated compounds, polychlorinated anisoles and even Ni-containing organic complex,
which are unexpected in environmental samples. Some considerations concerning the possible sources
of origin of these compounds in the environment are discussed.
© 2017 LECO. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

1. Introduction
Control of air pollution, especially in highly populated regions, is
a vital task for the environmental authorities. Regular monitoring of
environmental pollution is a common practice nowadays in many
cities and countries. Usually, the so-called priority pollutants (US
EPA, 2012) are detected and quantified on a regular basis during
those monitoring activities. However, with the social and economic
changes around us, the environment is also changing and new, not
previously reported, pollutants are appearing. Recently, several
thousand novel organic compounds were identified in the envi-
ronmental samples around the world and were included in the lists
of emerging contaminants, since many of those compounds may
present an environmental and human health hazard (Lebedev,
2012, 2013; Richardson and Ternes, 2011; Richardson, 2012).
*
This paper has been recommended for acceptance by Charles Wong.
* Corresponding author.
E-mail address: a.lebedev@org.chem.msu.ru (A.T. Lebedev).
Moscow, Russia is one of the most populated cities in the world,
with the metropolitan population reaching 12 million according to
the Federal Service of State Statistics (ROSSTAT). Moscow is also an
important industrial center. There are several power plants, mul-
tiple industrial factories, waste incinerators, and even oil refineries.
All are located within the city limits or in close proximity to Mos-
cow and contribute to air pollution. Also, as in any major metro-
politan region, one of the main sources of air pollution is car traffic.
According to the latest reports there are 4.3 million vehicles (both
cars and trucks) registered just in Moscow only. And with added
cars and trucks from the Moscow region, as well as transit traffic,
the total number of vehicles traveling daily the streets of Moscow is
estimated at about 6.5 million. Stationary laboratories monitoring
air pollution in Moscow are currently tasked to measure only
several targeted pollutants mostly inorganic species and some
simple organic molecules like BTEX (benzene, toluene, ethyl-
benzene and xylenes). These laboratories do not screen Moscow air
for pollutants beyond this short list (Polyakova et al., 2012). Hence,
many organic pollutants that are hazardous for the environment
remain undetected, including those from the US EPA priority

http://dx.doi.org/10.1016/j.envpol.2016.12.049
0269-7491/© 2017 LECO. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250
pollutants list (US EPA, 2012) as well as from the list of emerging
contaminants (Lebedev, 2012, 2013; Richardson and Ternes, 2011;
Richardson, 2012).
Besides the classical methods of direct (real time or near-real
time) analysis of air, there are indirect approaches to study atmo-
spheric pollution. One of them involves analysis of snow layers,
since accumulation of air pollutants in the snow is a very efficient
method of passive sampling, especially in the regions with cold
climate or in the highlands (Zoccolillo et al., 2007; Schneidemesser
et al., 2008; Herbert et al., 2004). Analysis of snow was efficiently
utilized in our previous studies in Moscow (Russia), Karelia
(Russia), Finland, and the Baikal Lake (Russia) regions (Polyakova
et al., 2000; Lebedev et al., 2003). Most recently, we have re-
ported new data expanding our understanding of composition of
Moscow air using snow analysis (Polyakova et al., 2012; Mazur
et al., 2016).
Mass spectrometry provides the best analytical tools, combining
selectivity, sensitivity, reliability, and information capacity for tar-
geted or non-targeted methods of environmental analysis
(Lebedev, 2013; Magi and Di Carro, 2016). Based on our years of
experience to date, we could claim that GC-MS combined with
electron ionization (EI) is one of the most reliable, precise, and
efficient method for identification of volatile and semi-volatile
organic compounds in the environment (Lebedev, 2012; Lebedev
et al., 2015). The GC-MS identification of knowns (by matching
against standard and user spectral libraries) and structural eluci-
dation of unknowns becomes considerably more reliable if com-
plemented by accurate mass measurements (Lebedev et al., 2013).
The accurate mass data becomes especially important when
implementing “manual” (i.e. not library-based) identification of the
analytes by using rules of fragmentation of organic molecules in EI
sources that are well-described in the literature (see e.g. Ture cek
and McLafferty, 1993) and the proposed empirical formula for un-
ambiguous confirmation of unknowns. In the present study we
used gas chromatography coupled to high resolution time-of-flight
mass spectrometry (GC-HRTMS) to investigate organic compounds
in snow samples. We report the presence of several new, previously
not discussed, pollutants in Moscow snow, accumulated during the
winter of early 2016. In our recent article (Lebedev et al., 2013) we
have already reported several rather rare pollutants detected in the
Moscow snow. This included a simple analyte, i.e., dichlornitro-
methane, which to the author's knowledge had been reported as an
environmental pollutant only once in the past (Laniewski et al.,
1998) but was persistently occurring in our samples. Dichloroni-
tromethane has also been reported as a disinfection by-product in
drinking water (Plewa et al., 2004a; Krasner et al., 2006), however
in our opinion, waste incinerators are the most probable source of
dichloronitromethane in the atmosphere. Here we report detection
of several peculiar and more complex organic molecules present in
the Moscow air and propose possible rationalization of their
sources, from which they are released into environment.
2. Materials and methods
2.1. Snow sampling
Three snow samples were collected in March of 2016 near the
Lomonosov Moscow State University campus, Moscow, Russia. N1
was taken from a snow layer near a busy highway, N2 was collected
in a nearby park and N3 was a fresh snow sample, taken at the same
location as N2 (in the park). The first two samples were collected by
piercing through the snow cover with a 10 cm internal diameter
tube. The thickness of the snow layer during the sampling was
30e35 cm. N3 was collected during the snowfall by taking 5 cm
deep of the upper layer of the fresh snow from an area of
243
approximately 3 m2. Each snow sample was placed into a 3 L glass
container and melted at room temperature. The melted water was
then filtered through a paper filter with pore size 23 mm. Further
sample preparation for GC-MS analysis was done according to the
US EPA Method 8270 (Method 8270 D, 2007). Triplicate extraction
of 1 liter of melted water with 60 ml of dichloromethane at pH 11
and pH 2 was followed by solvent evaporation to 0.5 mL. The
concentrated basic (pH 11) and acidic (pH 2) dichloromethane ex-
tracts were combined before GC-HRTMS analysis.
2.2. Accurate mass GC-MS analysis
All data were obtained using high resolution Folded Flight Path
(FFP®) multiple reflecting geometry time-of-flight (TOF) mass
spectrometer Pegasus® GC-HRT (LECO Corporation, Saint Joseph,
MI, USA) coupled to an Agilent 7890A Gas Chromatograph (Agilent
Technologies, Palo Alto, CA, USA). The system was controlled by
ChromaTOF-HRT® software (Version 1.91, LECO Corporation),
which was also used for spectra collection and data processing. The
data were acquired using 10 full scan MS spectra (10e800 m/z
range) per second in high resolution mode (50000 or above at
FWHH of m/z 218.9851), with high mass accuracy (<1 ppm), reli-
ably determining elemental composition of all ions of interest in
mass spectra. The multi-point mass calibration on FC-43 (per-
fluorotributylamine - PFTBA) mass spectra was performed before
running the samples as a part of the automated tuning routine. The
mass spectrometer's hardware and acquisition software allows
minimizing mass drift during data collection. The electron ioniza-
tion source temperature was kept at 270
C, while the electron
energy was 70 eV.
2.3. Chromatographic separation
Chromatographic separation of the snow extracts was per-
formed using an Rxi-5SilMS 30 m  0.25 mm (id) x 0.25 mm (df)
(Restek Corporation, Bellefonte, PA) column with a constant helium
flow of 1 mL/min. All injection volumes were 1 mL, splitless for 60 s,
and thereafter purged with 20 mL/min flow. The septum purge flow
was 3 mL/min. The injector and the transfer line temperature were
set at 270
C and 320
C, respectively. The GC oven program was as
follows: 0.5 min isothermal at 50
C, then 10
C min1 ramping to
320
C and 8 min isothermal hold at 320
C.
2.4. Chromatographic deconvolution and mass spectra elucidation
using high mass accuracy data
The ultra-high resolution time-of-flight mass spectrometer, and
Pegasus GC-HRT especially, is an ideal GC-MS detector for screening
and quantitating the unknowns as it collects high resolution and
high mass accuracy, full mass range mass spectra at very high rate
without any data loss, thus providing highly reliable data suitable
for automatic accurate spectral deconvolution of the coeluting
analytes present in the samples in the wide concentration range.
The ChromaTOF-HRT software ability to automatically find chro-
matographic peaks and deconvolute the analytes' mass spectra
from the coeluting and background ions is a critical feature of the
screening instruments, since the analyst doesn't know the expected
composition of the sample and thus is unable to develop chro-
matographic methods with full separation of all analytes. If the
deconvoluted mass spectrum (called Peak True spectrum in
ChromaTOF-HRT software) is relatively free from significant in-
terferences, the resulted mass spectrum could be searched against
the standard EI spectra library (NIST14 in this study). The accurate
mass data is used then to confirm the library search results via
matching masses of all ions in the Peak True spectrum to the
244 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250
elemental composition of the analyte proposed by the library
search (ca. Fig. 2). However, if the corresponding spectrum is absent
in the library or the resulted match has a very low similarity score,
the accurate mass information from the Peak True spectrum is used
to elucidate chemical formula and molecular structure of the ana-
lyte of interest using conventional rules of EI fragmentation (see e.g.
Turecek and McLafferty, 1993).
Up to five hundred analytes were detected in each of the snow
samples in this study (Fig. 1) by using High Resolution Deconvo-
lution® (HRD®) automated peak finding algorithm built-in in the
ChromaTOF-HRT software. Among the detected features were
multiple analytes of interest as well as chemical background
compounds, such as residual gas components, column and septa
bleed, etc. It is very much expected that in such rich data the
multiple chromatographic peaks representing individual analytes
may coelute very closely and even exactly overlap on top of each
other, making automatic deconvolution difficult and sometime
practically impossible. The issue of coeluting and overlapping peaks
becomes an even more difficult problem to address when the
relative concentration of the coeluting compounds is significantly
different. The pollutants and especially peculiar pollutants are
present in samples at ppb and even ppt concentration levels, thus
making the task of their detection, accurate deconvolution from the
interfering compounds and reliable identification very challenging.
In such difficult cases we implemented a “manual” deconvolution
method described below.
2.5. Manual deconvolution and elucidation
One of such challenging cases requiring “manual” deconvolu-
tion is shown as an example in Fig. 2: two compounds are eluting
very close to each other, with their peaks separated by only 0.2 s.
The automated deconvolution returns just one found peak with
Peak True mass spectrum shown in Fig. 2b, which is clearly a
mixture of mass spectra of at least two analytes. There are ions
most likely belonging to the spectrum of ethyl ester of N,N-dieth-
ylcarbamodithioic acid (chemical formula C7H15NS2, m/z 177.0640)
and there are also ions belonging to the compound with a probable
molecular ion mass 146.0362. Typically, we consider formulae as-
signments as a very good probable match if the resulted m/z value
of the empirical formula falls within 5 ppm or less error comparing
Fig. 1. Total Ion Chromatograms of the snow samples analyzed in this study.
to the experimental data. The elemental formulae of the ions cor-
responding to the chemical formula of the ethyl ester of N,N-
diethylcarbamodithioic acid were confirmed with mass accuracy
within 1 ppm (HRMS) (Fig. 2c). After removing ions not matching
the elemental composition of the analyte (Fig. 2c, in green), the
edited Peak True mass spectrum was reviewed again for confir-
mation to a new elemental composition, considering molecular ion
accurate mass m/z 146.0362 (Fig. 2d). The good match was calcu-
lated as C9H6O2 with mass error 0.2 ppm, suggesting that the
interfering compound was coumarin (Fig. 2e). These were, typically,
the steps used for identification of compounds of interest in diffi-
cult cases of close coeluting and overlapping peaks.
3. Results and discussion
3.1. N,N-diethylcarbamodithioic acid derivatives
The N,N-diethylcarbamodithioic acid derivatives were reported
in Moscow snow samples for the first time in 2011 (Polyakova et al.,
2011). In that work we identified two compounds of that group
using standard library search (NIST14) of the automatically
deconvoluted peaks: N,N-diethylcarbamodithioic acid methyl and
ethyl esters. At that time we did not have a good explanation for the
source of these compounds in the samples and were not absolutely
sure of their correct identification. Further studies of the Moscow
snow have demonstrated sporadic presence of these compounds.
Finally, in the present study we have reliably confirmed the pres-
ence of the methyl and ethyl esters of N,N-diethylcarbamodithioic
acid in the evaluated samples and defined their structures, using
everything available from our GC-HRTMS tool box, including
automatic peaks deconvolution, followed by NIST and accurate
mass user library search, as well as “ manual” deconvolution and
elucidation, described above (Fig. 2).
The same method was used for the detection and identification
of N,N-diethylcarbamodithioic acid methyl ester (Fig. 3). Some
interfering fragments were present in the Peak True spectrum,
because of a closely eluting interfering compound.
N,N-diethylcarbamodithioic acid was also detected in the sam-
ples and easily identified (Fig. 4), using NIST library search of the
Peak True spectrum and accurate mass data to confirm elemental
composition of the ions in mass spectrum.
 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250 245

Fig. 2. a) Reconstructed ion chromatogram plots (normalized) for ethyl ester of N,N-diethylcarbamodithioic acid (red, m/z 177.0642, C7H15NS2, mass error 0.6 ppm) and unknown
compound (blue, m/z 146.0362, C9H6O2, mass error 0.2 ppm), b) Mass spectrum of ethyl ester of N,N-diethylcarbamodithioic acid (C7H15NS2, m/z 177.0640) coeluting with another
compound with molecular ion mass 146.0362 Da, c) Spectra table (left) with automatically assigned chemical formulae to the ions corresponding to the chemical composition of
ethyl ester of N,N-diethylcarbamodithioic acid (C7H15NS2). Ions with not assigned formulae belong to the interfering compound. Peak True spectrum (Fig. 2c right) with ion peaks
not belonging to the ethyl ester of N,N-diethylcarbamodithioic acid marked by green color, d-e) The edited Peak True mass spectra after ions not matching mass accuracy criteria for
elemental composition of the corresponding compounds are removed: ethyl ester of N,N-diethylcarbamodithioic acid (d) and coumarin (e). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

Earlier we also detected another N,N-diethylcarbamodithioc
acid derivative, which was identified as N,N-diethylthiocarbamoyl
chloride (C5H10ClNS) (Lebedev et al., 2013). Its structure was
elucidated using the rules of fragmentation of organic compounds
under electron ionization. Herein we have found one more deriv-
ative of the N,N-diethylcarbamodithioic acid eluting at the RT
851.8 s (Fig. 5). The most probable molecular ion (m/z 230.9698) of
this compound indicates the presence of an element with a notable
negative mass defect. Considering the relatively high intensity of
the [Mþ2] ion it should probably contain two chlorine atoms. Ac-
curate mass measurement gives us a suggested elemental compo-
sition of the ion as C6H11Cl2NS2 with an error of -3 ppm.
The elemental compositions of the abundant and structurally
important fragment ions from this spectrum (Fig. 5) were also well
matching elemental composition of the proposed molecular ion.
Some other low intensity ions present in the spectrum but not
matching the proposed elemental composition are related to
closely coeluting unknown (to the authors) compounds. Some
matched fragment ions in this spectrum were the same as in N,N-
diethylthiocarbamoyl chloride spectrum, suggesting that the new
compound has somewhat similar structure as N,N-diethylth-
iocarbamoyl chloride. The difference appears when considering
fragment ions with m/z 179.9695 (C5H7ClNSþ þ
2 ), 82.9449 (CHCl2 )
þ
and 79.9481 (CHClS ). These ions indicate the presence of a
dichloromethyl group, most probably located next to the sulfur
atom, in the molecule. After considering all the information we
propose that the that the detected unknown compound should be
dichloromethyl N,N-diethylcarbamodithioate (Fig. 5.)
We have also detected bis(diethylcarbamodithioato-S,S') nickel
(II) in N1, which was our most unexpected finding. Despite the fact
that the Peak True mass spectrum had a reasonably good similarity
score with the library spectrum (Fig. 6), only accurate mass data
have convinced us that identification of this nickel complex was
correct: the experimental value of the molecular ion m/z 353.9858
matches molecular ion formula C10H20N2NiSþ 4 with 0.2 ppm mass
accuracy.
Detection of all the above mentioned substances should not be
unexpected in environmental samples, as they are all multipurpose
chemicals. Bis(diethylcarbamodithioato-S,S')nickel(II) has been re-
ported to be an efficient catalyst for styrene oligomerization and
co-oligomerization with ethylene (Azizov et al., 1984). It has also
been studied as an additive to remove zinc, copper and/or iron
impurities from solution associated with nickel electroplating
baths (Merker et al., 1969). We also propose that as with bis(di-
butylcarbamodithioato-S,S')nickel(II), the bis(diethylcarbamodi-
thioato-S,S')nickel(II) could be used as an antioxidant and
antiozonant in the rubber industry for tire protection (Milne, 2005).
So the main source of this compound in the environment should
probably involve cars' and trucks' tires and any other plastic and
rubber objects. The N,N-diethylcarbamodithioic acid could be a
degradation product of the nickel complex or its esters. Derivatives
of carbamothioc and dithioic acids are also known to possess pes-
ticidal properties (Melnikov, 1971). Thus, the sodium salt of N,N-
diethylcarbamodithioic acid has been widely used in production of
various herbicides, nematicides and fungicides. Methyl and ethyl
esters of N,N-diethylcarbamodithioic acid could also be used as
nematicides, while S-methyl N,N-diethyldithiocarbamate was re-
ported to be a key intermediate in the metabolism of disulphiram, a
246 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250

Fig. 3. N,N-diethylcarbamodithioic acid methyl ester: ‘Edited” True Spectra table (left), reconstructed ion chromatogram (red) with coeluted compound (blue) (top right), and Peak
True and NIST Library spectra (bottom right). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. N,N-diethylcarbamodithioic acid: True Spectra table (left), Peak True (top right) and NIST Library spectra (bottom right).

drug used in alcohol abuse treatment (Hawkins, 1996). N,N-dieth- applied for different synthetic transformations: conversion of
ylthiocarbamoyl chloride can be used as a synthetic intermediate, phenols to thiophenols (Newman and Karnes, 1966), conversion of
as its analogue, N,N-dimethylthiocarbamoyl chloride, is widely allylic alcohols to 1,3-rearranged S-allyl dialkylthiocarbamates
 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250 247

Fig. 5. The reconstructed ion chromatogram plot for m/z 230.9704 (left) and Peak True mass spectrum of the compound with an RT 851.8 s in the snow sample N1 with elemental
compositions of most important ions (right). The proposed structure of the analyte e dichloromethyl N,N-diethylcarbamodithioate (C6H11Cl2NS2) is shown on the spectrum plot.

Fig. 6. The reconstructed ion chromatogram plot for m/z 353.9858 (left) and Peak True (right, top) and NIST Library (right, bottom) spectra of the compound eluting at RT 1586 s in
the snow sample N1. The compound is identified as bis(diethylcarbamodithioato-S,S')nickel(II) (C10H20N2NiS4).

(Hackler and Balko, 1973), dehydration of primary and secondary
alcohols (Newman and Hetzel, 1969) etc. Although, similarly as for
dichloromethyl N,N-diethylcarbamodithioate, it is very difficult to
define the particular source of their release in the environment.
3.2. p-Methoxychlorophenols
Polychlorinated compounds are commonly present in the
environmental samples of any kind (air, water, soil, sediments).
Usually, these compounds are of anthropogenic origin, as pesticides
or other industrial products, and are often hazardous for the
environment. Some of these substances are well known as persis-
tent organic pollutants (POPs). However, one of rather unusual
compounds of this sort was found in snow samples N1 and N3.
Though the concentration of the substance was low and its Peak
True spectrum includes some interfering ions, the NIST library
search and accurate mass data allowed us to identify it as tetra-
chloromethoxyphenol (C7H4Cl4O2, m/z 261.8931, 1.1 ppm error).
Judging by the high intensity of the [M-15]þ ion (m/z 244.8725,
0.3 ppm error) the most probable structure would imply a hydro-
quinone derivative, where the loss of CH3 radical leads to formation
of a stable tetrachloroquinone structure. A search for plausible
sources of this contaminant led us to two possible scenarios. The
first one considers the fact that 2,3,5,6-tetrachloro-4-
methoxyphenol is a natural halogenated compound produced by
various fungi. Drosophilin A (DA), or 2,3,5,6-tetrachloro-4-
methoxyphenol, is a natural antibiotic first isolated by F. Kava-
nagh and co-workers (Kavanagh et al., 1952) from the Agaricus
subatratus mushroom. A separate study was carried out to identify
the ligninolytic basidiomycete strains capable of DA biosynthesis in
different culture conditions (Teunissen et al., 1997). This compound
was detected even in the upper levels of the food chain. Wild boars
248 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250

Fig. 7. The reconstructed ion chromatogram plot for m/z 248.9281 (left), Peak True (right, top) and NIST Library (right, bottom) spectra of the compound eluting at RT 701.4 s in the
snow sample N1. The compound is identified as 1-iodo-3-nitrobenzene (C6H4INO2, 0.13 ppm error).

having a special ration full of mushrooms were accumulating DA in 3.3. Halobenzenes

their fat tissues (Hiebl et al., 2011). The second scenario considers
biodegradation of the pentachlorophenol as a precursor of DA,
because no evidence of industrial production or application of the
latter was found in the literature. It was shown that several strains
of microorganisms could biodegrade pentachlorophenol to the
various products including DA (de Jong and Field, 1997; Reddy and
Gold, 2000).
Once we have identified DA, we have decided to check for the
presence of the other methoxyphenol derivatives with fewer
chlorine atoms numbers. The ion chromatograms plotted for the
accurate masses of molecular ions of the other chlorine derivatives
of the DA confirm the presence of compounds with elemental
compositions C7H6Cl2Oþ þ þ
2 , C7H5Cl3O2 and C7H4Cl4O2 . The Peak True
spectra of these three methoxyphenol derivatives were reviewed,
and based on the NIST library match and accurate mass match for
all fragment ions, their identification was confirmed. Therefore,
these compounds are likely metabolites of DA or
pentachlorophenol.
Halobenzenes are most widely present in the environment.
Many of them are included in the US EPA list of priority pollutants
(US EPA, 2012). The chlorinated derivatives of benzene are the most
widely present ecotoxicants among them (Lebedev et al., 2003; US
EPA, 2012). In our previous studies of Moscow snow we have
repeatedly detected chlorobenzene, dichlorobenzenes and tri-
chlorobenzenes (e.g. Polyakova et al., 2012).
The iodinated compounds are rather rare environmental pol-
lutants, although their environmental hazard is considered as quite
significant (Postigo et al., 2016; Plewa et al., 2004, 2008, 2010;
Richardson et al., 2008; Ding and Zhang, 2009; Gong and Zhang,
2015; Yang and Zhang, 2014; Liu and Zhang, 2014). Some iodine
derivatives, previously not reported in the environmental samples,
were identified in the present study. Chloroiodobenzene isomer
and 1-iodo-4-nitrobenzene were identified using NIST library
match and confirmed using accurate mass data of the molecular
and fragment ions (Figs. 7 and 8). Iodobenzenes are unusual

Fig. 8. The reconstructed ion chromatogram plot for m/z 237.9042 (left), Peak True (right, top) and NIST Library (right, bottom) spectra of the compound eluting at RT 513.6 s in the
snow sample N1. The compound is identified as 1-chloro-2-iodobenzene (C6H4ClI).
 D.M. Mazur et al. / Environmental Pollution 222 (2017) 242e250
Fig. 9. The reconstructed ion chromatogram plot for m/z 179.1182 (left), Peak True (right, top) and NIST Library (right, bottom) spectra of the compound eluting at RT 571.2 s in the
snow sample N1. The compound is identified as hexamethylphosphoramide (HMPA, C6H18N3OP, 0.1 ppm error).
ecotoxicants as they have been used in organic chemistry practice
in different synthetic reactions and functionalization (Ackermann,
2005; Dai et al., 2012; Taher et al., 2015; Mane et al., 2013). It is
difficult and intriguing to identify the source of these compounds,
so this needs further investigations.
3.4. Hexamethylphosphoramide (HMPA)
Another new peculiar environmental pollutant for the Moscow
region which was also detected in the snow samples is hexame-
thylphosphoramide (HMPA) (Fig. 9). This compound is used in a
number of applications (IARC, 1977; IARC, 1999). It is used in
chemistry research laboratories as a solvent for polymers, gases,
organic and organometallic compounds. HMPA is also known to be
used as a polymerization catalyst, a stabilizer against thermal
degradation in polystyrene, an additive to polyvinyl and polyolefin
resins to protect those polymers against degradation caused by UV
light. In addition, HMPA is also used as an antistatic agent and a
flame retardant as well as anti-freezing additive in jet fuels. Hence,
there are many ways for this pollutant to get into the environment,
making it hard to pinpoint its source at this time.
4. Conclusions
Besides the well-known chemicals from the list of priority pol-
lutants and emerging contaminants, more and more rather unex-
pected analytes are appearing in the environment presumably due
to human activity. The analytical approach using GC-HRTMS allows
reliable identification of these unusual compounds, even when
they present in the rich matrix and at very low concentration levels.
Elucidating structures of these molecules, which may often contain
“unusual” elements, is a very helpful and important step in the
future environmental and public health studies.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.envpol.2016.12.049.
249
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