The 1990 Toronto Personal Exposure Pilot (PEP) study

THE 1990 TORONTO PERSONAL
EXPOSURE PILOT (PEP) STUDY

JULY 1991

Environment
Environnement

Ontario

ISBN 0 7729 7%2 6

THE 1990 TORONTO PERSONAL EXPOSURE PILOT (PEP)

STUDY

ARB-207-90

Report prepared by:
R.W. BeU, R.E. Chapman, B.D. KruscheL
M.J. Spencer, K.V. Smith and M.A. Lusis

Report prepared for:

Atmospheric Research and Special Programs Section

Air Resources Branch

Ontario Ministry of the Environment

JULY 1991

o

RECYCUBLE

Cette publication technique
n'est disponible qu'en anglais.

Copyright: Queen's Printer for Ontario, 1991

This publication may be reproduced for non-commercial purposes

with appropriate attribution.

PIBS 1616
log 90-2207-207

Executive Summary

In a recent health survey sponsored by the Health Information Section of the
City of Toronto, 60% of all respondents identified environmental air pollution as a
major area of concern. In order to assess the total atmospheric concentration levels
of volatile organic compounds (VOCs), some of which are toxic (such as benzene),
to which people are exposed, a current air toxic VOC data base characterizing the
major microenvironments in which individuals work and/or live must be established.

A Personal Exposure Pilot (PEP) study was designed to supply preliminary
input to this much needed VOC data base with objectives of acquiring and analyzing
indoor air samples from the office and home environments, ambient samples from
the downtown and residential areas of Toronto, and samples as different staff
members commuted to and from work and as they spent their noon-hours outdoors
in the downtown area of Toronto.

Following an 8-day cycle from June to August, 65 field samples were
collected and subsequently analyzed. Each sample was scanned for over 130
different VOCs but the number was reduced to 45 and finally to 22 of the more
prevalent compounds in order to facilitate quality control, quality assurance,
interpretation and presentation.

Large variations in VOC concentrations were noted in the indoor environments
(office and home) and the indoor air quality appeared to be at least 2 to 5 times
worse than the outdoor air quality.

With respect to the outdoor and commuting microenvironments, the poorest
air quality was noted during the morning commutes and was thought to be due to
the poorer atmospheric dispersion conditions, higher traffic density and cooler
temperatures. The major source of ambient VOCs was deemed to be vehicular
emissions.

In general, no unusual odours were detected during any of the sampling
periods and all measured VOC concentrations were low.

Further work on personal exposure to toxic VOCs in Ontario urban areas,
similar to the present study, is strongly recommended.

TABLE OF CONTENTS

EXECUTIVE SUMMARY

1.0 Introduction / Background 4

2.0 Survey Method and Results

2.1 Method 5

2.2 Results

2.2.0 - Representative Chromatograms of PEP 7

2.2.1 - The Indoor Environments: Office and Home 8

2.2.2 - The Outdoor Environments: Downtown and Resid 10

2.2.3 - Outdoor Versus Indoor Air Quality 11

2.2.4 - The Commuting and Noon-Hour Programs

- The Morning Rush-Hour 12

- The Afternoon Rush-Hour 13

- Intercomparison 13

- The Noon-Hour Walk-Abouts 14

- The 4 Special Samples 15

2.2.5 - Comparisons with Other Ministry Studies

- The MOE 1990 Toronto Toxics

and Benzene Studies 15

3.0 Conclusions 18

4.0 References 19

APPENDIX A

(The Lab Work)

VOC Method Detection and Method Quantization Limits 21

The Shortened VOC Target List 22

APPENDIX B
(The Field Work and Results)

Representative Chromatograms of PEP - VOC Profiles / Fingerprints

Figure 1: The Indoor and Outdoor Samples 26

Figure 2: The Commuting and Noon-Hour Samples 27

The Indoor Environments: Office and Home

Table 1: Indoor Air at 880 Bay Street (Office) 28

Table 2: Indoor Air Comparisons (Office) 30

Figure 3: Indoor Air Comparisons 31

Table 3: Indoor Air (Home) 32

The Outdoor Environments: Downtown and Residential

Table 4: College Street VOC Results (Downtown) 34

Table 5: Garnock Avenue VOC Results (Residential) 36

Table 6: Ambient Concentrations (Diurnal Variations) 38

Figure 4: Diurnal Variations 39

Figure 5: Nighttime Comparison (Residential & Downtown) 40

Outdoor Versus Indoor Air Quality

Table 7: Outdoor Versus Indoor Air Quality 41

Figure 6: Outdoor Versus Indoor Air Quality 42

Figure 7: Time Budget Analyses (Ott) 43

The Commuting and Noon-Hour Sampling Programs

Table 8: The Morning Commuter Runs 44

Table 9: The Afternoon Commuter Runs 46

Table 10: The Noon-Hour Walk-Abouts 48

Table 11: The Commuting and Noon-Hour Intercomparisons 50

Figure 8: The Commuting and Noon-Hour Intercomparisons 51

APPENDIX C
(Other Ministry Work)

The 1989 ARB Benzene Study (Executive Summary and Results) 53

The Toronto Toxics Spring Study (Memorandum Excerpts) 55

The Toronto Toxics Summer Study (Memorandum Excerpts) 61

1.0 INTRODUCTION / BACKGROUND:

In Report *3, entitled Chemicals and Toxins', prepared by the Community
Health Information Section of the City of Toronto Department of Public Health,
nearly 1000 individuals of age 15 years or older were interviewed in 1988 as part of
a Toronto Community Health Survey. In this survey, questions were asked about
health problems that may be environmentally influenced and other concerns with the
Toronto environment in general. The survey findings reflected an increase in public
awareness and concern regarding the environment with most respondents being
dissatisfied with Toronto's environment. When respondents were asked to specify
their concerns about the environment, 92% identified one or more areas. Air
pollution with its associated problems were the most common (60% of the
respondents), followed by water (44%) and chemical pollution (18%).

During 1989, a controversy arose regarding acceptable benzene concentration
levels in the urban and rural environments. Following a worse case scenario, the Air
Resources Branch conducted an ambient air study in the summer of 1989 in order
to establish personal exposures to ambient benzene concentrations while refueling at
retail gas stations and while walking in downtown Toronto. From analyses of the
downtown samples, ambient benzene concentrations ranged from 3 to 24 |ig/m^
(micrograms per cubic metre) with a geometric mean of 9.8 fig/m^ and from the
refueling samples, the concentration range was 670 to 8640 |ig/m^ with a geometric
mean of 2890 ^g/m^ (An internal ARB report was prepared for this study and
excerpts are included in Appendic C.)

In late 1989, Toronto's Special Advisory Committee on the Environment
released a report that proposed several initiatives to deal with the major
environmental problems in the City of Toronto. The Environmental Protection Office
(EPO) of the Department of Health was charged with conducting environmental
assessments of atmospheric pollutants not routinely monitored by other regulatory
agencies (for example, the Ministry of the Environment (f\^OE), Environment Canada
(EC), etc.). The EPO retained the firm of Rowan, Williams, Davies and Inwin Inc.
(RWDI) to undertake an assessment of air quality as it pertains to toxic compounds.
Their air toxic study was to be composed of a historical review, an ambient air
program and a risk assessment evaluation. The RWDI ambient program was
conducted in March and June of 1990. Concurrent with this program, the Air
Resources Branch (ARB) also undertook a limited monitoring program in the same
general areas. ARB's program consisted of acquiring inhalation zone air samples
(i.e. acquired at nose level) during the morning, noon and afternoon rush-hour

periods. The results of the ARB program were presented to the Central Region of
MOE and the City of Toronto in two technical memoranda in the fall of 1990 and
excerpts are also included in Appendix C.

Realizing that people living and working in the City of Toronto may spend as
much as 90% of their time indoors and that commuting often constitutes a significant
percentage of the person's time spent in the Toronto airshed (sometimes as much
as 5 hours per day), an investigation into each of these microenvironments as well
as outdoors air was needed if any toxicity assessment studies were to be carried
out. (From analyses of data acquired in 44 different U.S. cities, W.R. Ott^ reported
that on the average, only 2% of an employed person's time was spent outdoors, 6%
in-transit, 28% indoors at work and 63% indoors at home.)

A considerable amount of work had been done with respect to determining
concentrations of the classical contaminants (such as sulphur dioxide, carbon
monoxide, oxides of nitrogen, etc.) in these microenvironments but little has been
done with respect to volatile organic compounds (VOCs). Therefore it was decided
to conduct a pilot study in order to obtain a better understanding of personal
exposure to this latter class of potentially toxic airborne pollutants.

The Personal Exposure Pilot (PEP) study's field objectives were to acquire
indoor air samples for the office and home environments, outdoor ambient air
samples for the downtown and residential areas of Toronto, and samples as
different staff members commuted to and from work and as they spent their noon-
hours outdoors in the downtown area of Toronto.

2.0 SURVEY METHOD AND RESULTS:

2.1 Method

The PEP field program started on June 11'^ and ran on an 8-day mid-week
cycle (a Tuesday, Wednesday or Thursday) until August 29'^

The field samples were collected by pumping air, at a constant flow rate set
in the range of 50 to 500 ml/min (millilitres per minute), through a three-layer
cartridge containing adsorbents Carbotrap B, Carbotrap C and Spherocarb. Most
volatile organics are trapped on these adsorbents whereas inorganics pass through.
In total, 65 field samples were collected and analyzed for VOC content by the gas
chromatograph flame ionization detector and mass selective detector (GC/FID/MSD)
system at ARB. Each sample was thermally desorbed by heating the cartridge,
under helium purge, to 300-350°C with the desorbed organic compounds being
passed to and collected in a specially designed cryogenic loop. The collected

organics were then flash vaporized onto the head of a triple GC capillary column
system held initially at -50°C (HP5880 system). The columns were 25 metre J&W
fused silica 0.25mm ID (millimetre internal diameter) capillary columns with I.Oiim
film thickness. Two of the columns (a DB-1 and a DB-5) were coupled to FIDs and
the third (a matched DB-1 column) was coupled to the MSD system. Once the
organics had been deposited at the head of these columns, a chromatographic
temperature program was started. The component peaks eluting from the columns
were identified and quantified using FID and MSD techniques. Each sample was
scanned for over 130 different VOCs whose identity was based on retention indices
stored in the GC/FID library. If an anomalous peak (unidentified VOC) appeared on
the resulting chromatograms or if confirmation was needed, an MSD scan was
performed on that particular peak. The MSD was a HP5970 unit with chemstation
and associated analytical software. Throughout all of the analyses, no significant
peaks apart from those registered in the system's library were identified. For both
quantification and identification (with confirmation), the number of VOCs were further
reduced to 45 of the more ubiquitous and prominent aliphatic and aromatic volatile
organics and their halogenated (chlorinated) counterparts. A list of the respective
method detection limits (MDLs) and method quantization limits (MQLs) and a table
of the use(s) and source(s) of these 45 VOCs are given in Appendix A.

The major microenvironments investigated during this study were as follows:

0 Indoor:

Eight indoor office samples were obtained in several offices and one
laboratory at the Air Resources Branch in downtown Toronto. The sampling
was done while the normal occupant was out of the office and the sampler
unit was usually placed atop the occupant's desk. The lab sample was
exposed in ARB's main organic analytical laboratory while routine work was
taking place. The monitoring was conducted between 9am to 4pm and all
offices and the laboratory were "Smoke-Free Wori<place Environments".

Four indoor home samples were obtained at different residences within
the Toronto airshed; namely, Oshawa, Thornhill, Scarborough and Richmond
Hill. The sampling was conducted overnight with durations up to sixteen
hours.

0 Outdoor:

Sixteen downtown ambient air samples were acquired near the
entrance to the Metropolitan Police Centre at College and Yonge Streets and

7 residential ambient samples were collected in the backyard of *18 Garnock
Avenue near Danforth and Broadview Avenue in Toronto. These two sites
were only 4 to 5 km apart but the surroundings were quite different: the
downtown site was characterized by a high traffic volume, asphalt, concrete
and many high-rise buildings whereas the residential site was characterized
by a much smaller traffic volume, some "Green" area(s) and low-rise
buildings. Through the use of sequential sampler units, consecutive 12-hour
samples were collected at each site and the air was sampled at a height of
1 .5 metres above ground.

Commuting and Noon-Hours:

In order to simulate the typical commuter's exposure to VOCs, several
staff members volunteered to participate in this phase of the study. They
collected air samples while enroute to and from their residences and work
and as they walked-about during the noon-hour periods in downtown Toronto.
All participants were non-smokers and did not wear any lotions or perfumes
during these periods.

The air samples were collected by personal sampler units and the air
was sampled within the inhalation zone of each participant. The samples were
usually 1 to 2-hours in duration and 11,8 and 8 VOG samples were collected
during the morning, noon and afternoon periods respectively.

Special Samples:

While fulfilling the objectives set out in Section 1.0, four special
composite samples were acquired during this study. The first 2 samples
depicted indoor VOC concentrations while the participant was attending
meetings; the 3"^ was acquired while the participant was at a barbecue; and
the 4'^ was an overall composite sample of the afternoon/morning commutes
and the overnight residential indoor air quality (a 16-hour sample).

2.2 RESULTS:

(For a detailed listing of results, please see appendix B.)

2.2.0 Representative Chromatograms of the Different Programs Within
PEP (Figures 1 and 2)

For a qualitative point-of-view, representative VOC fingerprint chromatograph
profiles of each of the aforementioned microenvironments are presented for the

reader's information. Each peak in these chromatograms represents a response from
a flame ionization detector to an organic compound as it eluted from a
chromatographic column. The time of elation (retention time) indicates the identity of
the organic and the area under each peak is directly proportional to its amount. This
amount divided by the sampled air volume is equal to the organic's concentration in
the air sampled.

These representative chromatograms are for qualitative comparisons only. As
mentioned earlier, the ARB GC/FID library had the ability of identifying over 130 of
these peaks and if some were considered to be significant, i.e. exhibit large areas,
and were not contained in the library, an MSD scan was performed on the peak and
its identity was resolved.

Each sample depicted in Figure 1 had been exposed for 8 hours and 36 litres
of air were sampled. The top 2 chromatograms are representative of the outdoors
environment (residential and downtown) and the bottom are representative of the
indoor environments (office and home). These samples clearly show the air quality
differences between the indoor and outdoor environments.

The samples shown in Figure 2 had been exposed for 1 to 2 hours with
approximately 10 to 12 litres of air sampled. The first chromatogram is indicative of
the morning commutes, the second indicative of the noon-hour walk-abouts and the
last (bottom) chromatogram indicative of the afternoon commutes. As in the previous
figure, these chromatograms clearly show different VOC profiles for each of these
periods.

2.2.1 The Indoor Environments: Office and Home

As noted in Table 1, 8 VOC samples were obtained between June 20"^ and
August 29'^ in 3 offices and the organic analytical laboratory at the Air Resources
Branch. In general, all targeted VOC concentrations were low with levels ranging
from less than the f\/lDL (Appendix A) to approximately 80 |ig/m^ The more
prominent VOCs were the low-boiling alkanes (propane to hexane; a maximum
concentration of 32 iig/m^), aromatics (benzene to xylenes; up to 63 |ig/m^) and
chlorinated aliphatics (1,1-dichloroethene (20 |ig/m^), 1,1,1-trichloroethane (65 |ig/m^),
tetrachloromethane (35 |j.g/m^), trichloroethene (81 |ig/m') and tetrachloroethene (35
^ig/m^)). Some high-boiler VOCs were also detected in these samples; namely,
nonane (12 ^g/m'), 1,3,5-trimethylbenzene (20 ^ig/m^), decane (35 ng/m^), 1,3,5-
trichlorobenzene (20 ng/m^) and 1 ,2-dichlorobenzene (20 ^ig/m'). Bruce A. Tichenor
et al.^ suggested that outgassing from chlorinated water was a major source of

8

trichloroethene and other chlorinated organics, and that perchloroethylene
(tetrachloroethene) was emitted from dry-cleaned clothes. Major indoor sources of
the higher ordered alkanes and aromatics are floor waxes, wood stains, furniture
polishes, room fresheners and adhesives.

Upon first inspection of the indoor office VOC data set, a significant decrease
in concentrations was noted in the four August samples as compared to the four
June/July samples. When the monthly averages of the 22 short-listed VOCs (Table
2) are displayed (Figure 3), this abrupt change in air quality was more noticeable.
From an elementary quantitative perspective, the total average concentration for the
22 VOCs detected in the June and July samples was 350 [ig/m^ whereas for the
August samples, this average was only 50 ng/m^ Many plausible reasons for this
apparent improvement in air quality were investigated; for example: i) the building's
air conditioner system had undergone extensive repair throughout the summer and
ii) a nearby source of VOCs had been removed from the vicinity of the building's air
conditioner intake manifolds (a nearby roofing operation). However after closer
examination, neither of these two reasons were justified: chronologically, the air
conditioner problems had been fixed by early July and the roofing operation had
ended June 20'^ Upon re-examining Table 1, the results obtained on July 13 were
also similar to those reported for August. This observation suggested that the
apparent improvement in air quality may be due to the inherent large variations in
indoor measurements and the relatively small sample size of the present study. This
hypothesis is also supported by B.A. Tichenor' as he stated, "(with respect to indoor
measurements), the range of concentrations for a specific compound can vary
widely between measurements" and that "In most studies, the concentrations of
specific organic compounds exceed the outdoor concentrations, indicating that the
major source of these compounds is indoors."

It was of interest to note that for the sample acquired in the analytical organic
laboratory, the number and concentrations of VOCs measured were similar to those
reported for the samples acquired in the offices. Two large fume hoods ensured 3 to
5 complete air exchanges per hour in this laboratory and emissions from the
analytical work were being vented through these hoods effectively and efficently.

Four indoor air samples were acquired overnight at different staff members'
homes. As noted in Table 3, apart from the expected low-boiling aliphatics that may
be attributed to natural gas (heating) and other petroleum byproducts, higher
ordered VOCs attributable to cleansers, detergents and solvents were detected. As
with the office samples, some of the more prominent VOCs were dichloromethane
(paint remover, cleaning solvent; 35 ^g/m^), 1,1,1-trichloroethane (a solvent/cleaner;
28 |J.g/m^), toluene (solvent; 89 ^g/nf), xylenes (solvent; 39 ^ig/m^), and

decane/nonane (detergents, floor waxes and room fresheners; 23 |ig/m').

It should be stated that all VOC concentrations measured in the
aforementioned indoor samples were low and that no significant nor unusual odours
were detected during any of the sampling periods.

2.2.2 The Outdoor Environments: Downtown & Residential

With respect to the ambient downtown VOC data (Table 4), the overall
average VOC concentrations were low and similar to other concentrations that have
been measured in the other urban airsheds (R. Beir, T. Dann^ and J.J. Shah®).
Apart from an obvious outlier toluene concentration of 520 |Ig/m^ average VOC
concentrations measured in the outdoor downtown environment were all less than 20
M.g/m^ and on the average, only 25 different VOCs were detected in each sample.

(With respect to toluene, the elevated concentration was detected during the
daytime but no obvious source was apparent. Some localized activity may have
taken place at this site as the more common sources of toluene are resins,
adhesives, paints and coatings, dyes and perfumes. The Ministry Air Quality
Standard for toluene is 2,000 ^g/m^)

Very low VOC concentrations were detected in the 7 ambient samples
acquired at the residential site on Garnock Avenue (Table 5). As with the downtown
site, all concentrations were less than 20 ng/rn^ and on the average, only 20
different compounds were detected in the samples.

The samples acquired at both outdoor locations generally had similar profiles;
that is, the dominant VOCs were the low-boiling alkanes (propane to hexane) and
aromatics (benzene, toluene and xylenes) and there were only trace amounts of the
chlorinated and substituted benzenes.

From a diurnal perspective, the ambient nighttime VOC concentrations
measured at the dowtown site were slightly higher than those measured overnight at
the residential site (Table 6 and Figures 4 and 5). These somewhat higher
concentrations were thought to have resulted from the poorer overnight atmospheric
dispersion conditions in the downtown area due to the high-rise buildings and the
relatively larger traffic volume.

The average benzene, toluene and xylene concentrations normalized to
ethylbenzene also lent some insight as to nature of the different sources in these
areas. When comparing with the results of Tom Dann's^ (1986) VOC sampling
program conducted on Breadalbane Avenue in Toronto, a degree of similarity was
noted.

10

Downtown

Residential

T. Dann

(College & Yonge)

(Garnock)

(Breadalbane)

Benzene/Ethylbenzene

2.1

2.0

2.5

Toluene/Ethylbenzene

5.7

6.5

10.0

Xylenes/Ethylbenzene

3.3

3.5

3.5

Breadalbane Avenue runs parallel to College Street and is approximately
0.3km to the north. Apart from the toluene/ethylbenzene ratio being somewhat
higher in Dann's work (we also detected a large variability in the concentrations for
this compound; a maximum of 520 [ig/m^ was detected but not included in the
above table entries), the normalized ratios are similar and suggests that the major
source(s) character in this area of Toronto has remained essentially unchanged
throughout the past few years; namely, vehicular emissions.

Furthermore, T. Dann's work also supports the relatively low ambient
concentrations of benzene detected during this study. As noted in Table 6, the
average benzene concentrations ranged from 2 to 3.3 ^g/m^ and from T. Dann's
work, a mean benzene concentration of 2.9 |xg/m^ was determined from the
analyses of the 13 samples collected during August and October of 1986 at
Breadalbane Avenue. (In addition, T. Dann also reported that between August 1984
and March 1986, the mean benzene concentration measured in 105 samples
acquired at the Junction Triangle area of Toronto was 9.0 ^g/m^ Bell" also reported
similar higher concentrations in the Junction Triangle during 1986.)

2.2.3 Outdoor Versus Indoor Air Quality

Upon comparing the indoor and outdoor VOC data sets acquired during the
PEP study, the indoor air quality was highly variable yet appeared to be as much as
2 to 5 times worse than the outdoor air quality (Table 7 and Figure 6). The totals
of the average short-listed 22 VOC concentrations for each of the four
microenvironments were as follows: 43 ^ig/m^ (outdoor, downtown), 32 ^ig/m^
(outdoor, residential), 201 ng/m^ (indoor, office) and 284 jig/m' (indoor, home).

Upon inspection of these data, the indoors appears to be a major source of
chlorinated and higher-ordered aliphatics; namely 1,1,1-trichloroethane (dry cleaning),
tetrachloromethane (floor waxes, furniture polishes, paints and adhesives),
tetrachloroethene (dry cleaning, paint removers and solvents), nonane and decane
(waxes, stains and room fresheners). These results are in keeping with the findings

11

of other workers (B.A. Tichenor (1988)' and H. Greim (1989f) and have major
implications as far as population exposure to toxic airborne substances is concerned.
As mentioned earlier, Figure 7, taken from Ott^ (1988), shows that on average, the
portion of time spent indoors by employed people in 44 different U.S. cities was
approximately 91%. One must therefore legitimately ask whether enough emphasis
is being placed on indoor air quality studies as compared with the current ambient
(outdoor) air monitoring programs.

2.2.4 The Commuting and Noon-Hour Programs
The Morning Rush-Hour:

Five ARB staff members participated in this phase of the PEP study in order
to characterize personal exposures to toxic VOCs during the morning rush-hour
periods. Each member employed different modes of transportation: apart from a
short walk, EP and MS used their own cars for the entire commute (approximately 1
hour, 6 samples); BK used his car for approximately 20% of his commutes and the
subway for the remainder (30 to 45 minutes, 2 samples); and RB and RC used their
cars for approximately 15% of their commutes, the train for approximately 70% and
walking or the subway for the remainder (1.5 hours, 3 samples).

Only 20 to 30 different VOCs were detected in each of the 1 1 morning rush-
hour samples (Table 8). The low-boiling alkane concentrations ranged to 160 |ig/m^
(pentane), the aromatics to 160 ^ig/m^ (toluene) and the chlorinated aliphatics to 310
|ig/m' (chloromethane). No unusual odours were detected during any of the
commutes.

From an empirical qualitative perspective, the cleanest commutes appeared to
belong to RB and RC, followed by BK, EP and finally MS. The 100 and 310 [ig/m^
chloromethane concentrations detected In the 2 samples acquired by the commuters
who used the train for a large percentage of their time may have been due to
outgassing from solvents used in the trains, the upholstery, etc. or more likely, both
people had to wait for the trains in a smoke-filled area (cigarette smoke is a major
source of chloromethane). It appears that MS had a dirtier car (elevated
concentrations of aliphatics and aromatics) than EP (although a similar type of VOC
profile was obtained for EP's commute, the aliphatic and aromatic concentrations
were somewhat lower whereas the chlorinated compound concentrations had
increased).

12

The Afternoon Rush-Hour:

The same staff members participated in the afternoon program and once
again, the data (Table 9) indicated that the participants who used their own cars
(EP and MS) had the highest exposure to VOCs and the participants who used
public transit (BK and RC) had the least. The overall VOC concentrations were
much less than the morning rush-hour commutes and usually only 20 to 30 of the
45 targeted compounds were detected in the samples. Apart from the 2 elevated
concentrations of 465 |ig/m^ (chloromethane; possibly cigarette smoke or dry
cleaning) and 105 [iglm^ (butane; possibly vehicular emissions), all concentrations
were less than 50 ^g/m^

Intercomparison of the Morning and Afternoon Commutes:

As noted in Table 1 1 and Figure 8, exposures to higher VOC concentrations
occurred during the morning commutes. Not considering the afternoon outlier
chloromethane concentration of 465 ^ig/m^ and only considering the 22 short-listed
VOCs, the total average concentrations for the afternoon and morning periods were
approximately 1100 and 2800 ^ig/m^ respectively. On this somewhat limited basis,
these data suggest that the morning commuters were exposed to almost 3 times as
much VOCs as the afternoon commuters.

It was thought that this disparity was due to better atmospheric dispersion
conditions normally present in the afternoons and the more broad-banded or
extended afternoon rush-hour period. In Toronto, the morning rush-hour usually
extends from 6:30 to 8:30am whereas during the afternoons, the rush-hour runs
from 4 to 7pm (2 versus 3 hours).

These observations are backed by similar assessments undertaken by several
other researchers. For example, a recent paper by C.C. Chan and J.D. Spengler of
the Harvard School of Medical Health (Boston)^ contained the following observations:

1 ) Higher traffic densities and the lower atmospheric dispersion rates in urban
street canyons are believed to be the main causes of measuring greater VOC
exposure in urban airsheds.

2) Commuters had the highest VOC exposures driving private cars and the
lowest exposures riding subways (in Boston).

2) No significant difference in in-vehicle VOC concentrations was found
between new and old cars, and between domestic and imported cars.

13

From the data acquired during the commutes, the benzene, toluene and
xylene concentrations normalized to ethylbenzene are as follows:

Junction Triangle' Afternoon Morning

Benzene/ethylbenzene 2.8 2.6 4.7

Toluene/ethylbenzene 7.4 5.4 8.6

Xylenes/ethylbenzene 4.3 4.0 4.2

T. Dann' analyses of 105 samples acquired at the Junction Triangle between August 1984 and March 1986.

From this analysis, the commuting aromatic profiles appear to be similar to
the long-term air quality aromatic profile of the Junction Triangle area. Major sources
of benzene are antiknock gasolines, rubber cements, solvents, paint removers, and
fumigants; major sources of toluene are adhesive solvents, gasolines, resins, oils,
and phenols; and major sources of xylenes are solvents, gasoline, protective
coatings, lacquers and rubber cements. All are characteristic of vehicular emissions,
in-vehicular environments and the solvent, paint and adhesive industries of the
Junction Triangle.

The Noon-Hour Walk-Abouts:

During the PEP study, eight 1-hour VOC ambient air samples were collected
by staff members as they walked-about in the downtown area of Toronto. The route
taken was a figure-eight pattern around the outdoor sampler site (Section 2.2.2) at
the College Street police station.

Upon examining the acquired VOC data (Table 10), very low concentrations
were measured and only half of the 45 targeted compounds were detected. The
maximum individual concentration was only 21 ^lg/m^

As a note of interest, 21 |ig/m^ of 1,2-dichlorobenzene was detected during
week 6 of this study and a trace amount was also reported in the outdoor ambient
samples acquired at the police station (Section 2.2.2, Table 4). The more common
sources of this contaminant are metal polishes, fumigants and insecticides. It
appears that the police kept the alcove area, where the outdoor sampler was
located and where the noon-hour participants stopped to have a rest during their
walk-abouts, very clean.

14

The 4 Special Samples: (Table 3)

- The 1" special sample was exposed for almost 2 hours at a barbecue.
Although high VOC concentrations were expected, the measured concentrations
were only indicative of background levels routinely detected in other urban airsheds
of Ontario.

- The 2"^ and 3"^ samples were exposed during a meeting. The samples were
of 1 hour or less and the measured concentrations were again very low. Although
there had been a considerable amount of cigarette smoke present, the measured
concentrations did not highlight this source (the maximum chloromethane, benzene
and toluene concentrations were only 6.5, 6 and 14 ^ig/m^ respectively).

- The 4"" sample was a 16-hour sample acquired during commuting to and
from work and overnight. Somewhat higher concentrations for the 45 selected VOCs
were recorded but the relative contributions from major sources (i.e. the home,
automobile and commuter train) could not be determined. The dominant VOCs
measured in this sample were butane (59 |ig/m^), pentane (35 |ig/m^), toluene (73
^ig/m^) and xylenes (35 ^ig/m^).

2.2.5 Comparisons with other Ministry Studies:

(For a detailed listing of the results from these studies, please see Appendix C.)

The MOE 1990 Toronto Toxics and Benzene Studies:

As mentioned in the Introduction and as noted in the introductory paragraphs
of the two memoranda pertaining to the Spring and Summer Toronto Toxics studies
conducted by ARB, these studies were run concurrent with another monitoring
program undertaken by the firm of RWDI. RWDI was retained by the Environmental
Protection Office of the City of Toronto to perform an environmental assessment of
gaseous toxic compounds in the downtown core area of Toronto.

For ease of comparison, the average concentrations for the low-boiling
alkanes and aromatics measured during the ARB Toronto Toxics and PEP studies
are presented below. The Toronto Toxic samples were ambient samples collected
along the busy traffic routes in downtown Toronto during the morning, noon and
afternoon rush-hour periods. They were one-hour inhalation zone samples and staff
members walked in figure eight patterns in the vicinity of the Royal Ontario Museum
and Old City Hall.

15

Volatile Organic Compounds
(Average Concentrations)

Toronto Toxics

PEP

Spring

Summer 1

Noon-Hour

Downtown

Residential

Number of samples

(17)

(12)

(8)

(16)

(7)

Propane

24

20

10

4

1

Chloromethane

4

<4

1

1

nd

Butane

20

11

5

5

6

Pentane

13

14

7

5

4

Benzene

12

10

4

3

2

Toluene

16"

22

9

8"

7

Tot. Xylenes

14

10

4

5

4

Ethylbenzene

3

3

2

1

1

Benz^Ethbenz.

4

3.3

2

3

2

ToluVEthbenz.

5.3

7.3

4.5

8

7

Xyls./Ethbenz.

4.7

3.3

2

5

4

Concentration units are ng/m'

Not including an outlier concentration of 221 ng/m'
" Not Including an outlier concentration of 520 ng/m'

As additional references, gasoline vapour and liquid phase hydrocarbon
compositions (M. Round®) and the average VOC concentrations acquired during the
ARB 1989 Benzene Study are summarized below. For the Benzene study, the one-
hour ambient samples were acquired along relatively busy streets in downtown
Toronto and the retail gas station samples were acquired during refueling of private
automobiles (inhalation zone samples with exposures of 1 to 3 minutes).

Liquid

Vapour

V/L Phase

Benzene

Study

(%)

(%)

Ratio

Ambient

Retail St'n

Number of samples

(12)

(7)

Propane

0.1

5.2

52

30

5,000

Butane

6.2

41.1

6.6

23

108,500

Pentane

4.0

5.6

1.4

13

30,000

Benzene

2.1

0.9

0.43

9

4,300

Toluene

10.4

0.8

0.08

22

3,500

Xylenes

4.9

0.1

0.02

15

1.000

Ethylbenzene

1.2

0.4

0.33

4

250

Benzene/Ethylbenzene

1.8

2.2

2.3

17.2

Toluene/Ethylbenzene

8.7

2.0

5.5

14

Xylenes/Ethylbenzene

4.1

0.3

3.8

4

16

From the data set above, the following may be stated:

0 The ambient walk-about samples of the Toronto Toxics and Benzene
studies are almost identical (in both the way they were carried out and
results). These samples were taken along the busy traffic arteries in
downtown Toronto and the results infer that vehicles are a major
source of VOCs in the area.

0 The normalization ratios for benzene, toluene and xylenes to
ethylbenzene for all ambient measurements (the PEP, Toronto Toxics
and the Benzene studies) appear to be fairly consistent: the first ratio
being between 2 and 4; the second being between 4.5 and 8 and; the
third being between 2 and 5. As anticipated, these ratios are not
similar to those reported by M. Round for pure gasoline vapour phase
composition. It is generally accepted that although the vehicle is the
major ubiquitous source of VOCs in urban airsheds, the specific source
is not just gasoline vapour emissions but rather a composite of many
point source emissions from the vehicle (for example, tailpipes, engine
compartments, greases and oils, hot soaks, etc.). The chromatographic
VOC profiles are slightly shifted towards the higher boilers, but the
major VOCs were the same in all samples, namely; propane, butane
and toluene which make up almost 50% of the vapour phase gasoline.

0 The PEP ambient VOC concentration results appear to be only half of
those reported for the other studies. The PEP samples were long-term
(12-hour) general air quality samples as compared to the short-term (1
to 2 hours) high impact, source specific samples (i.e. msh-hour, gas
stations, etc.) acquired during the other studies.

0 It is generally accepted that the greatest personal exposure to VOCs
occurs during refueling at gas stations. This point was very obvious
from the data of the 1989 Benzene study and was also stressed at a
gasoline exposure workshop planning group discussion^" held in the fall
of 1990 in Annapolis, Maryland. (The Exxon Company had conducted a
similar study in 1983 to assess gasoline exposures during self-service
refueling. From 134 samples, the total hydrocarbon average exposure
was 21 ppm (parts per million) with an average exposure time of 2.4
minutes during refueling and an average of 10.5 gallons being pumped.
Ubiquitious, background ambient total hydrocarbon concentrations
normally range from 1 .5 to 3 ppm.)

17

3.0 Conclusions:

The PEP study represents an initial step to assess, in a more comprehensive
manner, the exposure of individuals in the Toronto area to various VOCs (some of
which, such as benzene, are toxic). The VOC data set is very small and therefore
the following conclusions are to be regarded as only tentative. As a result of these
initial findings, the need for further work in this area is strongly recommended.

0 In general, all measured VOCs were low and none of the applicable Ministry
Air Quality Standards, Criteria or Guidelines were exceeded during this study.

0 Analyses of all field samples acquired during this study indicated VOC profiles
and concentrations similar to other work that the Ministry and other research
groups have done within these same microenvironments in which people must
work and live.

0 Since people usually spend in excess of 90% of their time indoors, air quality
of this microenvironment must be explored in greater detail if any personal
exposure assessments are to be carried out.

0 Highly vanable indoor air quality was noted during this study and
Investigations as to causality have to be carefully planned. Minimal
requirements would be concurrent indoor and adjacent outdoor air sampling
programs ...something that was not followed during this study. From the PEP
data set, the indoor air quality appeared to be as much as 2 to 5 times worse
than the outdoor air quality.

0 With respect to outdoor air quality, higher VOC concentrations were noted in
the downtown area due to lower atmospheric dispersion rates and the higher
traffic volumes. This was especially evident in samples collected overnight
and during the morning rush-hour (commuting) periods.

0 VOC concentrations measured during the morning commutes were almost 3
times higher than the afternoon commutes.

0 Commuting in personal vehicles resulted in greater exposures to VOCs than
commuting by public transport.

18

4.0 References:

1 . P.R.W. Kendall. Medical Officer of Health: Chemicals and Toxins, Report #3\
City of Toronto Department of Public Health, in a Series of 10 Reports:
released - September 1990.

2. W.R. Ott: Human Exposure to Environmental Pollutants; 81" Annual Meeting
of Air Pollution Control Assoc'n, June 1988.

3. B.A. Tichenor and M.A. Mason: Organic Emissions from Consumer Products
and Building Materials to the Indoor Environment; JAPCA 38 264-268 (1988)

4. R.W. Bell et al.: Comparison of Ambient Air Quality Surveys in the Junction
Triangle Area and Downtown Metropolitan Toronto; Air Resources Branch
Publication; ARB-099-85-ARSP

5. T. Dann et al.: Benzene in the Ambient Air of Canadian Urban Areas -
Sources and Exposures; PMD File - 4024 - 6; Pollution Measurement
Division, Environment Canada.

6. J.J. Shah and H.B. Singh: Distribution of Volatile Organic Chemicals in Out
door and Indoor Air; Environmental Science and Technology (Feature
Article), Vol 22, No. 12, pps 1381-1388 (1988).

7. H.Greim and H. Sterzl et al.: Indoor Air Pollution: a Review; Toxicological
and Environmental Chemistry, Vol 23, pp 191-206; Excerpts from a special
report to the German Council of Environmental Advisors (1987).

8. CO. Chan and J.D. Spongier: Commuter Exposures to Volatile Organic
Compounds; Proceedings of the 5*" International Conference on Indoor Air
Quality and Climate, Toronto, August 1990.

9. M. Round. N. Anderson. D. Brown et al.: Evaluation of the Health Effects
From Exposure to Gasoline and Gasoline Vapours; Final Report to NESCAUM
(Northeast States for Coordinated Air Use Management) Air Toxics
Committee, August 1989.

10. ENVIRON Corporation: Summary Report on Individual and Population
Exposures to Gasoline ; Gasoline Exposure Worl<shop Planning Group,
Exxon (unpublished data) pp 29, (1990).

19

APPENDIX A
(The Lab Work)

Method Detection and Method Quantization Limits 21

The Shortened VOC Target List 22

20

Method Detection & Quantitation Levels (MOLs & MQLs) - July '90

For 12 litre samples

HDL

HOL

ug/m**3

ug/m**3

1 Propane

0.3

< T

<

1.3

2 Chloromethane

0.7

< T

<

3.6

3 Chloroethene

0.5

< T

<

2.3

4 1,3-Butadiene

0.9

< T

<

4.7

5 Butane

0.4

< T

<

1.8

6 Acrylonitrile

0.9

< T

<

4.6

7 Pentane

0.4

< T

<

2.1

8 Isoprene

0.9

< 1

<

4.7

9 1,1-Oi chloroethene

0.4

< 1

<

2.1

10 Di chloromethane

1.3

< 1

<

6.3

11 Hexane

0.3

< 1

<

1.7

12 Tri chloromethane

1.8

< 1

<

9.0

13 1,2-Dichloroethane

0.2

< 1

<

1.0

14 1,1,1-Trichloroethane

4.6

< "

<

22.9

15 Benzene

0.3

<

<

1.5

16 Tetrachloromethane

5.1

< '

<

25.6

17 Cyclohexane

0.3

<

1.3

18 1,2-Dichloropropane

0.4

<

1.9

19 Trichloroethene

1.3

<

6.4

20 Heptane

0.7

<

3.4

21 1,1,2-Trichloroethane

0.6

<

3.0

22 Toluene

0.6

r <

3.0

23 1,2-Dibromoethane

1.6

r <

8.0

24 Octane

0.5

r <

2.4

25 Tetrachloroethene

1.4

r <

7.1

26 Chlorotjenzene

0.7

r <

3.7

27 Ethylbenzene

0.3

r <

1.6

28 m- Xylene

0.9

T <

4.3

29 p- Xylene

0.4

T <

2.0

total m,p-Xylenes

0.9

T <

4.3

30 Styrene

1.0

T <

4.8

31 1,1,2,2-Tetrachloroethane

1.5

T <

7.4

32 o-Xylene

0.8

T <

4.0

33 Nonane

1.0

T <

4.9

34 1,3,5-Trimethylbenzene

0.3

T <

1.2

35 1,2,4-Trimethylbenzene

0.7

T <

3.4

36 1,3-Dichlorobenzene

1.1

T <

5.6

37 Decane

1.8

T <

9.0

38 1,4-Dichlorobenzene

0.3

T <

1.7

39 1,2-Dichlorobenzene

1.4

T <

6.9

40 1,2-Di ethylbenzene

0.7

<

T <

3.3

41 Undecane

1.5

<

T <

7.3

42 1,2,4-Trichlorobenzene

0.6

<

T <

2.9

43 Naphthalene **

0.0

<

T <

0.0

44 Dodecane

1.0

<

T <

5.1

45 Tridecane

0.7

<

T <

3.6

** - no HDL nor MQL available for this compound

21

c e

a a
II

E E
66

S ^

22

^f 1

IE
•S.S

11

8 «

■S - •§

II!

3 3
11

P
- E

1 I'e'6'1 S-o 1

o
^■3

^5

^1

3 S-

I I

8- I

S a.

11

J3 -.■

i I I

I t

>> .5

C i >5 C C

O H

rt fO

I ^

1^

1 i 1 1

S 5 g

3 ^

24

APPENDIX B
(The Field Work and Results)

Representative Chromatograms of PEP - VOC Profiles / Fingerprints

Figure 1: The Indoor and Outdoor Samples 26

Figure 2: The Commuting and Noon-Hour Samples 27

The Indoor Environments: Office and Home

Table 1: Indoor Air at 880 Bay Street (Office) 28

Table 2: Indoor Air Comparisons (Office) 30

Figure 3: Indoor Air Comparisons 31

Table 3: Indoor Air (Home) 32

The Outdoor Environments: Downtown and Residential

Table 4: College Street VOC Results (Downtown) 34

Table 5: Garnock Avenue VOC Results (Residential) 36

Table 6: Ambient Concentrations (Diurnal Variations) 38

Figure 4: Diurnal Variations 39

Figure 5: Nighttime Comparison (Residential & Downtown) 40

Outdoor Versus Indoor Air Quality

Table 7: Outdoor Versus Indoor Air Quality 41

Figure 6: Outdoor Versus Indoor Air Quality 42

Figure 7: Time Budget Analyses (Ott) 43

The Commuting and Noon-Hour Sampling Programs

Table 8: The Morning Commuter Runs 44

Table 9: The Afternoon Commuter Runs 46

Table 10: The Noon-Hour Walk-Abouts 48

Table 11: The Commuting and Noon-Hour Intercomparisons 50

Figure 8: The Commuting and Noon-Hour Intercomparisons 51

25

Figure 1
Representative Chromatographic VOC Fingerprints

The Outdoor Environments

I"

i- •£-» :-:*:»t ••i.jt -

Downtown

Residential

•r-r..?.'

m=^

^p.

i^^

r •■"'

^''■■:

The Indoor Environments

Home

Office

m

26

Figure 2
Representative Chromatographic VOC Fingerprints

The Commuting and Noon-Hour Programmes

Morning Commute Noon-Hour Walk-About

; - „„. i _ ...

- — * "' ^" — ~' ■ "

••"> ^ ;.;;. * ' "*

— — — y.ti' V ■ ...

W^f":.u.

JT^sv.... ••" ... ^^

^=5^^

/»,tV.. — ■'••" i . ...

-rrr-* "■'"

-.*'.«■.. . ..

:t.«i7

Afternoon Commute

g^Jih

27

Table 1

in o- eo fM
^ n! ^" ^'

l-r^«NJs»>- r- r- t- t-

►- O- )- o-

V ^- )'>

00 ^
(NJ IM

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5 s.

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28

Table 1 ctd.

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O ^ •-' »^

o ^» o o 0>
K> o r^ u^ eo

t- t- »• o I-
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29

Table 2

Personal Exposure Pilot Study - Indoor Air Comparisons
(At 880 Bay Street; Regular Office Hours)

June & July
Sainples

August
Sairples

Avg.

Avg.

1 PROPANE

2 CHLOROHETHANE

3 BUTANE

4 PENTANE

5 1,1-DICHLOROETHENE

6 OICHLOROHETHANE

7 HEXANE

8 TR I CHLOROHETHANE

9 1,2-DICHLOROETHANE

10 1,1,1-TRICHLOROETHANE

11 BENZENE

12 TETRACHLOROMETHANE

13 TRICHLOROETHENE

14 TOLUENE

15 TETRACHLOROETHENE

16 ETHYLBENZENE

17 TOTAL M,P-XYLENES

18 STYRENE

19 NONANE

20 1,3,5-TRIHETHYLBENZENE

21 DECANE

22 1,2-DICHLOROBENZENE

9.8

2.3

6.1

0.6

18.0

2.9

16.7

3.9

8.7

1.2

1.9

1.1

22.2

2.1

3.8

36.8

12.2

14.2

1.6

23.5

28.3

3.1

44.3

5.5

25.1

2.6

7.0

1.0

22.9

3.3

5.6

0.4

9,4

0.6

15.1

2.6

17.9

1.5

10.9

2.0

All concentration units are ug/m3
C:\SYHPH0NY\PEP\1NWKC0M.WRI

30

Figure 3

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33

Table 4

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37

Table 6

PEPS 1990 VOC Results - Ambient Concentrations
(Diurnal Variations)

Downtown Sanples

Residential Samples

Sample:

Date sampled:

Night-time Day-time
Averages Averages

Night-time Day-time
Averages Averages

1 PROPANE

2 CHLOROMETHANE

3 BUTANE

4 PENTANE

5 1,1-DICHLOROETHENE

6 D I CHLOROMETHANE

7 HEXANE

8 TRICHLOROHETHANE

9 1,2-DICHLOROETHANE

10 1,1,1-TRICHLOROETHANE

11 BENZENE

12 TETRACHLOROHETHANE

13 TRICHLOROETHENE
U TOLUENE

15 TETRACHLOROETHENE

16 ETHYLBENZENE

17 TOTAL M,P-XYLENES

18 STYRENE

19 NONANE

20 1,3,5-TRIHETHYLBENZENE

21 DECANE

22 1,2-DICHLOROBENZENE

4.9

3.9

0.8

1.6

1.3

0.2

5.2

5.1

5.0

6.0

4.6

5.6

4.1

4.6

1.9

1.9

0.5

0.4

4.7

4.1
1.7

2.0

5.2

2.4

3.3
0.3

2.0

2.1
2.8

7.7

8.3

7.0

6.2

1.2

2.6

1.2

1.6

1.0

1.0

3.8

5.4

3.9

0.5

0.4

0.5

1.1

0.3

0.2

0.2

0.2

0.2

Number of VOCs Detected

13

13

All concentration units are ug/m3
C:\SYMPH0NY\PEP\0UTSUM.UR1

38

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40

Table 7

PEPS 1990 VOC Results
Outdoor versus Indoor Air Quality

Outdoor

Indoor

Downtown Residential Office Dcmestic

NLinber of Sanples

(16)

(7)

(8)

(4)

1 PROPANE

4.4

1.2

6.0

2.2

2 CHLOROHETHANE

0.8

0.0

3.7

5.5

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5.1

5.6

10.4

23.9

4 PENTANE

5.1

4.A

10.3

19.6

5 1,1-DICHLOROETHENE

1.9

0.4

5.0

5.4

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0.0

0.0

1.5

14.1

7 HEXANE

4. A

3.8

12.1

12.0

8 TRICHLOROHETHANE

1.7

0.0

0.0

12.0

9 1,2-DICHLOROETHANE

0.0

0.0

3.8

3.6

10 1,1,1-TRICHLOROETHANE

0.0

0.0

24.5

15.8

11 BENZENE

2.9

2.0

7.9

9.6

12 TETRACHLOROMETHANE

0.0

1.9

11.8

13.5

13 TRICHLOROETHENE

0.2

0.0

15.7

3.8

1« TOLUENE

** 8.0

6.5

24.9

58.0

15 TETRACHLOROETHENE

0.6

1.6

13.9

5.8

16 ETHYLBENZENE

1.4

1.0

4.0

7.4

17 TOTAL M,P-XYLENES

4.6

3.5

12.9

25.5

18 STYRENE

0.4

0.0

3.0

8.4

19 NONANE

0.8

0.2

5.0

10.1

20 1,3,5-TRIMETHYLBENZENE

0.1

0.2

8.9

8.1

21 OECANE

0.2

0.0

9.7

8.3

22 1,2-DICHLOROBENZENE

0.0

0.0

6.4

11.2

Concentration units are ug/m3
** The high downtown toluene outlier concentration (520 ug/m3) was
retnoved from the outdoor data set.

The above data were analyzed from samples exposed for 8 to 12-hours.
C:\SYMPHONY\PEP\OUTINSU.WRI

41

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49

Table 11

PEPS 1990 VOC Results

Short-Term High Impact Periods
(The Noon-Hour Walk-Abouts and the Afternoon/Horning Commutes)

Afternoon Horning

HiSTber of Samples (8) (8) (11)

1 PROPANE

9.9

6.0

15.6

2 CHLOROHETHANE

1.4

7.7

57.1

3 BUTANE

4.5

27.8

21.2

4 PENTANE

6.5

12.6

28.9

5 1,1-DICHLOROETHENE

1.7

3.6

4.3

6 OICHLOROMETHANE

0.0

0.0

1.2

7 HEXANE

3.9

6.4

17.3

8 TR I CHLOROHETHANE

0.0

0.0

0.0

9 1,2-DICHLOROETHANE

0.0

0.0

0.0

10 1,1,1-TRlCHLOROETHANE

0.0

0.0

1.0

11 BENZENE

4.4

7.0

23.5

12 TETRACHLOROHETHANE

0.0

0.0

19.7

13 TRICHLOROETHENE

0.0

0.0

2.9

U TOLUENE

8.9

14.7

43.2

15 TETRACHLOROETHENE

0.0

3.9

9.8

16 ETHYLBENZENE

1.7

2.7

5.0

17 TOTAL M,P-XYLENES

4.1

10.8

20.8

18 STYRENE

0.0

1.1

3.3

19 NONANE

0.4

3.3

3.5

20 1,3,5-TRIMETHYLBENZEME

0.0

0.5

0.7

21 DECANE

0.0

0.6

1.4

22 1,2-DICHLOROBENZENE

0.0

5.7

0.7

Concentration units are ug/m3

The above data were acquired from samples exposed for 1 to 2-hours.

C:\SYHPHONY\PEP\HGHIMPS.WRI

50

Figure 8

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APPENDIX C
(Other Ministry Work)

Excerpts from:

The 1989 Benzene Study 53

The Toronto Toxics Spring Study 55

The Toronto Toxics Summer Study 61

52

Laboratory Report : Benzene Study

(Internal Report at ARB, October 1989)
- Prepared by Mr. M.A. Sage -

Summary:

1. Samples were collected while walking along relatively busy traffic
arteries in downtown Toronto. It was hoped that the resulting benzene
and other volatile organic concentrations would be indicative of
exposures representative of those a pedestrian might experience in this
area. Twelve such samples were collected during the June -
September 1989 period.

2. Samples were also collected, at nose level, while refuelling over 1 to 3
minute periods at gasoline stations. Seven such samples were
collected during June - August 1989.

3. For the samples collected while walking downtown, benzene
concentrations ranged from 3 to 24 jig/m^ with an arithmetic average of
9.4 ^g/ml

4. For the gasoline station refuelling samples, the average benzene
concentration during the 1 to 3 minute periods was 4324 |ig/m^ with a
range of 674 to 8759 ^lg/m^

53

June

7

June

14

June

23

June

28

July

25

Aug

1

Aug

4

Aug

8

Aug

16

Aug

18

Aug

28

The Volatile Organic Compounds - 1989 Benzene Study

The Walking Samples
Benz. To!. Etben. Xyl. Cg C4

24 71 13 61 42 100 63

4 18 28 17 9

8 39 100 39 22

2 8 16 16 7
4 17 65 24 14

14 6 17 17 10

3 14 32 21 11
17 7 5 3
1 5 11 8 4
1 2 nd 3 1

nd nd 21 15 5

Sept 1 4 10 1 6 24 6 4

The Gas Station Samples

Benz. Tol. Etben. Xyl. C3 C4

11

25

21

50

9

16

9

32

10

12

9

22

4

9

6

8

3

3

June

14

1475

1049

54

211

1693

30308

829C

June

14

4572

2755

298

1341

7482

141409

na

June

23

8759

8643

551

2297

8906

247465

6106^

June

28

869

1672

77

344

1753

41190

1281(

July

17

6543

2254

116

660

2330

55537

241 0(

Aug

2

674

586

na

96

1912

13865

244C

Aug

8

7378

7256

379

1868

10905

228434

7075v

Concentration Units are iig/m'

Benz. - Benzene, Tol. - Toluene, Etben. - Ethylbenzene, Xyl. - Total Xylenes

C3 - Propane, C^ - Butane, C5 - Pentane

na - not available, nd - not detected

C;\WP50\SURVEYS\PEP\SAGEBEN.DOC

54

Highlights of the Spring Toronto Toxics Study of 1990: Excerpts from the pertinent
memorandum.

MEMORANDUM

May 28, 1989
To: Maris Lusis, Manager

Atmospheric Research and Special Programmes Section
Air Resources Branch

From: Ronald W. Bell, Co-ordinator

Field Support and Methods Development Group
Monitoring and Instrumentation Development Unit
Atmospheric Research and Special Programmes Section
Air Resources Branch

Subject: The Toronto Toxics Spring Study - 1990

The Environmental Protection Office (EPO) of the Department of Health for
the City of Toronto has been charged with conducting an environmental
assessment of gaseous toxic compounds in the downtown core area of Toronto.
The firm of Rowan, Williams, Davies & Irwin (RWDI) was retained by EPO to
undertake this assessment and as a component phase, a sp>edal air monitoring
programme for metals, volatile and semi-volatile organics commenced on March
27^, 1990. Their field programme consisted of collecting 48 and 24-hour samples at
3 different sites in downtown Toronto; namely at 206 Major Street (a residential
neighbourhood), at Queen and Bay Streets (Old City Hall) and at Bloor and
Avenue Roads (the ROM - Royal Ontario Museum).

Supplemental to this programme, the Air Resources Branch conducted a
high-impact study during these same times at the latter 2 sites. This study
consisted of VOC sampling during the morning, noon and afternoon rush-hour
periods on March 27^ and 28*. In total, 17 field VOC samples were collected and
later analyzed by the GC/FID/MS system at ARB. The samples were acquired
within the "inhalation zone" (i.e. at nose level) through the use of personal pumps
(Gilian) as staff members walked "figure eight" patterns in the vicinity of the
RWDI sampler units.

Results and Discussion

55

In summary, similar VOC signatures were recorded at both sampling

sites the identity and average concentrations of the selected (targeted)

VOCs were very similar and analyses of the duplicate samples yielded

almost identical results.

Vehicular emissions were highlighted by the pronounced variability in the
alkane and aromatic concentrations. Furthermore, very little variance was noted in
the chlorinated aliphatic concentrations throughout the entire study.

From an air quality perspective, none of the applicable Ministry Guidelines,
Criteria or Standards were exceeded for any of the detected VOCs and the
concentrations were as expected for a heavy industrialized urban airshed.

56

THE BAY STREET / QUEEN STREET "WALK-ABOUP'

57

THE AVENUE ROAD / BLOOR STREET "WALK-ABOUT'

Toronto Toxics Study - 1990

Date collected:

03/27/90

Sairpling period:

0805

-0905

0805

0905

1200

1300

1200

1300

1600

1700

1600-1700

Location:

City

Hall

ROM

City

Hall

ROM

City

Hall

ROM

D

D

D

D

0

1 PROPANE

9

35

9

12

14

26

6

10

11

16

40

2 CHLOROMETHAME

i,

6

2

6

3

4

3

4

2

2

4

3 CHLOROETHENE

4 1,3-BUTADIENE

5 BUTANE

8

20

12

12

11

14

8

12

13

15

28

6 PENTANE

5

18

7

9

7

11

5

6

7

11

18

7 ACRYLONITRILE

8 1.1-OICHLOROETHENE

9 DICHLOROMETHANE

2

10 HEXANE

2

8

3

4

3

5

3

3

4

6

8

11 TRICHLORQMETHANE

12 1,2-OICHLOfiO£THANE

13 1,1,1-TRICHLOftOETHANE

5

4

5

3

5

2

3

8

3

5

U BENZENE

5

17

8

10

6

9

4

6

7

12

19

15 TETRACHLOROMETHANE

19

9

8

12

10

12

16 CYCLOHEXANE

17 1,2-DICHLC«C5PROPANE

18 TR I CHLOROETHENE

2

19 HEPTANE

3

2

20 1,1,2-TRICHLOROeTHANE

21 TOLUENE

7

24

11

14

8

13

6

8

10

11

27

22 1,2-DIBROMOETHANE

23 OCTANE

24 TETRACHLOfiOETHENE

4

13

10

14

5

8

11

15

6

4

25 CHL0R08ENZENE

26 ETHYLBENZENE

5

2

3

1

5

27 TOTAL XYLENES

5

20

10

12

7

11

5

7

8

5

22

28 STYRENE

29 1,1,2,2-TETRACHLORO£THA«E

30 NONANE

31 1.3,5-TRIKETHYLBENZEIIE

3

2

32 1,2,4-TRIMETHYLBENZEME

5

2

3

4

33 DECANE

34 1.3-DICHL0R08ENZEHE

35 1,4-DICHLOROBENZENE

36 1,2-DICHLOROBENZENE

37 1,2-DIETHYLBENZENE

38 UNDECANE

39 1.2,4-TRICHLOROBENZEIC

40 NAPHTHALENE

41 OOOECANE

42 TRIOECANE

59

Toronto Toxics Study - 1990

Date collected:

03/28/90

Sanpling period:

0810-0910

0810-0910

1200-1300

1600-1700

1600-1700

Averages

Location:

City

Hall

D

32

ROM

ROM

City Hall

ROM

City Hall

ROM

1 PROPAKE

34

33

35

38

50

24.0

24.4

2 CHLOKMETHANE

5

3

10

2

4

3

3.7

4.2

3 CHLOROETHENE

4 1,3-BU7ADIENE

5 BUTANE

45

32

38

31

17

24

19.5

20.5

6 PEMTANE

23

22

22

17

15

17

13.2

12.5

7 ACRYLCWITRILE

8 1,1-DICHLOROETHENE

9 OICHLOROMETHANE

i»

35

5

9.2

0.8

10 HEXAME

10

10

11

9

7

8

6.1

6.4

11 TRICHLOROHETHAME

12 1,2-DICHLOROETHAME

4

3

0.4

0.4

13 1,1,1-TRICHLOROETHANE

7

7

6

11

9

6

5.2

5.3

U BENZEKE

20

19

23

U

13

18

11.9

12.7

15 TETRACHLOROHETHANE

15

13

20

9

10

12

8.7

8.8

16 CYCLOHEXANE

17 1,2-DICHLOROPROPANE

18 TRICHLOROETHENE

5

2

5

5

0.7

1.4

19 HEPTANE

3

3

3

3

2

3

1.2

1.4

20 1,1,2-TRICHLOROETHANE

21 TOLUENE

29

28

33

221

18

25

16.3

43.3

22 1,2-DI5R0MOETHANE

23 OCTANE

24 TETRACHLOROETHEME

4

4

8

5

4

5.3

8.3

25 CHLOROeENZENE

26 ETHYLBENZENE

5

5

6

4

4

5

2.1

3.3

27 TOTAL XYLENES

24

23

27

19

16

20

13.2

15.3

28 STYRENE

29 1,1,2,2-TETRACHLOROETHANE

30 NONANE

31 1,3,5-TRIMETHYLBEN2ENE

3

3

3

2

0.9

0.9

32 1,2,4-TRlMETHYLBENZENE

6

5

6

4

4

5

2.5

2.6

33 OECANE

3A 1,3-DICHLOROBENZENE

35 1,4-0ICHLOROBEN2ENE

36 1,2-OICHLOROBENZENE

37 1,2-OIETHYLBENZENE

38 UNDECAfcE

39 1,2,4-TRICHLOR08ENZEME

AO NAPHTHALENE

41 DOOECAWE

42 TRIDECANE

60

Highlights of the Summer Toronto Toxics Study of 1990: Excerpts from the pertinent
memorandum.

MEMORANDUM

September 4, 1990
TO: Maris Lusis, Manager

ARSP Section
Air Resources Branch
Ministiy of the Environment

FROM: Ronald Bell, Co-ordinator

FS & MD Group

ARSP Section, Air Resources Branch
Ministry of the Environment

SUBJECT: The Toronto Toxics Summer Study - 1990

The Environmental Protection Office (EPO) of the Department of Health for
the City of Toronto was charged with conducting an environmental assessment of
gaseous toxic compounds in tiKe downtown core area of Toronto. This assessment
consisted generally of three phases to be executed by the private consultant firm of
Rowan, Williams, Davies «Sc Irwin (RWDI).

The first phase required reviewing existing ambient air quality regulations
and guidelines for air toxics that exist in other jurisdictions in North America, and
reviewing other monitoring surveys for air toxics in the City of Toronto with the
objective of developing appropriate protocols for the second phase which was the
actiial sampling of ambient air. The third phase, involves a risk exposure
assessment based on the monitoring results obtained during the second phase.

With respect to the second phase, the Air Resources Branch conducted a
VOC study in the downtown core area of Toronto concurrent with the field
operations of RWDI during the spring (March) of 1990. The results of this study
were presented in a May 28 memorandum addressed to you entitied "The Toronto
Toxics Spring Study - 1990". As the next step of the second phase, another ambient
monitoring program was undertaken by RWDI on June 12 and 13* .

As mentioned in the May memorandum, RWDI's field program consisted of
collecting 48- and 24-hour ambient air samples at three different sites in the
downtown Toronto core; namely at 206 Major Street (an urban residential
neighbourhood), at Queen and Bay Sti-eets (Old City Hall) and at Bloor and
Avenue Roads (the ROM - Royal Ontario Museum) and analyzing these samples
for metals, volatile and semi-volatile organic compounds.

Concurrent vn\h the RWDI's June program, tiie Air Resources Branch
conducted its own VOC study at the latter two sites. As with the March study,
one-hour VCXT samples were acquired during the morning, noon and afternoon

61

rush-hour periods. In total, 12 ambient air Scimples were acquired within the
inhalation zone through the use of personal pumps as staff members walked figure
eight patterns in the vidnity of the RWDI sampler units at the ROM and Old City
Hall.

Results and Discussion

SUMMARY

From analyses of the 12 ambient air VOC samples collected during the Jime
study, vehicular emissions were deemed to be the major source of concern in this
downtown area of Toronto. From an air quality perspective, none of the applicable
Ministry Guidelines, Criteria or Standards were exceeded for any of the detected
VOCs and the concentrations were at expected levels for an urban airshed
influenced by vehicular emissions.

62

Toronto Toxics Study
- 06/12-13/90 {2nd week)

Sample:

Date sampled:

Sanpling period:

Location:

1 Propane

2 Chloromethane

3 Chloroethene
it 1 ,3-txjtadiene

5 Butane

6 Acrylonitri le

7 Pentane

8 Isoprene

9 1,1-di chloroethene

10 Oichloromethane

1 1 Hexane

12 Trichloromethane

13 1,2-dichloroethane

K 1 ,1,1-trichloroethane

15 Benzene

16 Tetrachloromethane

17 Cyclohexane

18 1 ,2-dichloropropane

19 Tri chloroethene

20 Heptane

21 1,1,2-trichloroethane

22 Toluene

23 1,2-dibro(noethane

24 Octane

25 Tetrachloroethene

26 Chlorobenzene

27 Ethylbenzene

28 total m,p-xylenes

29 Styrene

30 1,1 ,2,2-tetrachloroethane

31 o- xylene

32 Nonane

33 1,3,5-trimethylbenzene
3A 1 ,2,4-trimethylbenzene

35 1, 3- di chlorobenzene

36 Decane

37 1 ,4-di chlorobenzene

38 1,2-dichlorobenzene

39 1 ,2-diethylbenzene

40 Undecane

41 1 ,2,4-trichlorobenzene

42 Naphthalene

43 Dodecane

44 Tridecane

MJS#1 BDK#1 MJS#2

06/12/90 06/12/90 06/12/90

0820-0920 0826-0926 1200-1300

Avenue/Bloor Old City Hall Avenue/Bloor

27

38

T

5

T

3

24

4

25

T

T

5

18

T

15

6
17
T

5

T

3
6

T
T

12

BDIC#2 MJS#3 8DIC#3

06/12/90 06/12/90 06/12/90

1202-1302 1600-1700 1555-1655

Old City Hall Avenue/Bloor Old City Hall

T

20
T

T

T
4

28

T
14

6

15
T

5
T
3
6

T
T

63

Toronto Toxics Study
- 06/12-13/90 {2nd week)

Sainple:

Date sampled:

Sanpling period:

Location:

1 Propane

2 Chloromethane

3 Chloroethene

4 1,3-butadiene

5 Butane

6 Acrylonitrile

7 Pentane

8 Isoprene

9 1,1-di chloroethene

10 Oichloromethane

1 1 Hexane

12 Trichloromethane

13 1,2-dichloroethane

U 1,1,1-trichloroethane

15 Benzene

16 Tetrachloromethane

17 Cyclohexane

18 1,2-dichloropropane

19 Trichloroethene

20 Heptane

21 1,1,2-trichloroethane

22 Toluene

23 1 ,2-dibromoethane
2A Octane

25 Tetrachloroethene

26 Chlorobenzene

27 Ethylbenzene

28 total m,p-xylenes

29 Styrene

30 1,1,2,2-tetrachloroethane

31 o-xylene

32 Nonane

33 1,3,5-triinethylbenzene

34 1,2,4-triinethylbenzene

35 1,3-dichlorobenzene

36 Oecane

37 1 ,4 -di chlorobenzene

38 1, 2 -di chlorobenzene

39 1,2-diethylbenzene

40 Undecane

41 1 ,2,4-trichlorobenzene

42 Naphthalene

43 Dodecane

44 Tridecane

MJS#4

BDK#4

HJS«5

BDIC#5

MJS#6

BDK«6

06/13/90

06/13/90

06/13/90

06/13/90

06/13/90

06/13/90

0815-0915

0815-0915

1200-1300

1200-1300

1600-1700

1600-1700

Avenue/Bloor

Old City Hall

Avenue/Bloor

Old City Hall

Avenue/BLoor

Old City Hall

20

10

29

10

28

8

T

T

T

T

T

T

13

13

9

T
T

T
T

19

T
T

3

10

11
T
T

T
T

27

3
T

5

13

16

18

25

T

T

T

T

10

18

T

17

T

T

T
5

47

T
24

6
15

T

5

T

4
7

13

17

T

12
T
T

T
4

6A