Factorization Methods Applied to Characterize The

ORIGINAL PAPER

International Journal of Occupational Medicine and Environmental Health 2016;29(1):15 – 39 http://dx.doi.org/10.13075/ijomeh.1896.00509

FACTORIZATION METHODS APPLIED TO CHARACTERIZE THE SOURCES OF VOLATILE ORGANIC COMPOUNDS IN MONTREAL, QUEBEC EUGENIUSZ PORADA1 and TERMEH KOUSHA2 1 University of Québec at Outaouais, Gatineau, Canada Department of Computer Science 2 Ottawa University, Ottawa, Canada Department of Mathematics and Statistics

Abstract Objectives: The study objective was to assemble emission characteristics of the sources of the ambient volatile organic compounds (VOCs) and to elaborate methods of organizing them into the sources’ chemical profiles. Material and Methods: The UNMIX – sensor modeling method from the U.S. Environment Protection Agency (EPA) – was used to process the VOC concentration data acquired over the years 2000–2009 for 175 VOC species in 4 air quality monitoring stations in Montreal, Quebec. Results: The method enabled to assess VOC emissions from the typically distributed sources exist- ing in urban environment and VOC occurrences characterizing the local, or point-like, sources. The distributed sources were inextricably associated with hydrocarbons from exhaust, heavier hydrocarbons from contaminated urban soil, fugitive evaporations of gasoline and liquefied petroleum gases (LPG), leakage from the industrial and commercial use of solvents, and the inert, ozone depleting gases permeating urban atmosphere. The sources’ profiles were charted involving 60–120 VOC species per source. Spatial distribution of the sources was examined. Conclusions: The UNMIX application and the source profiling methods, by building robust chemical profiles of VOC sources, provided information that can be used to assign the measured VOC emissions to physical sources. This, in turn, provides means of assessing the impact of environmental policies, on one hand, and of industrial activities on the other hand on VOC air pollution.

Key words: Volatile organic compound, UNMIX, Receptor modeling, Source profile, Pulp industry, Principal components

INTRODUCTION due to the extent of exposure in the densely populated Man-made volatile organic compounds (VOCs) con- areas [1,4–10]. Atmospheric photochemistry converts tribute significantly to the urban air pollution. Widely the more reactive VOCs by oxygenation and through occurring VOCs, such as e.g., benzene, ethylbenzene, reactions with oxides of nitrogen to secondary VOCs, xylenes, 1,1,1-trichloroethane, trichloroethylene, tetra- free radicals, ozone, and subsequently to smog organic chloroethylene, carbontetrachloride, chloroform, are to aerosols [6,11,12]. xic and/or carcinogenic substances [1–3]. In large cities, Correlating VOC emissions from anthropogenic sourc- harmful effects of increasing ambient concentrations of es with public health indices allows to assess the im- pollutants are even more dangerous to the public health pact of VOC pollution on human health. The research

Received: November 14, 2014. Accepted: January 24, 2015. Corresponding author: E. Porada, 1081 Alenmede Cr., Ottawa ON, K2B 8H2, Canada (e-mail: [email protected]).

Nofer Institute of Occupational Medicine, Łódź, Poland 15 ORIGINAL PAPER E. PORADA AND T. KOUSHA

provides guidelines for planning emission control strat- MATERIAL AND METHODS egies. Achieving reduction in VOC concentrations in VOC measurements and data the ambient air comparable to the reduction of the “clas- As part of the National Air Pollution Surveillance (NAPS) sic” pollutants (from 1970 to 2008 particulate mat- federal program in Canada [31], air quality monitor- ter concentration in the ambient air has decreased by ing stations were installed across the country, several of over 50% [13,14]) seems feasible. them in Montreal, Quebec. The sensors operate basing Source apportionment of numerous VOC species have on gas chromatography/flame ionization detector sys- already been examined [15–24]. The research presents tem (GC/FID) for quantification of light hydrocarbons in the methods of modeling the ambient VOC multi-re- the C2 fraction, while a combined gas chromatography/ ceptors operating in the air quality monitoring stations. mass selective detector (GC/MSD) system operating in The chief methods applied are the Principal Compo- selected ion monitoring (SIM) mode is used for quantifi- nent methods – mainly the Positive Matrix Factoriza- cation of heavier hydrocarbons, in the C3 to C12 fractions. tion (PMF). Also Chemical Mass Balance (CMB) system The data used for this report consists of daily aver- provides methods of modeling the receptors [25,26]. ages of VOC species concentrations in the ambient air. The methods consist in constructing sources’ chemical Measurements of 175 species were taken each 6th day fingerprints – employing a menu of VOCs – in a form of in 4 monitoring stations located in the Great Montreal sources’ emission profiles, relying on the user-specified area (Figure 1). The concentrations are expressed in mi- inventory of the sources contributing to the measured crograms per cubic meter. totals. Stations 2 (No. 50104) and 3 (No. 50115) are located in The intricacies of organic air pollution and complex at- downtown areas, close to a large body of water, one of mospheric chemistry make it challenging to build a reli- them, i.e., station 2, is adjacent to a large multi-industrial able receptor model [26–29]. The VOC menu typically park. Station 1 (No. 50103) is located in the East Montreal lists the most prominent VOCs, with high signal/noise NAPS stations [No.] ratio (SNR), which allow a clear-cut profiling of the sour- 1: 50103 2: 50104 N ces. Thereby, some point sources, particularly the speciali 3: 50115 1 4: 50129 zed industrial plants and the associated waste streams, 3.5 km which yield quite distinct chemical fingerprints of low-con-

centration VOCs, may stay unresolved. 2 4 This research addresses the issue by developing robust 3 pulp and paper source discrimination routines, which also search for industry the low-emission sources that stay out in the usual hy- industrial park stations drocarbon background in the urban air. This is achieved by applying principal component (PC) methods imple- Montreal-East (station 1) – petrochemical industry district; light grey mented by the U.S. Environmental Protection Agen- (stations 2, 3) – densely populated urban area; dark grey – green terrains, suburbs, and semi-rural districts in the inner ring (station 4); cy (EPA): EPA UNMIX [30], which has the advantage white – body of water surrounding inner-ring Downtown Montreal. over the other PC methods of telling the user which Fig. 1. Demarcation of districts and localization of the National modeling attempt cannot be successful, thus, narrowing Air Pollution Surveillance (NAPS) monitoring stations the output to the reliable receptor models. in Montreal, Quebec

16 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER

zone, formerly a borough of Montreal, a concentration of not apply the “positive matrix” constraint; the emission the petrochemical and chemical industries in the Great profiles allow for negative values. Persistent negative val- Montreal area. Station 4 (No. 50129) is located on the pe- ues may signal VOC depletion in the atmosphere. ripheries of Montreal, in a more countryside-like region, Finally, UNMIX possesses an important feature, which but crossed by highways. In the neighborhood there is enables to make robust informed guesses regard- also a pharmaceutical industry. ing VOC sources: it fails to give results when the parti This report concerns VOC measurements taken over cular profiling cannot be made reliable. The success of the years 2000–2009, during the period when effects profiling depends, in an essential way, on the collec- of implementation of several international and federal tion of VOC species fed into the routine. By combining clean-air programs [14,32,33] were already clearly visible. all the results from the successful run – thus, combining The number of all the measured VOC species in each only partial reliable profiles defined in different limit- station was 175, but many measurements bore errors. In ed VOC ranges – more reliable exhaustive chemical de- this research, only the species that have 95% or more cor- scriptions of VOC sources can be produced. rect daily averages in the study period were considered. Therefore, the number of VOCs adequately measured The method of combining partial emission profiles and processed varies between 103 and 130, depending on into the sources’ extended profiles the monitor. Modeling the 175-VOC multi-receptor with UNMIX required applying the routine several hundred times in order U.S. EPA VOC data processing routines to produce sufficiently exhaustive library of the reliable The United States EPA makes 2 data processing ap- (according to UNMIX), but only partial (approximate- plications based on the Principal Component method, ly 30 VOCs could be fed at a time into the routine), emis- i.e., EPA PMF and EPA UNMIX available. The methods sion profiles. Thus, 500 to 700 (depending on the moni- perform linear modeling of many variables (VOC mea- tor) profiles were created to ensure that each of the 100 surements) with a few expressly constructed predictors or to 130 correctly measured VOCs participated in a success- factors – which are alleged apportionments of the mea- ful profiling. A successful model featured 5 to 8 sources, sured emissions among putative sources. The applications depending on the VOC menu under scrutiny. Incidentally, impose restrictions on the factors they generate in order to a consistency in the UNMIX results was observed: adding make the claim that the factors represent physical sources a new VOC species to the menu never made the number (and not only one of the large number of mathematically of supposed sources decrease. correct solutions to the modeling problem) realistic. This Two partial profiles defined on different lists of VOC spe- study exploits mainly UNMIX. cies may characterize the same source. If they do, they The UNMIX applies stronger than PMF’s requirements can be combined into one larger profile characterizing on the correlations between VOCs to consider them as the source with VOCs from both lists. The criteria and coming from the same source, which makes successful the procedure of combining partial profiles (defined on models more reliable. UNMIX deduces the number of short lists, circa 30 VOCs), into more exhaustive pro- sources from the geometrical properties of the VOC con- files (60–130 VOCs), are described below. centration data – this number is more reliable than the us- A profile describes a source of VOC emission in terms of er’s estimates that PMF requires to supply. UNMIX does the percentage of the measured total that is attributable

IJOMEH 2016;29(1) 17 ORIGINAL PAPER E. PORADA AND T. KOUSHA

to this source. Question arises when 2 partial profiles are involves remembering, for each VOC, how many times compatible, i.e., when they describe the same source. For it participated in the combining operations so far; if it the sake of this research, a heuristic measure of compat- appeared several times, its present value must be set to ibility between the 2 profiles was elaborated. the average of all its appearances. Usually, the closeness of 2 numeric values a, b is defined Combining was performed by a dedicated R program [34]. in terms of the absolute value of their difference: |a–b|. It has been verified that the collection of the final long However, for the percent values 0–100%, the distance be- profiles did not depend essentially on the way of selecting tween 0% and 40% (for example) would have more signif- the “opening” partial profiles and the order of searching icance than the numerically same distance between 60% the profile libraries. and 100%. Therefore, the distance between 2 percent- Two profiles generated by combining cycles were either age values was defined depending on their locations on strongly compatible (> 95%, meaning distance < 0.05) or the percent scale, and gauged using the following scale quite distant (< 90% compatible, distance 0.1). (The com- (in percent): –50, –20, –5, 8, 14, 21, 29, 40, 52, 70, 100, patibility measure – the set-up for measuring the distance 140 (the values out of 0–100% appear in order to gauge between 2 profiles – was tuned up to meet these criteria). the < 0 and > 100 UNMIX results). The distance between 2 values was set to the number of scale marks RESULTS AND DISCUSSION separating the values (a mark coinciding with a value UNMIX results, however in large part compatible was counted as 1/2), but only if that number was greater with PMF results, offer a new picture. The profiles con- than 2, otherwise it was set to 0. structed by the combining procedure are of 2 kinds: long The distance between 2 profiles was defined as a nor- profiles with scarce, or none, negative values, reproduc- malized weighted sum of distances between the profiles’ ible with PMF to a satisfactory degree (compatibility percentage values assumed on their common domain (on of 90% or more), and short profiles featuring significantly all shared VOCs). Average concentrations of VOC in more negative values. The number of the long profiles was the study period were taken for the weights. Normaliza- limited to 6–8, while the short ones (and, basically, not- tion signified dividing the computed distance by the maxi- extendable profiles: the profiling with extended VOC me mal possible distance, the latter being the number of nus fails) were as numerous as several dozen. It is argued marks on the scale (12 percentage values) times the sum in the discussion section that the appearance of “nega of the VOC weights on the common domain. Two profiles tive” sources in UNMIX profiles has a meaning different were compatible (were considered as describing the same than “error.” source) if, 1st, their distance was ≤ 0.05 and, 2nd, the Only the long profiles were tabulated and shown here. overlap of their VOCs was large enough to cover at However, shorter profiles exhibiting “negative” emissions least 1/2 of the shorter profile. This usually signified at from unidentified sources are required to balance more least 15 common VOCs, so incompatibility of 1 com- than 100% values of contributions from the reported mon VOC of an average concentration usually disqualified “positive” sources. A negative value may represent a defi- compatibility of the profiles. cit in the concentration of a species, which is more sus- Combining proceeded by taking a linear combination of ceptible to photochemistry than its companions in a given the 2 profiles where they overlapped, and their own values partial profile; the species undergoes losses uncorrelated where they did not. It is to be observed that combining with emissions, thus, displaying a behavior suggesting

18 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER

another source. Assuming that such a mechanism is at –– ethylene, a C2 unsaturated hydrocarbon, which is an im- work, the percent values reported here would represent portant natural plant hormone but also industrially recov- the initial, yet unaffected by the journey to the sensor, ered at a large scale from refinery gases, may have a load- emissions. ing in the “traffic” profiles – as a byproduct of gasoline combustion; however, its source appears to be the station- The “traffic” source in Montreal, Quebec ary combustion engines rather than the urban transit. The “traffic” profiles in Tables 1–4 are labeled T. In all Heavier unsaturated hydrocarbons in paraffin series, non- the tables, CAS is the Chemical Abstracts Service registry ane, decane, undecane, and dodecane, may occur in gaso- number. line and in the exhausts – most often the nonane – but they The center of the Montreal urban agglomeration shows have dominant sources in releases from consumer prod- abundant reactive species, which can be associated with ucts (mainly from industrial synthetic building materials exhaust, while in boroughs, where petrochemical industry and housing equipment [35]), from the industrial waste is located, only more inert combustion products persist. streams and the contaminated urban soil [36–40], though The “traffic” source appears responsible for concen- environmental behavior of the vapors from the subsur- trations of a multitude of C4–C8 alkanes and alkenes, face gasoline contamination of soil and groundwater the most prominent being the unsaturated hydrocarbons is not a well understood phenomenon. used for gasoline blending and/or enhancing the octane content. The easiest way to recognize the “traffic” species Industrial park in a downtown area is to observe their hourly pattern of ambient concentra- The National Air Pollution Surveillance stations 2 tion [18,20–22,24]. When only daily averages are avail- (No. 50104) and 3 (No. 50115) (Figure 1) are located able, the following VOCs can be used as “traffic” source symmetrically vis-à-vis pulp and paper industry sites, in indicators: a densely populated town center. The pulp and paper in- –– 2-methylpentane, a volatile but pervasive isomer of oc- dustry is represented by 2 large plants. Montreal is also tane, a flag exhaust gas; an important administrative center for the pulp, paper, –– 1-butene/isobutene, utilized for the production of gas- and wood industries in North America. oline blending components, also 2-methyl-2-butene, Figure 1 shows a large industrial park, Technopôle Angus, used in North American specialty blendings; adjacent to the station No. 50104. Incidentally, this recep- –– hexane, constituting more than 1% in gasoline; tor captures VOCs typical of industrial sources. Table 1 –– pentane, its isomer 2,2-dimethylpropane in particular, shows models for receptors 2 and 3, employing the same constituting more than 1% in gasoline; set of VOCs and the same ordering of the set; this was –– cyclohexane, produced in exhaust from benzene react- the set of all the VOCs captured in station 3, located at ing with hydrogen; a distance of 2.5 km from the industrial park. Some of –– heptane, and its isomers 2,4-dimethylpentane and the profiles for station 2 are quite compatible with profiles 3-methylhexane, components of high-octane gasoline, for station 3, but in the former, “industrial,” station 2 new up to 6%; sources appear. Moreover, every profile for the “industri- –– 2,3,4-trimethylpentane, mainly used in aviation in- al” station has an extension by up to 30 additional VOCs, dustry for production of specialty gasoline, wherein it which were invisible in station 3. Table 2 lists addition- constitutes circa 2%; al VOCs for station 2 and their allocation to their sources.

IJOMEH 2016;29(1) 19 ORIGINAL PAPER E. PORADA AND T. KOUSHA 1.71 0.19 0.32 1.16 1.01 1.94 0.19 0.85 1.23 0.08 0.24 0.06 0.20 0.30 0.28 0.44 0.43 0.03 0.36 0.38 7.73 0.32 0.09 0.14 0.47 0.32 0.28 0.22 3.82 concentration 9 F –1 17 20 22 50 41 40 51 56 60 65 43 73 76 56 36 25 37 34 31 31 45 54 55 56 41 7 6 6 7 9 1 E –1 18 –1 –6 –4 13 19 14 –9 14 –1 11 11 14 9 9 6 4 4 9 8 6 7 I. –1 17 21 19 25 –5 10 16 20 13 16 17 21 23 17 14 11 13 10 24 5 1 8 4 8 6 8 8 8 4 0 4 7 7 5 3 5 3 4 7 8 2 F. 62 27 31 –1 20 12 13 Downtown station No. 50115 6 6 T. 10 32 24 46 25 41 30 45 29 22 –7 –6 19 10 18 18 33 27 42 42 40 30 36 24 23 11 42 4.59 0.18 0.27 1.09 1.19 1.73 0.19 0.71 1.14 0.07 0.22 0.06 0.19 0.32 0.33 0.56 0.58 0.03 0.31 0.34 6.47 0.31 0.08 0.13 0.45 0.25 0.26 0.22 3.59 concentration 5 8 D –9 28 22 51 31 40 29 55 14 13 61 58 15 16 78 46 –10 110 103 9 C 32 14 10 17 16 –1 –3 67 12 21 19 23 23 23 23 20 25 18 3 4 1 7 3 1 8 7 7 5 9 B 22 –1 10 17 28 25 44 40 77 74 19 22 37 –3 49 16 12 7 6 8 5 2 4 9 8 5 7 6 0 A 19 15 –2 33 12 19 11 54 43 28 33 –5 11 12 –1 –3 –4 0 I. 45 14 48 –6 32 25 42 20 17 –7 –0 –3 16 23 24 –2 6 4 7 5 5 4 1 4 8 9 5 2 3 4 7 8 7 1 0 3 0 3 9 F. 83 –2 11 11 –1 24 Industrial park station No. 50104 T. 46 –1 30 59 75 55 45 40 33 40 29 25 47 12 40 34 43 44 71 42 68 53 35 20 43 –26 –20 –12 –16 VOC 1-pentene freon-22 octane hexane dichloromethane 2-methylpentane cis -2-pentene methylcyclopentane ethylbenzene iso-propylbenzene n-propylbenzene n-butylbenzene 1,4-diethylbenzene nonane dodecane undecane decane 1-octene 1,3,5-trimethylbenzene methylcyclohexane toluene cyclopentane trans -2-hexene indane 2-methyl-2-butene 3-methylheptane 1,2,3-trimethylbenzene styrene m - and p -xylene CAS inert gases (I.), and industrial sources A–F for 2 NAPS stations in Montreal center freon-22 (F.), profiles of distributed sources: traffic (T.), 1. Percentage Table in 2000–2009 109-67-1 75-45-6 111-65-9 110-54-3 75-09-2 107-83-5 627-20-3 96-37-7 100-41-4 98-82-8 103-65-1 104-51-8 105-05-5 111-84-2 112-40-3 1120-21-4 124-18-5 111-66-0 108-67-8 108-87-2 108-88-3 287-92-3 4050-45-7 496-11-7 513-35-9 589-81-1 526-73-8 100-42-5 108-38-3

20 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER 0.17 0.31 0.30 1.68 0.17 1.13 0.39 0.09 0.34 0.64 0.40 2.20 0.17 0.50 0.05 0.57 0.02 0.02 0.03 0.04 0.03 0.07 0.03 0.34 0.32 0.88 0.03 0.31 0.03 0.10 0.06 0.79 0.12 9 9 2 27 23 18 39 17 35 47 23 18 24 43 32 17 33 28 28 30 26 63 22 26 51 31 53 44 30 38 9 3 6 4 4 8 8 14 –2 10 –1 –3 22 12 17 12 93 45 30 15 30 25 11 22 10 23 12 11 1 7 2 1 8 9 2 6 8 6 3 5 5 4 24 16 22 23 23 23 –2 18 10 16 47 36 28 25 29 30 20 12 –3 3 5 4 2 7 2 4 6 6 5 8 2 3 4 3 3 2 7 4 1 3 4 7 3 6 4 0 3 5 13 10 10 19 6 40 37 41 43 28 43 67 35 37 38 25 44 28 33 34 26 14 13 14 32 26 14 41 42 27 33 31 16 21 22 35 31 0.13 0.25 0.28 1.13 0.17 0.88 0.38 0.07 0.34 0.55 0.38 2.41 0.14 0.36 0.04 0.45 0.03 0.02 0.03 0.05 0.03 0.06 0.03 0.30 0.31 0.70 0.03 0.24 0.03 0.08 0.05 0.63 0.09 2 2 0 5 –2 12 –7 15 –5 12 26 17 –4 74 30 67 –4 –8 13 –25 –26 –18 –54 –61 –20 8 6 8 21 19 29 45 50 32 33 34 33 39 59 74 31 10 32 31 24 14 10 21 17 18 18 7 4 5 8 8 7 6 5 8 5 4 4 30 –4 –7 –6 –3 –3 15 –3 –8 15 35 35 27 37 31 –1 –7 –0 –3 –1 19 7 4 1 9 8 0 4 1 3 3 19 –3 17 10 23 11 11 23 14 14 14 41 25 11 –3 18 18 12 27 16 13 13 –5 22 41 27 74 30 42 14 67 16 18 41 50 44 4 7 6 1 0 2 2 4 2 7 2 2 2 4 6 3 6 5 2 4 0 3 8 6 2 5 3 5 8 10 –9 51 10 6 8 49 40 53 60 53 56 34 54 36 42 36 43 63 54 16 15 10 12 75 32 30 46 38 57 40 64 53 68 52 40 46 2,4-dimethylpentane 2-methylheptane cyclohexane 1-hexene propylene 1-butene/isobutene trans -2-butene cyclopentene trans -2-pentene heptane 2,2-dimethylbutane pentane 2,3,4-trimethylpentane 2,2,4-trimethylpentane 2,2,5-trimethylhexane tetrachloroethylene dibromochloromethane 1,2-diethylbenzene sec-butylbenzene 3,6-dimethyloctane trans -2-heptene 1,3-diethylbenzene iso-butylbenzene 2-methyl-1-butene cis -2-butene 3-methylhexane 2,2-dimethylpropane 2,3-dimethylpentane 1-methylcyclohexene 1-methylcyclopentene 2,2-dimethylpentane 2-methylhexane 2,5-dimethylhexane 108-08-7 110-82-7 592-41-6 115-07-1 115-11-7 624-64-6 142-29-0 646-04-8 142-82-5 75-83-2 109-66-0 565-75-3 540-84-1 3522-94-9 127-18-4 124-48-1 135-01-3 135-98-8 15869-94-0 14686-13-6 141-93-5 538-93-2 563-46-2 590-18-1 589-34-4 463-82-1 565-59-3 591-49-1 693-89-0 590-35-2 591-76-4 592-13-2 592-27-8

IJOMEH 2016;29(1) 21 ORIGINAL PAPER E. PORADA AND T. KOUSHA 0.07 0.21 4.04 4.24 3.83 4.38 1.87 2.86 0.14 1.19 0.77 0.03 0.46 0.06 0.29 0.73 0.38 0.05 0.03 0.17 2.01 5.22 0.47 0.09 1.30 1.26 0.07 0.34 1.20 concentration 6 0 9 F 48 14 –4 23 21 –3 16 13 16 19 43 44 37 44 31 34 25 31 42 30 36 32 31 51 0 5 4 8 3 8 5 0 2 0 5 8 0 E 32 –3 –3 –9 –5 18 32 18 17 17 18 20 16 –1 –3 –6 8 1 5 5 3 6 7 7 7 I. 12 21 50 31 65 16 36 16 13 12 15 14 24 –5 10 11 11 12 11 14 8 0 2 5 8 8 9 6 5 7 5 5 1 5 5 8 5 5 4 6 7 5 7 F. 16 –8 10 10 11 –1 Downtown station No. 50115 6 6 0 T. –0 63 72 61 83 39 43 34 33 26 29 15 15 15 23 18 33 45 44 39 46 43 37 30 31 27 0.09 0.18 2.92 4.57 3.91 2.91 1.76 2.90 0.15 1.18 0.77 1.11 0.05 0.26 0.61 0.29 0.05 0.03 3.43 0.12 1.58 5.34 0.41 0.08 1.13 1.16 0.07 0.22 1.06 concentration D C 31 48 3 3 7 4 6 9 3 0 5 9 4 0 3 0 3 7 8 B 19 –1 –5 10 17 12 11 72 –2 10 15 7 4 1 1 8 8 4 1 7 A 34 17 –0 13 32 43 53 32 52 62 27 57 41 –2 19 11 12 10 –5 22 8 5 I. 62 50 42 42 62 75 49 74 58 37 20 15 17 20 21 65 37 48 44 35 28 34 14 22 –1 –9 6 2 1 0 6 3 2 6 4 8 7 5 1 2 4 6 1 1 9 5 6 3 4 9 1 9 0 F. 11 13 Industrial park station No. 50104 0 2 3 T. 14 14 59 60 38 –7 –2 –2 –5 68 44 45 –6 27 55 35 36 40 50 44 50 47 42 46 55 30 VOC chloroform ethane butane isobutane ethylene freon-11 freon-12 freon-114 chloromethane freon-113 1,4-dichlorobenzene trans -3-methyl-2-pentene 2-ethyltoluene 3-ethyltoluene isoprene dibromomethane 3-methyl-1-pentene propane 1-propyne benzene isopentane 2,3-dimethylbutane cis-3-methyl-2-pentene 3-methylpentane o -xylene cis -2-hexene 1,3-butadiene 1,2,4-trimethylbenzene p -cymene CAS 67-66-3 inert gases (I.), and industrial sources A–F for 2 NAPS stations in Montreal center freon-22 (F.), profiles of distributed sources: traffic (T.), 1. Percentage Table in 2000–2009 – cont. 74-84-0 106-97-8 75-28-5 74-85-1 75-69-4 75-71-8 76-14-2 74-87-3 76-13-1 106-46-7 616-12-6 611-14-3 620-14-4 78-79-5 74-95-3 760-20-3 74-98-6 74-99-7 71-43-2 78-78-4 79-29-8 922-61-2 96-14-0 95-47-6 7688-21-3 106-99-0 95-63-6 99-87-6

22 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER 0.17 0.04 0.09 0.04 0.04 0.15 0.13 0.42 0.03 0.13 0.01 0.03 0.17 0.13 0.52 0.07 0.07 3.76 0.19 2.48 0.01 0.32 0.10 0.05 0.02 concentration 8 –0 14 7 8 –9 38 D 15 24 11 –20 –19 –49 –14 –23 –38 7 38 26 14 20 35 C 29 36 68 32 71 29 57 52 –7 20 22 17 22 4 4 11 0 9 14 5 5 9 6 2 5 8 3 5 2 B –5 –9 –4 14 13 23 10 –1 12 –10 0.19 0.05 0.11 2 6 5 14 24 10 29 A 27 28 63 55 31 26 42 45 44 32 35 36 68 13 22 Industrial park NAPS station No. 50104 4 I. 83 74 29 64 40 12 –5 15 20 15 22 –10 –24 5 12 –2 3 2 4 7 2 1 1 2 8 5 5 3 0 4 1 F. 35 34 21 15 –2 –2 –1 38 53 41 14 22 11 6 6 1 8 4 3 19 16 T. –9 23 –3 39 16 20 36 24 –4 45 54 58 38 19 –13 –24 –14 12 –2 10 VOC cis -1,4/t-1,3-dimethylcyclohexane cis -1,2-dimethylcyclohexane MIBK acrolein propionaldehyde cyclohexene 2-pentanal chlorobenzene bromoform benzaldehyde 2-pentanone/isovaleraldehyde naphthalene bromodichloromethane 1,2-dichloroethane acetone hexanal formaldehyde vinylchloride 4-ethyltoluene 4-methylheptane cis -4-methyl-2-pentene 2,2,3-trimethylbutane 1,1,1-trichloroethane chloroethane bromomethane CAS 2207-03-6 2207-01-4 108-10-1 107-02-8 123-38-6 110-83-8 110-62-3 108-90-7 75-25-2 100-52-7 590-86-3 91-20-3 75-27-4 107-06-2 67-64-1 66-25-1 50-00-0 75-01-4 622-96-8 589-53-7 4461-48-7 464-06-2 71-55-6 Surveillance. volatile organic compound; NAPS – National Air Pollution Chemical Abstracts Service registry number; VOC – CAS – are bolded, undetermined values blank. Values ≥ 25% not seen in a distant downtown station No. 50115 2. Extensions of profiles for industrial park station No. 50104: volatile organic compounds (VOCs) Table 75-00-3 74-83-9

IJOMEH 2016;29(1) 23 ORIGINAL PAPER E. PORADA AND T. KOUSHA

Table 2 briefly presents the local VOC pollution features. And so, trichloroethylene, produced from ethylene (but 0.08 0.11 1.42 0.15 1.92 0.03 0.12 0.05 banned from the food and pharmaceutical industries in

concentration the majority of the world due to concerns about its toxicity [41]), here supplements the usual occurrences of eth- 3 2 14 D ylene in the urban traffic and in the banks of inert gases. Acetaldehyde, another derivative of ethylene, used in an array of specialized industries manifests a similar behav-

7 ior. It can be released to the environment during produc- C 40 29 27 tion, use, transportation, and storage. Also power plants, refineries, cement kilns, lumber mills and paper mills release acetaldehyde into the air. 6 4 6 5 B 25 49 –1 Other aldehydes in Table 2, such as methyl ethyl ketone (MEK), 2-pentanal, and benzaldehyde, accompanied by chlorobenzene, have significant loadings in the “inert 3 2 8 2 A 10 22 12 16 gases” profile due to their longer half-life of the reactions with hydroxyl radicals (several days, or months in the case

Industrial park NAPS station No. 50104 of bromoform, or chloromethane) and/or slow volatiliza- I. 11 98 24 48 44 tion rate [42,43]. Tables 2 and 3 show profiles labeled F. – for freon-22, which practically alone forms the profiles. This inert gas 7 5 3 3 3 appears to be a separate source, as it has a different emis- F. –3 –4 –2 sion pattern from other freons: it supplements the formerly widely used ozone-depleting freon-11 and freon-12 and it escapes to the atmosphere from many of its uses T. 16 29 –6 70 36 44 63 14 such as: propellant, refrigerant, foaming agent, solvent and degreaser, fire extinguishing agent, and dry cleaning agent. Other freons may form the profile labeled I. – for “Inert,” as their longevity allows to detect them long after they were fazed-out. Profiles A, B, and C in Table 1 (industrial park station 2)

VOC and their extensions in Table 2 describe industrial sources located in the nearby industrial zone. The presence of the non-traffic hydrocarbons in paraffin series C9–C12, trans -2-octene cis -1,3-dimethylcyclohexane MEK trichloroethylene acetaldehyde 2,2-dimethylhexane 2,4-dimethylhexane trans -1,4-dimethylcyclohexane nonane to dodecane are suggestive of industrial sites. Particularly decane, which is universally used in petroleum, gasoline, plastics, rubber, and paper-processing CAS 13389-42-9 638-04-0 78-93-3 79-01-6 75-07-0 590-73-8 589-43-5 not seen in a distant downtown station No. 50115 – cont. 2. Extensions of profiles for industrial park station No. 50104: volatile organic compounds (VOCs) Table 2207-04-7 MIBK – methyl isobutyl ketone; MEK – ethyl ketone. Other abbreviations as in Table 1. are bolded, undetermined values blank. Values ≥ 25% industries, participates widely in organic synthesis, in jet

24 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER 0.10 0.33 0.35 0.49 0.06 0.63 0.97 0.45 1.25 0.84 0.29 0.14 2.12 0.53 8.85 0.05 0.10 6.50 0.10 0.06 0.11 1.02 0.02 0.03 0.04 0.14 0.19 0.07 4.71 concentration 9 5 8 1 6 L 19 19 14 20 22 17 14 30 78 44 68 76 62 28 37 32 54 37 39 47 48 46 77 –11 6 5 1 4 9 8 8 3 6 4 1 3 7 9 6 9 7 9 7 6 5 5 0 14 K 17 12 11 18 24 2 6 1 8 6 2 3 6 8 3 9 7 6 7 J 19 –2 17 –9 40 26 10 –4 21 16 20 20 16 13 7 7 5 8 9 I 40 66 88 65 77 69 76 62 98 68 54 83 33 79 40 71 80 28 29 40 52 24 10 15 2 2 5 0 1 8 3 3 4 6 3 9 1 6 9 7 16 –3 –5 –1 –2 –4 19 23 –1 18 14 13 H –1 industry zone NAPS station No. 50103 Petrochemical 1 8 1 2 0 3 0 7 6 6 1 31 28 54 56 56 59 –2 –2 17 –2 –4 10 16 17 G 17 13 –14 –22 4 1 9 7 6 28 29 24 24 10 18 13 –1 T. 24 21 11 14 16 22 20 14 10 –4 10 –12 VOC trans -2-butene 1,2-dichloroethane 1,4-dichlorobenzene 2,4-dimethylpentane o -xylene cis -3-methyl-2-pentene octane cyclohexane a-pinene 2,3-dimethylbutane trichloroethylene 1,2-dichloropropane trans -2-hexene 2,2-dimethylhexane cis -2-butene iso-butylbenzene nonane 2,5-dimethylbenzaldehyde 2,2,5-trimethylhexane dibromochloromethane 1,3-dichlorobenzene benzylchloride cis -1,4/t-1,3-dimethylcyclohexane 1,3,5-trimethylbenzene 1,3-butadiene n-butylbenzene trans -1,3-dichloropropene p -cymene 2,2-dimethylbutane CAS 624-64-6 107-06-2 106-46-7 108-08-7 95-47-6 922-61-2 111-65-9 110-82-7 80-56-8 79-29-8 79-01-6 78-87-5 4050-45-7 590-73-8 590-18-1 538-93-2 111-84-2 5779-94-2 3522-94-9 124-48-1 541-73-1 100-44-7 2207-03-6 108-67-8 106-99-0 104-51-8 10061-02-6 99-87-6 75-83-2 and 6 other sources (G–L) for NAPS station No. 50103 located in the petrochemical industry zone of Montreal-East profiles of traffic source (T.) 3. Percentage Table in 2000–2009

IJOMEH 2016;29(1) 25 ORIGINAL PAPER E. PORADA AND T. KOUSHA 0.47 0.09 0.73 0.06 0.25 0.66 0.27 0.03 0.11 2.68 0.14 0.59 0.63 0.04 0.04 0.14 0.28 0.08 0.03 0.93 0.13 0.05 0.02 0.04 0.03 0.15 0.15 0.04 concentration 4 6 4 7 9 9 4 3 7 6 L 11 24 12 16 13 36 35 36 14 13 –1 12 21 20 27 30 22 22 4 3 7 1 8 3 1 7 6 6 5 5 59 31 31 K 32 43 63 60 51 69 10 11 15 14 10 14 15 7 4 4 3 2 8 3 J 69 57 65 63 68 29 47 58 66 35 11 11 11 –8 –2 –2 14 16 10 5 8 2 5 6 3 9 2 4 4 8 3 I 11 19 16 18 10 13 17 10 12 15 –6 12 –2 21 17 10 5 4 7 1 6 3 4 2 1 12 48 33 34 33 63 30 64 46 47 33 54 38 29 34 33 32 12 H 15 industry zone NAPS station No. 50103 Petrochemical 3 3 1 6 5 4 0 4 0 9 2 4 2 6 8 8 2 11 18 17 11 24 11 17 17 24 G 10 25 5 4 4 4 26 64 20 –2 T. 14 14 11 12 10 13 48 97 32 54 53 25 VOC chloroform 2-ethyltoluene o -tolualdehyde decane hexane 1,1,2,2-tetrachloroethane hexachlorobutadiene trans -1,2-dimethylcyclohexane 1,1-dichloroethane cis -3-heptene MEK freon-11 trans -1,4-dimethylcyclohexane 2,2,3-trimethylbutane camphene 3-methyl-1-pentene isopentane ethylbromide m -tolualdehyde 2,2-dimethylpentane 1-octene pentane undecane trans -4-methyl-2-pentene chlorobenzene 1,1,1-trichloroethane 1-butene/isobutene cis -1,3-dimethylcyclohexane CAS 67-66-3 611-14-3 529-20-4 124-18-5 110-54-3 79-34-5 87-68-3 6876-23-9 75-34-3 2097503 78-93-3 75-69-4 2207-04-7 464-06-2 79-92-5 760-20-3 78-78-4 74-96-4 620-23-5 590-35-2 111-66-0 109-66-0 1120-21-4 674-76-0 108-90-7 71-55-6 115-11-7 and 6 other sources (G–L) for NAPS station No. 50103 located in the petrochemical industry zone of Montreal-East profiles of traffic source (T.) 3. Percentage Table in 2000–2009 – cont. 638-04-0

26 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER 0.31 3.65 0.33 0.17 0.03 0.07 0.12 0.88 0.92 1.38 0.20 0.20 0.60 4.51 6.56 0.38 0.27 0.57 5.52 0.62 1.77 0.35 0.11 0.18 1.22 0.53 0.52 0.51 1.09 0.64 2.80 0.05 10.03 2 4 2 4 6 5 6 3 2 8 6 23 –4 27 45 44 46 40 42 62 53 68 51 19 29 12 10 26 16 88 62 10 1 1 3 6 6 6 2 7 5 1 3 10 14 11 12 –3 –4 11 15 22 23 17 22 15 71 65 61 92 27 65 37 25 59 5 1 2 5 2 9 4 0 8 –1 –3 –4 13 17 16 21 22 24 15 –2 27 27 31 44 38 –3 61 27 80 42 30 57 0 6 9 9 1 –2 16 22 –4 21 67 53 50 33 41 70 57 69 22 17 10 34 25 42 –6 14 22 –5 44 37 28 47 26 5 2 4 7 3 7 7 5 4 3 4 3 6 9 3 4 3 1 1 4 7 80 12 –2 –1 –3 17 12 –3 –1 17 10 –4 6 4 4 6 2 7 2 5 0 4 0 2 3 0 2 0 1 36 65 30 54 62 31 –2 –1 –1 –2 –6 12 13 10 –10 –15 5 1 5 0 7 8 4 3 –6 18 21 15 17 24 13 16 18 78 39 26 44 46 10 67 64 66 –9 24 ethylene crotonaldehyde 2,5-dimethylhexane 2-methylhexane heptane limonene bromodichloromethane bromoform dibromomethane ethane cis -2-pentene 2-methyl-2-pentene 4-ethyltoluene 1-hexene 2-methylpentane 2,3,4-trimethylpentane 2,3-dimethylpentane 3-methyl-1-butene hexylbenzene cis -1,2-dichloroethylene 1-undecene trans -1,2-dichloroethylene 2,2-dimethylpropane cyclopentane 3-methylhexane 1,1,2-trichloroethane dichloromethane dodecane 2,2,4-trimethylpentane 1,4-diethylbenzene 1-decene isoprene 1,1-dichloroethylene 74-85-1 4170-30-3 592-13-2 591-76-4 142-82-5 5989-27-5 75-27-4 75-25-2 74-95-3 74-84-0 627-20-3 625-27-4 622-96-8 592-41-6 107-83-5 565-75-3 565-59-3 563-45-1 1077-16-3 156-59-2 821-95-4 156-60-5 463-82-1 287-92-3 589-34-4 79-00-5 75-09-2 112-40-3 540-84-1 105-05-5 872-05-9 78-79-5 75-35-4

IJOMEH 2016;29(1) 27 ORIGINAL PAPER E. PORADA AND T. KOUSHA

fuel research, and in the manufacturing of paraffin products. It is also used in cleaning agents. 0.03 0.01 0.21 0.24 0.15 0.07 0.02 0.15 0.25 Vinylchloride (highly toxic, flammable, and carcinogenic

concentration organochloride, important monomer) and its precursor, 1,2-dichloroethane, as well as naphthalene, chloro- 5 9 7 3 8 L 16 20 ethane, and 1,4-dichlorobenzene appearing in source A, –17 –23 suggest local manufacturing of polymer materials, including the polyvinyl chloride (PVC), specialty polymers such 8 8 7 6 2 5 3 as synthetic textile fibers, dyes, and possibly organoalumi- K 18 17 num compounds [1,44]. The source corresponding to profile B is characterized by high participation of isoprene in the emission. This 2 4 4 2 J –9 12 72 hydrocarbon released into the atmosphere by hundreds of million tons by trees, is also a chemical raw material used to make polymeric materials and synthetic versions 3 3 1 4 I 14 10 –5 23 –2 of the natural rubber. Profile C shows numerous compounds used in the research laboratories, in the synthesis of fine organic chemi- 2 5 16 21 24 15 23 14 19 H cals, and in the biomanufacturing: 2-pentanal, 1,2-di- industry zone NAPS station No. 50103 Petrochemical methylcyclohexane, cis-1,4/t-1,3-dimethylcyclohexane, and trans-1,4-dimethylcyclohexane. The tetrachloroethylene 5 9 6 present here is an excellent solvent for organic materials 20 16 G 13 10 51 31 and degreaser. Methyl isobutyl ketone (MIBK) is used as a solvent for nitrocellulose, lacquers and certain polymers, and resins. Alkene 1-butene/isobutene, besides being used 1 T. 17 15 23 11 –12 in the production of octanes, is also used to manufacture other chemical products, such as polyethylene, polypro- pylene resins, polybutene, butylene oxide, and MEK. Profile D is distinguished by styrene, a precursor to po lystyrene and several copolymers. Approximately 7 million tons are produced worldwide annually from ethyl

VOC benzene, which in turn is prepared on a large scale by alkylation of benzene with ethylene. Styrene is employed in preparing materials such as rubber, plastic, insulation, 3-methylheptane 4-methylheptane tert-butylbenzene 1,2-dichlorobenzene formaldehyde freon-114 propionaldehyde freon-113 freon-12 fiberglass, pipes, automobile and boat parts, food contain- ers, and carpet backing [45]. Compound 1,3,5-trimethylbenzene, which has shorter half-life time (12 h) than sty- CAS 589-81-1 589-53-7 98-06-6 95-50-1 50-00-0 76-14-2 123-38-6 76-13-1 and 6 other sources (G–L) for NAPS station No. 50103 located in the petrochemical industry zone of Montreal-East profiles of traffic source (T.) 3. Percentage Table in 2000–2009 – cont. 75-71-8 and 2. Abbreviations as in Table 1 are bolded, undetermined values blank. Values ≥ 25% rene, is still present in the vicinity of petrochemical and

28 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER

chemical industrial sites; it is an important solvent used assigned to the industrial sources. On the other hand, in coatings, cleaners, pesticides, and inks. Alkene trans- organochlorides such as 1,1,1-trichloroethane, 1,2-dichlo- 2-hexene occurs in similar circumstances; however, it is roethylene, and specialty compounds such as 4-methyl- used in smaller quantities and most often in the research 2-pentene (which tends to appear in the “traffic” profiles), facilities. are arguably the fairly persistent remains of discharges Columns under “Downtown station No. 50115” in Table 1 from industrial factories (textile processing and dyeing) show profiles for the station at some distance (2.5 km) rather than from fuel combustion in motor vehicles. from the industrial park. The T., F., and I. profiles have Another characteristic of the petrochemical industry pro- their versions here, still reminiscent of the corresponding files is the absence of emissions of liquefied petroleum profiles for the “industrial” station 2. Profile E is char- gases (LPG): propane, butane, propylene, butadiene, acterized by strong presence of dibromochloromethane, butylene, and isobutylene. Therefore, these emissions, which is a quite stable trihalomethane (half-life counted occurring in other regions, appear to be escapes from in months) appearing in the atmosphere as a by-prod- the consumer widespread usage of LPG. uct of the water treatment and disinfection procedures. Petrochemical industry involves petroleum refining pro- The compound may be present nearby a drinking water cesses, creating point-like sources of fugitive organic pol- treatment plant. Profile F is an agglomeration of the “in- lutants and more dispersed sources in a form of effluents dustrial” profiles seen in station 2, which escape a closer and waste streams. The refining processes and operations analysis. It appears to be the image of the industrial pol- are of several basic types [46–49]. The 3 predominant ones lution already scrambled by the atmospheric chemistry – are: fractionation (distillation into fractions of hydrocar- due to 2.5 km distance from the pollution sources. bon compounds of differing boiling-point ranges), dividing molecules by thermal and catalytic cracking, and rearrang- Petrochemical industrial suburb (Montreal-East) ing molecules with isomerization and catalytic reforming. Montreal-East, formerly a borough, the precincts where Combining molecules through alkylation (introducing al- petrochemical industry was located, is the East-North ex- kyl groups, such as methyl, –CH3, or ethyl, –C2H5, group, tremity of the city of Montreal, Quebec. Three important into organic compound [50,51]), polymerization (convert- refineries operated here during the time period for which ing light olefin gases including ethylene, propylene, and this analysis was performed. Also the chief petrochemical butylene into hydrocarbons of higher molecular weight and plants are located in this region. higher octane number that can be used as gasoline blend- Table 3 shows the source profiles produced in NAPS sta- ing stocks), hydrogenation (addition of hydrogen atoms to tion 1 (No. 50103) situated in the Montreal-East indus- the molecule [52,53]), dehydrogenation (catalytic elimina- trial zone (time period: 2000–2009). Here, the “traffic” tion of hydrogen atoms from molecules), gas-phase pho- profile is characterized by the “lingering exhaust” finger- tochemical reactions, coal carbonization, and many other prints, consisting of a strong presence of volatile 2-meth- reactions most often involving ethylene or benzene [54–56] ylpentane in the air, but also of low-volatility cyclopen- also has great technological importance. tane. The specialty gasoline component, 2,3,4-trimeth- It appears that the processes result in releasing a pletho- ylpentane, is also present. Yet the traffic’s typical emis- ra of compounds that usually are reported to us as “sol- sions of hexanes, pentanes, heptanes, and octanes are vents” [47,57] into the environment. Specialty solvents detected only in their most lingering forms and must be and useful intermediates such as 2-methyl-2-pentene,

IJOMEH 2016;29(1) 29 ORIGINAL PAPER E. PORADA AND T. KOUSHA

cis-3-methyl-2-pentene, 2,4-dimethylpentane, trans-4-me- the chlorinated solvents. Occurrence of trichloroeth- thyl-2-pentene, trans-2-hexene, cis-1,4/t-1,3-dimethylcy- ylene, 1,1,2-trichloroethane, and 1,1-dichloroethylene, clohexane, cis-2-pentene, iso-butylbenzene, 2-ethyltolu- which arise in some refinery processes, here, most likely, ene, or 4-ethyltoluene can be observed. It is not known to are results of operations of a textile industrial unit. the authors if the compounds are targeted in the refinery operations, or if they are by-products. Suburban district Other compounds, such as octane, heptane, 2,4-dime Table 4 presents a model for the peripheral station 4 thylpentane, 2,2-dimethylpentane, 1,4-diethylbenzene, (No. 50129), located in a suburban district surrounded 2-methylhexane, 3-methylhexane, 1-hexene are clearly by agglomerations of pharmaceutical companies and targeted in operations of distillation, while nonane, do- research laboratories (almost 200 pharmaceutical com- decane, cis-2-butene may come from the cracking, dis- panies are located in and around Montreal). The model tillation, and/or catalytic dehydrogenation operations. shows typical distributed sources: T. (traffic), F. (fre- Also 2,2-dimethylbutane, 2,3-dimethylbutane, 2,2,4-tri- on-22), I. (inert), but also a local source of emissions methylpentane are targeted in the operations of alkyla- characteristic for organic synthesis in the pharmaceutical tion of ethylene. Benzylchloride is targeted in photo- industry, labeled Pha. Indeed, the manufacture of phar- chemical reaction of toluene with chlorine. Cyclohexane maceutical products involves mainly species such as: dec- is produced by hydrogenation of benzene, and xylenes are ane, 2-, 3-, 4-ethyltoluene, 1,2,3-trimethylbenzene, iso- targeted in the processes of catalytic reforming and coal butylbenzene, indane, and also chloroform – a common carbonization. solvent used in a laboratory. Table 3 exhibits a number of species occurring only in this A separate source, labeled Ch. for “Chemical manu- zone. Apart from p-cymene, there also appear monoter- facturing” is distinguished by the compounds such as penes camphene and a-pinene, however, indicating sepa- 3-methyl-1-pentene, bromoform, dibromomethane, fre- rate sources. They are probably sequels of wood pulping ons, and 1,2-dichloropropane, which are important inter- and traditional timber industry, or the naturally occurring mediates in the production of many chlorinated chemi- wood terpenes. cals, mainly solvents, degreasers and pesticides. Aldehydes such as propionaldehyde, tolualdehydes, Finally, source X cannot be easily qualified. It is distin- and MEK come from those sources, rather than from guished by a massive emission of ethylene, simple un-

traffic or petrochemical plants. On the other hand, other saturated hydrocarbon (C2H4) widely used in the petro-

aldehydes, crotonaldehyde and 2,5-dimethylbenzal chemical and chemical industries, and 1-propyne (C3H4) – dehyde – important building blocks in the organic chemis a specialty fuel for not-industrial application, extremely try – are probably produced in refinery operations. flammable unsaturated aliphatic alkyne. Refineries also produce important intermediates in the manufacture of chlorinated pesticides and solvents, Citywide features of the hydrocarbon pollution chloroform, bromoform, dichloromethane, bromodi- Short chain haloalkanes such as dichloromethane and chloromethane, dibromomethane, 1,1-dichloroethane, dibromomethane, very common solvents and reagents, 1,1,2,2-tetrachloroethane, 1,2-dichloropropane, and trans- formerly widely used in preparation of pesticides and fu- 1,3-dichloropropene [1], while hexachlorobutadi- migants – but toxic when released to the atmosphere – ap- ene is released as a by-product in the manufacture of pear in all the 4 stations in Montreal and have manifold

30 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER

1.51 0.21 0.03 0.04 0.09 0.11 0.26 0.14 0.02 0.02 0.10 0.01 0.63 1.98 0.08 1.06 0.72 0.12 0.39 0.05 0.03 0.19 0.19 0.12 0.20 3.29 0.21 concentration 1 1 2 9 X 18 20 30 57 73 61 55 60 1 3 4 6 0 4 0 2 8 8 10 –1 10 –1 –5 –2 –2 14 –4 14 –7 11 36 50 –5 11 Ch. 4 12 61 62 61 55 50 67 48 22 63 55 78 Pha. NAPS station No. 50129 Peripheral 9 8 4 0 3 I. –4 17 10 17 10 –5 11 22 13 76 68 68 77 76 28 22 –2 –8 13 14 12 –18 4 9 4 8 1 9 0 2 0 2 1 2 5 3 7 7 8 3 4 1 F. 73 36 25 31 40 13 11 6 8 3 9 T. –5 10 13 13 16 16 14 23 24 24 –1 18 18 12 24 27 27 29 24 26 71 79 66 VOC freon-22 styrene 1-octene 2,2,5-trimethylhexane 1-hexene 2-ethyltoluene 3-ethyltoluene 4-ethyltoluene sec-butylbenzene 3,6-dimethyloctane 1,2,3-trimethylbenzene iso-butylbenzene dichloromethane ethylene 1-propyne benzene propylene 1,3-butadiene 3-methylhexane indane 1,3-diethylbenzene decane undecane dodecane 2,2-dimethylbutane isopentane 2,3-dimethylbutane CAS 75-45-6 inert gases (I.), and industrial sources pharmaceutical (Pha.), chemical manufacturing (Ch.), freon-22 (F.), profiles of distributed sources: traffic (T.), 4. Percentage Table and unknown (X) for NAPS station No. 50129 located at Montreal periphery in 2000–2009 100-42-5 111-66-0 3522-94-9 592-41-6 611-14-3 620-14-4 622-96-8 135-98-8 15869-94-0 526-73-8 538-93-2 75-09-2 74-85-1 74-99-7 71-43-2 115-07-1 106-99-0 589-34-4 496-11-7 141-93-5 124-18-5 1120-21-4 112-40-3 75-83-2 78-78-4 79-29-8

IJOMEH 2016;29(1) 31 ORIGINAL PAPER E. PORADA AND T. KOUSHA

0.59 0.03 0.64 0.40 0.04 0.12 0.62 0.10 0.94 0.43 3.51 2.33 2.95 0.07 0.51 3.59 1.98 0.19 1.41 0.10 0.65 0.16 0.14 0.14 0.03 0.32 0.26 concentration 4 X 22 15 14 13 21 19 28 45 24 33 10 33 3 8 2 1 2 7 2 0 1 3 3 0 –1 10 –4 –5 –3 –3 –6 –3 –3 –4 16 17 Ch. –14 –24 4 8 16 20 15 Pha. NAPS station No. 50129 Peripheral 2 6 7 2 9 6 7 3 I. 15 22 22 –2 36 47 28 27 56 25 22 18 16 11 22 11 12 18 1 1 2 5 5 1 3 0 2 4 1 3 5 5 2 9 4 1 4 3 6 3 4 F. –3 –1 –1 –2 T. 50 65 59 64 28 31 34 37 58 33 39 78 64 48 39 40 44 66 61 49 48 60 50 51 58 44 49 VOC o -xylene cis -3-methyl-2-pentene 3-methylpentane methylcyclopentane iso-propylbenzene 1,3,5-trimethylbenzene ethylbenzene n-propylbenzene 2-methylpentane 1,2,4-trimethylbenzene propane isobutane butane 2,4-dimethylpentane 1-butene/isobutene toluene m and p -xylene methylcyclohexane pentane 1-pentene hexane cyclohexane octane nonane cyclopentene heptane tetrachloroethylene CAS inert gases (I.), and industrial sources pharmaceutical (Pha.), chemical manufacturing (Ch.), freon-22 (F.), profiles of distributed sources: traffic (T.), 4. Percentage Table and unknown (X) for NAPS station No. 50129 located at Montreal periphery in 2000–2009 – cont. 95-47-6 922-61-2 96-14-0 96-37-7 98-82-8 108-67-8 100-41-4 103-65-1 107-83-5 95-63-6 74-98-6 75-28-5 106-97-8 108-08-7 115-11-7 108-88-3 108-38-3 108-87-2 109-66-0 109-67-1 110-54-3 110-82-7 111-65-9 111-84-2 142-29-0 142-82-5 127-18-4

32 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER 0.02 0.03 0.18 0.03 0.02 0.16 0.14 0.21 0.14 0.15 0.18 0.03 0.35 0.12 0.08 0.06 0.15 0.02 0.59 0.05 0.19 2.62 0.03 1.72 0.63 0.13 2.70 1.16 0.08 0.04 0.03 4 6 7 43 52 55 67 41 62 65 53 65 65 40 35 23 –11 4 7 8 2 12 21 23 12 –4 10 –6 –9 52 43 56 53 26 55 41 48 50 41 35 46 54 30 –11 –16 –17 4 4 4 1 5 3 12 11 16 22 19 –9 19 19 12 16 16 6 0 4 0 7 0 16 23 14 16 15 23 27 35 39 28 29 23 11 40 26 26 50 29 30 32 44 22 20 12 18 2 1 1 3 6 2 4 2 5 2 0 5 4 3 5 2 2 3 6 7 3 7 7 6 5 7 6 11 18 14 13 48 55 66 54 37 81 66 36 25 55 84 49 27 28 70 33 72 26 –9 –5 –16 –15 –28 –20 –23 –13 –17 –16 –13 –26 –13 cis -1,4/t-1,3-dimethylcyclohexane trans -1,4-dimethylcyclohexane cyclopentane trans -2-hexene 2,2-dimethylpropane 2-methyl-2-butene 2-methyl-1-butene 2,2,4-trimethylpentane 2,3-dimethylpentane cis -2-butene trans -2-butene cis -2-hexene 2-methylhexane 2-methylheptane cis -2-pentene cis -1,3-dimethylcyclohexane trans -2-pentene 3-methyl-1-pentene carbontetrachloride 1,2-dichloroethane 1,1,1-trichloroethane ethane bromoform freon-11 freon-113 freon-114 freon-12 chloromethane bromomethane dibromomethane chloroethane 2207-03-6 2207-04-7 287-92-3 4050-45-7 463-82-1 513-35-9 563-46-2 540-84-1 565-59-3 590-18-1 624-64-6 7688-21-3 591-76-4 592-27-8 627-20-3 638-04-0 646-04-8 760-20-3 56-23-5 107-06-2 71-55-6 74-84-0 75-25-2 75-69-4 76-13-1 76-14-2 75-71-8 74-87-3 74-83-9 74-95-3 75-00-3

IJOMEH 2016;29(1) 33 ORIGINAL PAPER E. PORADA AND T. KOUSHA

sources. This happens regardless of the efforts to curb their release into the environment [32,58,59]. Their 0.15 0.02 0.02 0.06 0.07 0.05 0.12 0.03 presence in the environment is still a result of different

concentration product/waste streams coalescing in evaporations into atmosphere. The toxicity of trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane, and X 20 24 bromoform) is widely discussed [60–67], but their usage as water disinfectant persists. They form in the atmosphere as a quite stable byproduct when chlorine is added to water to kill bacteria and, therefore, appear in each monitor- 26 93 10 –5 –3 Ch. ing station. They are also used on a smaller scale in laboratories in chemical manufacturing [67,68]. Trichlorobenzenes are hardly detectable in the urban at- 5 74 20 11 20 24 23 mosphere in Montreal (they have a relatively short half- Pha. life in the atmosphere), and their possible source: volatil- ization from sediments and soils [63,69–73] is not detected. Dichlorobenzenes (1,2-, 1,3-, 1,4-) appear in emissions NAPS station No. 50129 Peripheral 0 3 I. 18 16 16 from petrochemical factories and from manufacture of polymers, while chlorobenzene, the production of which in the U.S. declined considerably in the 2nd half of last century, is still detectable in emissions from automotive 3 5 6 7 4 2 3 8 F. industries, where it is used as a solvent to degrease automobile parts [1]. Great restrictions on the use of chlorofluorocarbons (fre-

T. ons: 11, 12, 113, 114) as refrigerants and propellants have –5 20 22 18 20 17 20 –24 been imposed since 1980 [14]. They have now been largely replaced by hydrochlorofluorocarbon freon-22. The chlorofluorocarbons, as very inert gases, still persist in the atmosphere accompanied by the abundant chlorinated hydrocarbons, chloroform and chloromethane, however, never in a company of freon-22. This suggests that sources VOC of freon-22 and the ozone-depleting freons are different: the former has a source in the industry and in the consumer goods, while the latter ones are inert atmospheric chloroform 1,2-dichloropropane 2,2-dimethylpentane 2,5-dimethylhexane 2,4-dimethylhexane 4-methylheptane 3-methylheptane 1-methylcyclopentene vestiges of formerly massive releases from the wide industrial and consumer usage. The Montreal “traffic” source, in comparison to the traffic CAS inert gases (I.), and industrial sources pharmaceutical (Pha.), chemical manufacturing (Ch.), freon-22 (F.), profiles of distributed sources: traffic (T.), 4. Percentage Table and unknown (X) for NAPS station No. 50129 located at Montreal periphery in 2000–2009 – cont. 67-66-3 and 2. Abbreviations as in Table 1 are bolded, undetermined values blank. Values ≥ 25% 78-87-5 590-35-2 592-13-2 589-43-5 589-53-7 589-81-1 693-89-0 in Mexico City [24] and locations in China [21–23], is more

34 IJOMEH 2016;29(1) SOURCES OF VOCs IN MONTREAL ORIGINAL PAPER

loaded with species related to octane content in the gaso- The “negative” sources present a complex picture and line and to gasoline combustion products, such as ethylene. they require further investigation: preliminary seasonal It is not clear whether the distinction reflects differences in analysis of the ambient concentrations of VOCs sug- urban transit technologies and/or in fuel additives or results gested that specific air masses could be responsible for of the methodology applied. The chloroethane used in lead- affluence of some species, at the same time causing deed gasoline, but banned in Canada since 1980, disappeared pletion of other species. If confirmed, this would explain from the traffic source. Its counterpart in the unleaded the heterogeneous nature of sensor models generated gasoline, methyl tert-butyl ether (MTBE), is also absent. with EPA UNMIX.

Methodological aspects ACKNOWLEDGMENTS Factorization methods as PMF, but also UNMIX, pref- The authors want to thank Dr. Mietek Szyszkowicz from Health erentially treat the variables with higher average values. Canada for the instructive discussions concerning our method- Therefore, the highest-concentration VOC species are ology and Janina Porada, MS, from the Abbott Corporation given priority in emission profiles. The highest concentra- for her proof-reading of the chemical content. Environment tions should be the 1st to divulge their sources, however, Canada was very supportive when accessing their repositories the UNMIX application also makes it possible to discern of VOC data. some lower-concentrations VOCs that persistently accom- pany the high-concentration species, providing chemical REFERENCES data, which facilitate identification of the sources. 1. Agency for Toxic Substances and Disease Registry. Atlanta: The lowest-concentration VOCs are the most problemat- The Agency [updated 2008 Aug 14; cited 2014 Oct 31]. Chem- ic, particularly when dealing with point sources: environ- ical classification. Available from: http://www.atsdr.cdc.gov/ mental influence of VOCs destroys the relationship be- substances/ToxChemicalClasses.asp. tween the source emission pattern and the measurements 2. International Agency for Research on Cancer. Some in- performed by a distant receptor. In the case of the distrib- dustrial chemicals and dyestuffs. In: IARC Monographs on uted sources, the lowest-concentration VOCs tend to form the evaluation of carcinogenic risks to humans. 1982 [cit- noise-like background for the more prominent VOCs. ed 2014 Nov 2];29:1–416. Available from: http://apps.who. UNMIX would refuse to produce results when the mea- int/bookorders/anglais/detart1.jsp?sesslan=1&codlan=1&co surements cannot be reliably “unmixed” even when as- dcol=72&codcch=29. suming “negative” sources, i.e., taking into account an 3. U.S. Environmental Protection Agency. Washington (DC): environmental depletion of VOCs. The Agency [updated 2013 Aug 8; cited 2014 Oct 31]. But, when with some VOC menu UNMIX achieves suc- Evaluating exposures to toxic air pollutants: A citizen’s cess, the measured VOC concentration becomes a sum guide (EPA 450/3-90-023). Available from: http://www.epa. of the positive inputs from VOC emissions by physical gov/ttnatw01/3_90_023.html. sources – reduced by VOC depletion due to reactions in 4. Wieslander G, Norback D, Edling C. Airway symptoms the atmosphere. The removal of VOC, largely depend- among house painters in relation to exposure to volatile ing on the weather and not necessarily correlated with an organic compounds (VOCS) – A longitudinal study. Ann input from a physical source, is represented as separate Occup Hyg. 1997;41:155–66, http://dx.doi.org/10.1093/ann “negative” sources. hyg/41.2.155.

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