Organophosphate Esters (OPEs) as Emerging Contaminants in the Environment: Indoor Sources and
Transport to Receiving Waters.
by
Jimmy W Truong
A thesis submitted in conformity with the requirements for the degree of Masters of Applied Science
Department of Chemical Engineering and Applied Chemistry University of Toronto
© Copyright by Jimmy W Truong 2016
ii
Organophosphate Esters (OPEs) as Emerging Contaminants in the Environment: Indoor Sources and Transport to Receiving
Waters
Jimmy W Truong
Masters of Applied Science
Department of Chemical Engineering and Applied Chemistry
University of Toronto
2016
Abstract
Organophosphate esters (OPEs) are high usage chemical additives that are of increasing concern
because of growing evidence of potential toxicity and ubiquitous occurrence in the environment.
This thesis summarizes the analysis, sources and environmental abundance of OPEs using
Toronto as a case study. This was accomplished by documenting concentrations, loadings and
factors influencing 19 OPEs in three Toronto streams during high and low flow periods, final
effluent from three waste water treatment plants (WWTP), urban rain and near shore water from
Lake Ontario. Tris (2-chloropropyl) phosphate (TCPP) was found at the highest concentrations
in streams and WWTP effluent. Estimated mass loadings showed that WWTP discharges
contributed significantly to the mass of OPEs entering into nearshore Lake Ontario, however,
streams and rain could contribute equal or higher loadings during wet periods. These results
suggested two major pathways to Lake Ontario: direct discharge from WWTP; and atmospheric
deposition and wash-off into streams.
iii
Acknowledgments
I would like to acknowledge and personally thank my supportive supervisor Miriam Diamond,
and co-supervisors Paul Helm and Liisa Jantunen for providing me with ideas and encouraging
me to always strive for perfection. Their belief in me and guidance helped me prevail through all
my ups and downs. Our mutual collaboration and constant discussions have shaped me into the
man I am today.
This body of work would not be possibly if not for all past and former members of the Diamond
Group, who how been at times comrades, friends and mentors. I would like to thank my all my
colleagues, especially, Joe Okeme and Aman Saini for all their advice on my work and helping
me navigate through my degree, and Congqiao Yang for her aid in analytical chemistry.
Additionally, I would like to thank my parents and family for encouraging me and believing in
my success and to all my friends who have kept me going and would not let me give up. I would
like to acknowledge Dano Morrison, for our mutual competition to finish our theses and publish
our papers; Stephanie Vaughn, for her weekly visits, cupcakes and positive energy; Erika
Dawson, for our love of adventure and her inspirational career advice; and Craig Christensen, for
your love and support during my dark period – without all of you I would not be here today.
iv
Table of Contents
Acknowledgments ..................................................................................................................... iii
Table of Contents ...................................................................................................................... iv
List of Tables ............................................................................................................................ vi
List of Figures .......................................................................................................................... vii
List of Appendices .................................................................................................................. viii
Introduction ........................................................................................................................... 1
1.1 Background .................................................................................................................... 1
1.2 Organophosphate Esters .................................................................................................. 1
1.3 Measurement in Outdoor Environment: .......................................................................... 2
1.4 Transport from Indoor to Outdoor Environment: ............................................................. 3
1.5 Toxicity .......................................................................................................................... 4
1.6 Research Objectives: ....................................................................................................... 4
1.7 References ...................................................................................................................... 6
Organophosphate esters flame retardants and plasticizers in urban rain, streams, and
wastewater effluent entering into Lake Ontario .....................................................................10
Abstract ................................................................................................................................10
2.1 Introduction ...................................................................................................................11
2.2 Methods .........................................................................................................................13
2.3 Results and Discussion ..................................................................................................17
2.4 Conclusion .....................................................................................................................29
2.5 References .....................................................................................................................30
Isomers of Tris(chloropropyl) Phosphate (TCPP), Replacement Flame Retardant in
Technical Mixtures and Environmental Samples ...................................................................33
Abstract ................................................................................................................................33
3.1 Introduction ...................................................................................................................34
3.2 Methods .........................................................................................................................35
v
3.3 Results and Discussion ..................................................................................................36
3.4 Conclusion .....................................................................................................................44
3.5 References .....................................................................................................................46
Is Spray Polyurethane Foam (SPF) Insulation a source of Tris(chloropropyl) phosphate
(TCPP) to the Indoor Environment? ......................................................................................48
Abstract ................................................................................................................................48
4.1 Introduction ...................................................................................................................49
4.2 Methods .........................................................................................................................51
4.3 Results and Discussion ..................................................................................................53
4.4 Conclusion .....................................................................................................................58
4.5 References .....................................................................................................................59
Conclusion............................................................................................................................62
5.1 Future Work ..................................................................................................................63
Appendices................................................................................................................................64
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List of Tables
Table 3.1. TCPP1-3 concentration average and ranges measured in Toronto stream, rain and
WWTPs: mean ± stdev (range) (µg/L). .................................................................................43
Table 4.2. Comparison of ∑TCPP concentrations in insulated house dust and air to reported
literature values. ...................................................................................................................55
vii
List of Figures
Figure 2.1. Sampling locations in the Toronto, Ontario, Canada area for streams ......................14
Figure 2.4. Average relative composition profile of OPEs measured in Toronto urban water. ...23
Figure 2.5 Principle Components Analysis (PCA) on concentrations the 8 OPE compounds
quantified in this study. .........................................................................................................24
Figure 2.6. Estimated instantaneous ΣOPE loadings (Kg/day) from sample locations at
Etobicoke Creek, Don River, and Highland Creek, and three Waste Water Treatment
Plants (WWTP). ...................................................................................................................26
Figure 3.1. Chromatogram of the TCPP isomers from AccuSTD TCPP standard ......................37
Figure 3.2. GC-MSD full scan of the AccuSTD mix. ................................................................38
Figure 3.3. Box plot showing TCPP1/TCPP2 ratios in the Sigma and AccuSTD standards,
urban tributaries, WWTP effluent and rain water. .................................................................44
Figure 4.1. Box plots of TCPP1/TCPP2 isomer ratios from standards, insulation, insulated
house samples and dust. ........................................................................................................56
Figure 4.2. TCPP concentrations in dust from insulated/non-insulated Vancouver homes. ........57
viii
List of Appendices
Appendix 1 - Supporting information for Chapter 2: Organophosphate esters flame
retardants and plasticizers in urban rain, streams, and wastewater effluent entering into
Lake Ontario .........................................................................................................................67
Appendix 2 – Supplementary Information for Chapter 3: Isomers of Tris(chloropropyl)
Phosphate (TCPP), Replacement Flame Retardant in Technical Mixtures and
Environmental Samples…………………………………………………….. ........................ 87
Appendix 3 - Supporting information for Chapter 4: Is Spray Polyurethane Foam (SPF)
Insulation a source of Tris(chloropropyl) phosphate (TCPP) to the Indoor Environment? ... 106
1
Introduction
1.1 Background
Organophosphorus esters (OPEs), which are used as flame retardants (FRs) and plasticizers, are
high production volume chemicals that have been measured at elevated levels in media ranging
from indoor air and dust to Arctic air. Interest in these compounds has arisen because they are
being used as alternatives to brominated flame retardants (BFRs) such as polybrominated
diphenyls (PBDEs) for which new production and new uses have been controlled. Action has
been taken to control all PBDE mixtures in Canada, U.S., Europe and internationally because of
their behaviour as persistent organic pollutants (POP). Canada is currently assessing several
OPEs under the Canadian Environmental Protection Act (CEPA) to determine if any OPEs
should be classified as toxic (for listing under Schedule 1) and subject to control. This follows
from controls of certain OPEs that have been implemented in some jurisdictions such as the
European Union and California. This thesis addresses the lack of Canadian data for OPEs by
providing data relevant to Canada and Ontario. Data are presented on the distribution, levels and
sources from residential inputs of OPEs into the environment. Toronto, Canada, was used as a
case study. This allowed comparison with previous research on PBDE in some of the same
locations (Melymuk et al. 2014).
1.2 Organophosphate Esters
OPEs are high production volume chemicals. The halogenated (mostly chlorinated) compounds,
Cl-OPEs, tend to be used as flame retardants (FRs) and the non-halogenated (Non-Cl OPEs)
compounds are mostly used as plasticizers. However, other uses include as additives to floor
waxes, hydraulic fluids, lacquers, paint, glue, textiles, rubber, epoxy resins, polyurethane foam
and cosmetics (REF). For example tris(2-chloroisopropyl) phosphate (TCPP) and tris(2-3-
dichloropropyl) phosphate (TDCPP) are widely used as flame retardants in flexible foam used
for upholstered furniture and automotive seats (e.g., as a replacement for penta-BDE) and
electronics (Van der Veen & de Boer 2012). TPhP is added at 18-35% by weight to LCD
2
screens, and tris(o-cresyl) phosphate (ToCP) is used in the manufacturing of lacquers, synthetic
fabrics and as a waterproofing agent (Van der Veen & De Boer 2012)(Marklund et al. 2003).
The total consumption of OPEs in Europe in 2006 was estimated to be ~91,000 tonnes (Regnery
& Püttmann 2010). Globally, total production in 2013 represented 30% of global flame retardant
market at over 620 kilotons of OPEs (China Market Research Reports 2014). Since OPEs are
typically added to polymers rather than being chemically bonded, they are subject to release into
the environment via volatilization, dissolution and abrasion (e.g., Rauert et al. 2014). OPEs have
vapour pressures that are orders-of-magnitude higher than most other halogenated flame
retardants such as polybrominated diphenyl ethers or PBDEs (Bergman et al. 2012). Their high
vapour pressures increase the likelihood of release from a product or material. As PBDEs and
other brominated flame retardants have been phased out due to national and international
regulations and policies and PBDE-containing products are retired (Abbasi et al. 2015), the
inventory of OPE-containing products is expected to increase.
1.3 Measurement in Outdoor Environment:
OPEs have been detected globally in a variety of environmental media including indoor dust and
air (Reemtsma et al. 2008)(Stapleton et al. 2009), wastewater (Meyer & Bester 2004),
groundwater (Fries et al. 2001)(Regnery & Püttmann 2010), surface water (Andresen et al.
2007)(Wolschke et al. 2015), and sediments (Cao et al. 2012). The presence of OPEs in air in
remote locations raises concerns about their potential for long range transport. These reports
include OPEs in the Norwegian and Canadian Arctic (Salamova et al. 2014)(Sühring et al. 2016),
Antarctic and the North Sea (Möller et al. 2011). Sühring et al. (2016), found 14 OPEs
dominated by tris(chloroethyl) phosphate (TCEP), TCPP, TDCPP in air across the Canadian
Arctic. The occurrence of Cl-OPEs was reported by Laniewski et al. (1998) who found TCEP
and TCPP in rainwater from Ireland and in snow from Poland and Sweden. The occurrence of
OPEs in remote locations is not consistent with their estimated atmospheric half-lives, which
were estimated to be less than the 2-day criterion under the Stockholm Convention and for
3
which long range atmospheric transport capability was not suggested (Zhang and Sühring et al.
2016). However, high concentrations of non-CL OPEs measured in Arctic air without a clear
geographic pattern suggest that they do undergo long range atmospheric transport (Sühring et al.
2016).
Generally, OPEs are not degraded or removed in waste water treatment plants (WWTPs) (Meyer
& Bester 2004)(Marklund et al. 2005a)(Schreder & La Guardia 2014). As such, effluent from
WWTPs are thought to be the main sources of OPEs to receiving surface waters (Fries et al.
2001)(Andresen et al. 2004). However, Jantunen et al. (2013) reported elevated concentrations of
non-Cl OPEs and Cl- OPEs in rural Ontario and urban Toronto streams that ranged from 10-
1600 ng/L, suggesting sources of OPEs to surface waters in addition to WWTP discharges.
1.4 Transport from Indoor to Outdoor Environment:
OPEs have been measured in indoor air and or dust in the US, Europe (Brommer et al.
2012)(Marklund et al. 2003) (Sjödin et al. 2001), Japan (Tajima et al. 2014)(Kanazawa et al.
2010), and to a limited extent in Canada (Shoeib et al. 2012) . Some of the highest concentrations
of flame retardants measured indoors and outdoors are those of TDCPP (Abbasi et al. 2016) and
TCPP (Brommer et al. 2012)(Stapleton et al. 2009). Some of these concentrations can be orders
of magnitudes higher than PBDEs. Evidence has been lacking regarding the sources of these
compounds into the indoor environment and the pathway from indoors to outdoors. TCPP has
been shown to be in polyurethane foam in couches (Stapleton et al. 2012), and emission of TCPP
from spray polyurethane foam has been demonstrated in chamber studies (Poppendieck et al.
2014). However, other than circumstantial evidence, no conclusive evidence as of yet has linked
the occurrence of OPEs indoors and outdoors to these products.
Schreder et al (2015) suggest that laundry waste water is an efficient conduit for the transfer of
OPEs from the indoor environment into the waste water stream. Saini et al. (2016) substantiated
this contention by showing that fabric could accumulate OPEs from indoor air followed by
released of more than 80% into laundry water. Thus, OPEs accumulated by clothing from indoor
4
air and then released through laundering could be a major source of OPEs to receiving waters.
Furthermore, many studies show evidence OPEs partitioning onto particles in the urban
environment (Marklund et al. 2005b)(Regnery & Püttmann 2009)(Shoeib et al. 2014). This urban
particulate matter could be transported long distances by streams via runoff or wet deposition,
similarly to other SVOCs (Csiszar et al. 2014)(Melymuk et al. 2014).
1.5 Toxicity
The acute toxic effects of OPEs are well-documented and related to their neurotoxicity due to
binding to the acetylcholine esterase enzyme (Van der Veen & de Boer 2012). For example,
triphenyl phosphate (TPhP) is a suspected neurotoxin and the most acutely toxic OPE
(Verbruggen 2005). TPhP is thought to behave similarly to organophosphate ester pesticides
(IPCS 1991).
However, acute toxicity is of limited relevance to environmental exposures. Documentation of
OPE toxicity at more environmentally relevant chronic low doses is sparse. Cl-OPEs such as
TDCPP and TCEP have been shown to exert development and carcinogenic effects in organisms
such as, daphnia, algae, zebrafish and rats (Van der Veen 2012)(National Research Council
2000). TCPP, TCEP, TPhP, TDCPP and have also been shown to cause endocrine disruption by
effecting steroidogenesis and metabolism in zebrafish and MVLN cell lines (Liu et al. 2012).
Recent evidence shows that these compounds impair zebrafish swimming behaviour (Sun et al.
2016)(Dishaw et al. 2014)(Wang et al. 2013), and have developmental effects on zebrafish
embryos (Dishaw et al. 2014). However, knowledge is incomplete regarding the effects of
chronic, long-term, low dose exposure on aquatic organisms, and effects due to exposure to
mixtures, which is the reality of environmental exposures.
1.6 Research Objectives:
Given the uncertainty in toxicity data and their widespread use, there is a need to evaluate the
levels of OPEs in Toronto and Canada with the aim of assessing their risk and to identify factors
that influence their input to the aquatic environment. The goal of this thesis was to provide data
and insights to enable the evaluation of OPEs. This was accomplished by measuring levels and
5
loadings of OPEs in the urban aquatic environment, and investigating a potentially large source
of the most abundant OPE, TCPP. In this thesis, my research is presented in the form of three
research papers from Chapters 2 -5 as follows.
Ch. 2: Organophosphate esters flame retardants and plasticizers in urban rain, streams, and
wastewater effluent entering nearshore Lake Ontario
Aims: To monitor the concentrations of 19 OPEs in the urban aquatic environment through
different pathways (streams, WWTP effluent, rain), and conditions (wet and dry periods), and to
approximate loadings into Lake Ontario.
Ch.3: Isomers of Tris(chloropropyl) Phosphate (TCPP) in Technical Mixtures and
Environmental Samples. Formatted for submission to Journal of Analytical and Bioanalytical
chemistry
Aim: To evaluate, verify and adapt analytical methods for measuring TCPP in environmental
samples. This included clarifying the ambiguity in the literature regarding TCPP identification
and quantification, and verifying the identity and developing quantification methods for
measuring TCPP and its isomers.
Ch4. Is Spray Polyurethane Foam (SPF) Insulation a source of Tris(chloropropyl) phosphate
(TCPP) to the Indoor Environment?
Aim: To investigate the source of the most highly detected OPE (TCPP) in indoor air and dust by
linking TCPP in SPF insulation to indoor levels using concentrations and ratios of TCPP
isomers.
6
1.7 References
Abbasi, G. et al., 2016. Product screening for sources of halogenated flame retardants in Canadian
house and office dust. Science of The Total Environment, 545-546, pp.299–307.
Andresen, J. A, Grundmann, A. & Bester, K., 2004. Organophosphorus flame retardants and
plasticisers in surface waters. The Science of the total environment, 332(1-3), pp.155–66.
Andresen, J.A. et al., 2007. Emerging pollutants in the North Sea in comparison to Lake Ontario,
Canada, data. Environmental toxicology and chemistry / SETAC, 26(6), pp.1081–9.
Bergman, Å. et al., 2012. A novel abbreviation standard for organobromine, organochlorine and
organophosphorus flame retardants and some characteristics of the chemicals. Environment
International, 49, pp.57–82.
Brommer, S. et al., 2012. Concentrations of organophosphate esters and brominated flame
retardants in German indoor dust samples. Journal of environmental monitoring : JEM,
14(9), pp.2482–7.
Cao, S. et al., 2012. Levels and distributions of organophosphate flame retardants and plasticizers
in sediment from Taihu Lake, China. Environmental toxicology and chemistry / SETAC,
31(7), pp.1478–84.
China Market Research Reports. Global and China flame retardant industry report, 2014. Research
In China at China Market Research Reports
http://www.chinamarketresearchreports.com/114859.html (accessed June 30, 2016)
Csiszar, S.A., Diamond, M.L. & Daggupaty, S.M., 2014. The magnitude and spatial range of
current-use urban PCB and PBDE emissions estimated using a coupled multimedia and air
transport model. Environmental science & technology, 48, pp. 1075-1083
Dishaw, L. V et al., 2014. Developmental exposure to organophosphate flame retardants elicits
vvert toxicity and alters behavior in early life stage zebrafish. Society of Toxicology, pp.1–
10.
Fries, E. & Puttnam, W., 2001. Occurrence of organophosphate esters in surface water and ground
water in Germany. J. Environ. Monit., 5, 346–352, pp.621–626.
International Panel on Chemical Safety (IPCS), 1991. Environment Health Criteria (EHC) 111
Triphenyl Phosphate. United Nations Environment Programme, and World Health
Organisation, Geneva.
Jantunen, L. et al., 2012. Organophosphate flame retardants in southern Ontario tributaries and
precipitation. Poster presentated at the Eastern Canada Trace Organic Workshop
Kanazawa, a et al., 2010. Association between indoor exposure to semi-volatile organic compounds
and building-related symptoms among the occupants of residential dwellings. Indoor air,
20(1), pp.72–84.
7
Liu, X., Ji, K. & Choi, K., 2012. Endocrine disruption potentials of organophosphate flame
retardants and related mechanisms in H295R and MVLN cell lines and in zebrafish. Aquatic
Toxicology, 114-115, pp.173–181.
Marklund, A., Andersson, B. & Haglund, P., 2003. Screening of organophosphorus compounds and
their distribution in various indoor environments. Chemosphere, 53(9), pp.1137–46.
Marklund, A., Andersson, B. & Haglund, P., 2005a. Organophosphorus flame retardants and
plasticizers in Swedish sewage treatment plants. Environmental science & technology,
39(19), pp.7423–9.
Marklund, A., Andersson, B. & Haglund, P., 2005b. Traffic as a source of organophosphorus flame
retardants and plasticizers in snow. Environmental science & technology, 39(10), pp.3555–
62.
Melymuk, L. et al., 2014. From the city to the lake: loadings of PCBs, PBDEs, PAHs and PCMs
from Toronto to Lake Ontario. Environ. Sci. Technol., 48, pp. 3732−3741
Meyer, J. & Bester, K., 2004. Organophosphate flame retardants and plasticisers in wastewater
treatment plants. Journal of environmental monitoring : JEM, 6(7), pp.599–605.
Möller, A. et al., 2011. Organophosphorus flame retardants and plasticizers in the atmosphere of
the North Sea. Environmental pollution, 159(12), pp.3660
National Research Council, 2000. Toxicological Risks of Selected Flame-Retardant Chemicals,
National Academy Press, N.W. Washington D.C
Poppendieck, D. et al., 2014. Long Term Emission from Spray Polyurethane Foam Insulation.
Proceedings of 13th International Conference on Indoor Air Quality and Climate, Indoor
Air, pp.HP0126
Rauert, C. et al., 2014. A review of chamber experiments for determining specific emission rates
and investigating migration pathways of flame retardants. Atmospheric Environment, 82,
pp.44–55.
Reemtsma, T. et al., 2008. Organophosphorus flame retardants and plasticizers in water and air I.
Occurrence and fate. Trends in Analytical Chemistry, 27(9), pp.727–737.
Regnery, J. & Püttmann, W., 2009. Organophosphorus flame retardants and plasticizers in rain and
snow from middle Germany. CLEAN - Soil, Air, Water, 37(4-5), pp.334–342.
Regnery, J. & Püttmann, W., 2010. Seasonal fluctuations of organophosphate concentrations in
precipitation and storm water runoff. Chemosphere, 78(8), pp.958–64.
Salamova, A., Hermanson, M.H. & Hites, R. a, 2014. Organophosphate and halogenated flame
retardants in atmospheric particles from a European Arctic site. Environmental science &
technology, 48(11), pp.6133–40.
8
Schreder, E.D. & Guardia, M.J. La, 2014. Flame retardant transfers from U.S. households dust and
laundry wastewater to the aquatic environment..Environment Science and Technology, 48,
11575-11583
Shoeib, M. et al., 2014. Concentrations in air of organobromine, organochlorine and
organophosphate flame retardants in Toronto, Canada. Atmospheric Environment, 99,
pp.140–147.
Shoeib, M. et al., 2012. Legacy and current-use flame retardants in house dust from Vancouver,
Canada. Environmental Pollution, 169, pp.175–182.
Sjödin, a et al., 2001. Flame retardants in indoor air at an electronics recycling plant and at other
work environments. Environmental science & technology, 35(3), pp.448–54.
Stapleton, H.M. et al., 2009. Detection of organophosphate flame retardants in furniture foam and
U.S. house dust. Environmental science & technology, 43(19), pp.7490–5.
Stapleton, H.M. et al., 2012. Novel and high volume use flame retardants in US couches reflective
of the 2005 PentaBDE phase out. Environmental Science and Technology, 46(24),
pp.13432–13439.
Sühring, R. et al., 2016. Organophosphate esters in Canadian Arctic air : occurrence, levels and
trends. Environ. Sci. Technol., 50 (14), pp. 7409–7415.
Sun, L. et al., 2016. Neurotoxicology and teratology developmental exposure of zebra fish larvae to
organophosphate flame retardants causes neurotoxicity. Neurotoxicology and Teratology
55, pp.16–22.
Tajima, S. et al., 2014. Science of the Total Environment Detection and intake assessment of
organophosphate fl ame retardants in house dust in Japanese dwellings. Science of the Total
Environment, The, 478, pp.190–199.
Van der Veen, I. & de Boer, J., 2012. Phosphorus flame retardants: properties, production,
environmental occurrence, toxicity and analysis. Chemosphere, 88(10), pp.1119–53.
Verrbruggen, E.M., et al., 2005. Environmental Risk Limits for Several Phosphate esters, with
possible application as flame Retardant. RIVM Report 601501024/2005.
Wang, Q. et al., 2013. Exposure of zebrafish embryos / larvae to TDCPP alters concentrations of
thyroid hormones and transcriptions of genes involved in the hypothalamic – pituitary –
thyroid axis. Aquatic Toxicology, 126, pp.207–213.
Wolschke, H. et al., 2015. Organophosphorus fl ame retardants and plasticizers in the aquatic
environment : A case study of the Elbe River , Germany. Environmental Pollution, 206,
pp.488–493.
Zhang, X. et al., 2016. Chemosphere novel flame retardants : Estimating the physical – chemical
properties and environmental fate of 94 halogenated and organophosphate PBDE
9
replacements. Chemosphere, 144, pp.2401–2407.
10
Organophosphate esters flame retardants and plasticizers in urban rain, streams, and wastewater effluent entering nearshore Lake Ontario
Abstract
Organophosphate esters (OPEs) are chemical additives that can be released from products and
building materials into the environment via volatilization, dissolution and abrasion. OPEs are a
concern because of recent reports of high concentrations indoors, in surface waters, and their
potential toxicity to aquatic biota and humans. With Toronto, Canada, as the case study, we
documented concentrations of OPEs in three streams during high and low flow periods, final
effluent from three waste water treatment plants (WWTP), urban rain and nearshore Lake
Ontario waters. Eight of the 19 OPEs had detection frequencies above 30%: TBEP, TCPP,
TCEP, TDCPP, TnBP, TPhP, TEP, TPPO. WWTP effluent had the highest range of total OPE
(ΣOPE) concentrations of 1.2-12 µg/L, followed by rivers during high flow periods of 0.78 – 8.1
µg/L, rivers during low flow periods (0.47 - 4.8µg/L), and then rain (0.18-4.7 µg/L). The lowest
concentrations were measured in nearshore water in Lake Ontario (0.19 – 0.69 µg/L). The most
abundantly measured OPEs were Tris butoxyethyl phosphate (TBEP), Tris chloropropyl
phosphate (TCPP), and Tris chloroethyl phosphate (TCEP). ΣOPE concentrations in rivers at
high flow exceeded that at low flow by a factor of two (ANOVA, p<0.05). Estimated mass
loadings on a daily basis showed that WWTP contributed significantly to the mass of OPEs
entering Lake Ontario from Toronto, however, during wet periods, streams and rain could
contribute similar or greater loadings. Compound patterns were similar across streams and
WWTPs. These results suggest that OPEs are ubiquitous in the environment because of their
diffuse use and that WWTP and urban streams are effective at conveying OPEs from the urban
environment to nearshore Lake Ontario.
11
2.1 Introduction
Organophosphate ester (OPEs) compounds are high production volume chemicals that have been
used since the 1950s in a wide range of applications. Non-chlorinated OPEs (Non-Cl-OPEs) tend
to be used as plasticizers whereas chlorinated OPEs (Cl-OPEs) tend to be used as flame
retardants (Van der Veen & de Boer 2012). As high production volume chemicals, OPEs have a
very wide range of uses including plasticizers in floor waxes, hydraulic fluids, lacquer, paint,
glue, textiles, rubber, epoxy resins and cosmetics as well as flame retardants in flexible and rigid
polyurethane foam and polymers used in electronic casings. In 2016, their estimated global usage
was 620 kT, representing 30 % of the global flame retardant market (China Market Research
Report 2016).
Sheldon and Hites (1978) first documented concentrations of ~0.3-3 μg/L of two OPEs, Tri (tert-
-butyl phosphate (TnBP ) and Tris(2-butoxyethyl) phosphate (TBEP), in the Delaware River.
They characterized the compounds as plasticizers which had the highest concentrations of nearly
100 compounds identified. Fukushima et al. (1992) reported that OPEs were ubiquitous in
several Japanese surface waters as far back as 1976. Total OPE concentrations ranged from low
to 28 μg/L, dominated by TCPP at 13 μg/L in the Yamato River. They commented that
concentrations of Tris(1,3-dichloro-2-propyl) phosphate (TDCPP) increased from 1976 to 1987
but that levels then decreased. Marklund et al. (2005), Reemstma et al. (2008) and others also
measured μg/L levels of OPEs in surface waters from industrialized countries in Europe.
Stackelberg et al. (2004) reported frequent detection in finished drinking water at a treatment
plant in the U.S. of Tris(2-chloroethyl)phosphate (TCEP) and TnBP which they attributed to
consistent presence in the intake water sampled and minimal removal by conventional drinking
water treatment processes.
Saeger et al. (1979) wrote that OPEs would not be expected to be environmental contaminants of
concern because of their purported low aqueous solubility, moderate potential for
bioconcentration factor (BCF), and that they would readily undergo primary and ultimate
biodegradation by ambient microbial populations. Howard and Muir (2010), in their search for
commercial chemicals that could be persistent and bioaccumulative, noted that Triphenyl
phosphate (TPhP) was a high production volume (HPV) chemical in 2006 with a high predicted
12
BCF, which put it on the list of chemicals of concern. However, other trihaloalkyl phosphates
such as TCPP were excluded from the priority list because their BCFs were predicted to be low.
Currently concerns have turned towards OPEs. They have been measured in air and water from
remote locations (Salamova et al. 2014)(Sühring et al. 2016)(Möller et al. 2012) suggesting their
potential for persistence and long range transport (Zhang and Sühring et al. 2016). The toxicity
of OPEs have been studied since the 1970s, but were mostly abandoned in the 1990s as they
were deemed to be of moderate toxicity and found at levels below the experimental toxic
threshold (Reemtsma et al. 2008). However, studies in zebrafish have shown endocrine
disrupting potential that affect impacting swimming behaviour (Sun et al. 2016)(Dishaw et al.
2014) and metabolism (Liu et al. 2012) at environmentally relevant concentrations.
In general, the sources of industrial chemicals such as OPEs are now well understood. Urban
areas, as geographic centres of human activities and infrastructure, have elevated concentrations
in air, water and soils of a wide range of chemicals including flame retardants and plasticizers
(Hodge et al. 2007)(Venier et al. 2014). Melymuk et al. (2014) reported loadings for 2008-2009
from the City of Toronto to adjacent Lake Ontario, of the flame retardants polybrominated
diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), synthetic musks and polycyclic
aromatic hydrocarbons (PAH). Toronto has urban and regional populations of 2.6 and 6.3
million, respectively. PBDE loadings to Lake Ontario from streams passing through Toronto
were roughly equivalent to those from the city’s waste water treatment plants (WWTPs).
Loadings from atmospheric deposition, including rain, constituted <5% of the total estimated.
The results, along with multimedia modelling of PBDEs in Toronto (Csiszar et al. 2013)(Csiszar
et al. 2014), suggested that the transport pathways of PBDEs were as follows: from primary
emissions from PBDE-containing products to indoor air followed by release to outdoor air,
deposition to urban surfaces, and wash-off to surface waters at stormwater. A large but unknown
fraction of stormwater is routed through WWTP. Of surprise was the large contribution of
PBDEs from WWTP which was hypothesized to originate from domestic and some industrial
waste water discharges, as well as stormwater routed through the plants.
13
In this study, we assessed the concentrations and compound patterns of OPEs in urban waters of
the City of Toronto, Ontario, Canada, with the aim of gaining a better understanding of key
loadings pathways (rainwater, run-off through streams, and WWTP effluents) to adjacent Lake
Ontario. Observed levels and compound patterns were compared and discussed in the context of
source contributions across the watersheds and sewer-sheds, and whether concentrations in urban
waterways are approaching levels that may be of concern to aquatic organisms. The streams and
WWTPs were the same as those sampled by Melymuk et al. (2014).
2.2 Methods
Sample collection
Urban stream, final wastewater effluent from three WWTPs, and rainwater samples were
collected in the Toronto, Ontario area from May to December 2014 and May to September 2015.
The streams sampled were Etobicoke, Don and Highland Creek with watershed areas of 204,
316, 88.1 km2. Note that the Don River receives discharge from a WWTP serving approximately
55,000 people, located 2 km upstream of the sampling site. The three WWTP sampled directly
treat a combined population of 2,718,000 million. Two of the 3 WWTPs also treat some
industrial discharges. Nearshore waters in Humber Bay and Toronto Harbour were collected on 3
occasions between June and November 2014. Sampling locations are indicated in Figure 2.1.
14
Figure 2.1. Sampling locations in the Toronto, Ontario, Canada area for streams [Etobicoke
Creek (1), Don River (2), Highland Creek (3)], wastewater effluents [plants A, B, and C], rain
waters (R), and nearshore lake waters [Humber Bay and Toronto Harbour (#)].
The following methods were used to collect samples for OPE analysis. Stream samples consisted
of grabs collected using Teflon-lined tubing and filled into pre-cleaned 1 L glass jars using a
remotely-triggered ISCO 6712 automated pumps (Avensys Solutions Inc., Toronto, Canada).
The sampling sites were located at Toronto Region Conservation Authority / Water Survey of
Canada (WSC) monitoring sites at Etobicoke Creek, Don River, and Highland Creek. Samples
were collected during dry and wet weather conditions, and periodically samples were collected
prior to and during rain events at a frequency of every 4 hours over a 24 hour period. Final
wastewater effluent samples were comprised of hourly samples composited over a 24 hour
period and filled into pre-cleaned 4-L Winchester bottles using ISCO 6712 pumps. Rainwater
was collected in 1 L glass amber bottles using a pre-cleaned 17.75 cm steel funnel during rain
events at the downtown University of Toronto campus. Nearshore surface waters adjacent to
Toronto were collected directly into 1 L amber glass bottles using a sampling pole off of a
15
vessel. Upon retrieval, stream and effluent samples were transferred into pre-cleaned 1 L amber
glass bottles. A 40 mL aliquot of dichloromethane (DCM), the extraction solvent, was added to
each sample as a preservative, and samples were stored refrigerated until extraction and analysis.
Additional stream samples were collected for analysis of chloride, suspended solids, and
turbidity by the Ministry of the Environment and Climate Change laboratory. Samples were
taken by the ISCO pumps and transferred to 500 mL polyethylene terephthalate bottles. Water
level and discharge data were obtained from the Water Survey of Canada’s online database
(http://wateroffice.ec.gc.ca/).
Extraction and Analysis
Extractions and analyses were based on previously described methods (Jantunen et al. 2013,
Saini et al. 2016). The extraction method was validated by extracting and analysing 500mL of
HPLC water spiked with all OPE analytes (Table A1.1) and analysing duplicate samples.
Extraction recoveries were monitored by spiking samples with surrogate standards (d15-
triethylphosphate, d21-tripropylphosphate, d27-tributylphosphate, and 13C18-triphenylphosphate
[Wellington Laboratories Inc., Guelph, Canada]) prior to liquid-liquid extraction with DCM.
After 3 sequential DCM extractions, aliquots of DCM were combined and dried over sodium
sulphate, then reduced to 1 mL volume using a Turbovap® II evaporator (Biotage, Charlotte,
USA), solvent exchanged into isooctane and reduced to 0.5 mL under a gentle nitrogen stream
for analysis. Mirex was added as an injection standard prior to quantitative analysis.
Extracts were analyzed by gas-chromatography with mass selective detection (GC-MSD, Agilent
Tech 7890A, Agilent Technologies, Santa Clara, USA) in electron impact (EI) mode (Agilent
5975L Inert Mass Spectrometer,) for a suite of 19 OPEs (TEP, TiPP, TPrP, TBP, TBPO, TCEP,
TCPP, TPP, TDCPP, TPhP, TBEP, EHDPP, TEHP, TPPO, ToCP, DOPP, TmCP, TpCP, TPPP;
see Table A1.1 for definitions and CAS numbers). Standards for quantitation were obtained from
Accustandard Inc. (New Haven, USA). Target analytes were separated on a DB-5 column (0.25
μm film thickness x 30 m length x 0.25 mm [Agilent Technologies]) with the following
temperature program: 90°C hold for 1 minute, ramp 20°C/min to 150°C, 5°C/min to 200°C and
hold for 5 minutes, then ramp at 20°C/min to 310°C and hold for 10 minutes. Samples were
injected splitless (2µL, split opened after 1.0 min). Helium was used as a carrier gas at 40 cm3/s.
16
The injector, transfer line, ion source, and quadrupole temperatures were 250°C, 250°C, 150°C,
and 100-106°C, respectively. Quantitation was undertaken using an eight point calibration curve,
which was rerun after each 10 samples for accuracy. TCPP was quantified as the sum of two
isomers (TCPP1 and TCPP2 see Table A1.1). Peaks were included if the signal to noise ratio
exceeded 3:1 and the retention time was within ±0.2% of the corresponding peak in standard
runs. Quantitation and qualifier ions are listed in Table A1.1 of the supporting information.
QA/QC
Field blanks for stream, wastewater, and nearshore lake samples were collected frequently
(n=20) and consisted of HPLC grade water transferred either to 1 L ISCO bottles in the unit
carousel and then to 1 L amber glass bottles, or directly to 1 L amber glass bottles directly at
field sites, and then carried though the laboratory procedures for analysis. Replicate stream
samples (n=6) and duplicate WWTP samples (n=6) were also collected periodically.
The method detection limit (MDL) of each OPE compound was defined as the average field
blank plus three standard deviations. Results were blank corrected by subtracting the average
blank using the following criteria: samples were not blank corrected if the MDL was < 10% of
total sample concentration; blank corrected if the MDL between 10% - 35% of sample
concentration; and rejected if the MDL> 35% of sample concentration (See Table A1.2).
Extraction efficiency was monitored using blank HPLC water spiked with target analytes and via
the recovery surrogates added to each sample. Recoveries of target OPE analytes in blanks
spikes ranged from 70-110% (Table A1.2). Surrogate recoveries ranged from 51-110% across all
compounds; samples were not recovery-corrected (Table A1.3). Percent differences of individual
OPEs ranged from 5-29% in duplicate wastewater samples, and 8-45% in replicate stream and
nearshore lake samples (Table A1.4).
17
Data analysis
Samples with OPEs with detection frequencies greater than 30% were included in statistical
analyses (TEP, TBP, TCEP, TCPP, TDCPP, TPhP, TBEP and TPPO). Values below detection
limits were not included in the ΣOPEs subjected to statistical analyses, but field blank values
were substituted for <DL for analysis of the relative contribution of compounds. Statistical
analyses were performed using R-studio (Version 0.99.878) for principal component analysis
(PCA) and Spearman Correlations; Graphpad Prism (Version 6.01, 2012) for non-parametric
tests (Kruskal-Wallis ANOVA (KW-ANOVA) with Dunn’s multiple comparisons), and
Microsoft Excel 2013 for graphing.
Chemical loadings were calculated for ∑OPEs and individual compounds to provide an
indication of the relative contributions of each pathway (streams, WWTP effluent, and rainfall)
to nearshore waters of Lake Ontario. Details of the calculations are listed in Appendix 2.1. For
streams, instantaneous loadings (kg/day) were calculated as the product of sample concentration
(ng/L) and co-located WSC discharge data (m3/s) at the time the sample was taken. Estimated
loads via WWTP effluents were calculated from the average daily influent flows (million liters
per day) for 2014 and 2015 (City of Toronto, 2015; 2016) and the individual 24 hour composite
sample concentrations (µg/L). Loadings from rainfall (kg/day) were estimated assuming rainfall
during each event (mm) fell in one day evenly across the area of the City of Toronto (630 km2)
multiplied by the sample concentrations (µg/L).
2.3 Results and Discussion
OPE Detection Frequencies and Concentrations
Detection frequencies for the OPE compounds with over 30% detection in rain, streams, WWTP
effluent, and nearshore water are summarized in Tables A1.5-A1.10. TCPP, TCEP and TBEP are
typically found at greater than 80% detection frequency. Eight of the 19 OPE compounds
analyzed that were observed with detection frequencies greater than 30% in WWTP and stream
samples were: TEP, TBP, TCEP, TCPP, TDCPP, TPhP, TEHP, TBEP, TPPO. TCPP, TCEP and
TBEP. These frequently detected eight OPE compounds are the focus of the following summary
of occurrence, statistical analyses, loading estimates, and discussion. Infrequently detected OPE
18
compounds in this study included: TiPP, TPrP, TBPO, EHDPP, TEHP, ToCP, DOPP, TmCP,
TpCP and TPPP.
Rainwater Detection frequencies were generally low (0-25%) in the 16 rain samples collected
(Table A1.5). The exceptions were TBEP, TCEP and TCPP with detection frequencies of 69-
75%. ΣOPE concentrations ranged from 0.18-4.7 μg/L, with a median of 1.0 μg/L (Figure 2.2).
Median and maximum concentrations of TBEP, TCEP and TCPP were 0.21 (max. 2.32), 0.16
(1.44) and 0.78 (0.92) μg/L, respectively (Table A1.5). Median and maximum concentrations
measured here were similar to those in urban rain sampled in Frankfurt Germany in 2008, for
TCEP (median 0.073; max. 0.338 μg/L), an order-of-magnitude higher for TBEP (0.025; 0.16
μg/L), and similar for TCPP (0.74; 2.7 μg/L) (Regnery and Puttnam (2010). Scott et al. (1996)
measured concentrations of up to 0.05 μg/L for TCEP in rain sampled from rural sites nearby
Lake Ontario in the early 1990s, which is consistent with lower concentrations at distance from
an urban area which act as a source of compounds such as flame retardants (Melymuk et al.
2012).
Figure 2.2. ΣOPE concentrations (μg/L). Boxplots showing median concentrations with
interquartile ranges. Outliers are represented as dots. Stream and WWTP samples are displayed
from left to right corresponding to west to east in the City of Toronto. N.S is Lake Ontario
nearshore water.
19
Stream waters Detection frequencies of OPEs in stream waters ranged from 30-99% for all three
streams during low and high flow conditions and increased during high flow conditions (Table
A1.6-8). TBEP, TCPP and TCEP had detection frequencies of 86-100%. Concentrations were
not significantly different among the three streams in dry or wet weather (ANOVA, p>>0.05).
ΣOPEs in stream samples ranged from 0.47-4.8 µg/L during low flow conditions and from 0.79-
8.1 µg/L during high flow conditions across the three streams (Tables A1.6-1.8). The similarity
in concentrations suggests that the sources of OPEs to rivers are diffuse due to their ubiquity in
the urban environment, as was found in German rivers (Wolschke et al. 2015) (Andresen et al.
2004). ΣOPE median concentrations were significantly greater by a factor of 1.6 (Highland
Creek) to 2.0 (Etobicoke Creek and Don River) higher during wet weather (KW-ANOVA,
p<0.05). This is likely due to direct inputs from wet deposition, surface runoff, and direct input
from drainage systems (Wang et al. 2015)(Wolschke et al. 2015)(Marklund et al. 2005b).
OPE concentrations in Toronto streams are in similar ranges to those reported by Cristale (2013)
from the River Aire in the UK and Spanish rivers sampled in 2011. Most other studies of river
waters measured maximum concentrations of the main OPE compounds (TBEP, TCPP, TCEP)
below µg/L levels reported here (Fukushima et al. 1992)(Wei et al. 2015)(Wolschke et al. 2015).
Wastewater effluents Detection frequencies were highest in WWTP of the waters sampled here,
ranging from 60-100% for all eight quantified OPEs in WWTP samples (Table A1.8), with
medians ranging from 6.3 - 8.3 µg/L among the 3 WWTPs. The three WWTP (A-C) did not
differ significantly in their ΣOPE median concentrations (KW-ANOVA, p>>0.05). The OPE
compounds in order of most to least abundant were TBEP, TCPP, TDCPP and TCEP, except for
WWTP(B) where TCPP was found at higher concentrations than TBEP. This overall pattern
reflects which OPEs are used most in this waste water catchment area as WWTP do not
effectively remove chlorinated OPEs (Marklund et al. 2005)(Schreder & Guardia 2014). High
concentrations of TBEP, a non-CL OPE are most likely due to its ubiquitous use and larger
volume of production than other Cl-OPEs.
These high concentrations in WWTP effluent are consistent with other studies (Bester
2005)(Meyer & Bester 2004)(Andresen & Bester 2006)(Marklund et al. 2005)(Andresen et al.
20
2004), where the median concentration of TCPP (3.4 µg/L), TCEP (0.95 µg/L) and TPhP (0.051
µg/L) in Toronto WWTPs sampled in 2014 were similar to those measured in Germany and
Sweden in 2003 (Meyer & Bester 2004)(Marklund et al. 2005). However concentrations of
TBEP and TDCPP in Toronto were double (3.0, 1.0 µg/L), and TnBP was substantially lower in
Toronto than in German WWTPs (0.082 – 1.2 µg/L)(Meyer & Bester 2004), which could also
represent a change in usage in the 10 years. More recently, Schreder and LaGuardia (2014)
detected ΣCl-OPEs in WWTP effluent collected in 2012 from Vancouver, Washington
exceeding a mean of 10 µg/L, about an order-of-magnitude higher those measured here. The
most abundant compounds they measured were TCPP > TDCPP> TCEP, which is similar to this
study.
Nearshore waters Lake Ontario nearshore waters had the lowest detection frequencies ranging
from 0-60% (Table A1.10). These samples had the lowest concentrations of all waters tested
with ΣOPE median concentrations ranging from 0.19 – 0.69 µg/L. These low concentrations
were expected as the lake dilutes loadings from various urban pathways. The most frequently
detected OPEs in nearshore waters were TBEP, TCPP and TCEP, ranging from below the limit
of detection for each to 0.30 µg/L for each compound. The other OPEs were infrequently
detected (<11%), and had median concentrations below the limit of detection.
Andresen et al. (2007) reported concentrations ranging from 0.02-0.05 µg/L for Cl-OPEs
(TCPP,TCEP and TDCPP), and 0.02-0.17 µg/L for non-Cl OPEs (TnBP, TPhP and TBEP) in
Hamilton Harbour sampled in 2005, ~54 km west of Toronto, also on the shore of Lake Ontario.
In comparison, higher concentrations were measured here for Cl-OPEs in Toronto nearshore
water (LOD – 0.6 µg/L) , perhaps due to increased usage of OPEs in the intervening 10 years or
due to a greater inputs from the larger population of Toronto versus Hamilton. Andresen et al.
(2007) found that concentrations decreased and stabilized with increasing distance from
Hamilton Harbor at 0.3 to 3.2 ng/L for the Cl-OPEs, suggesting the dilution effect from the lake
and relatively stability of these compounds in Lake Ontario Water. The stability of these OPEs in
Great Lakes water was corroborated by Venier et al. (2014) who reported the OPE
concentrations in remote sites in Lakes Michigan, Huron and Erie. Lake Erie had the highest
ΣOPE concentrations (0.1 ± 0.04 µg/L, where TBEP>TCPP>TCEP) followed by Lake Michigan
then Lake Huron. The higher concentrations of OPEs in urban waters are a source to
21
“background levels” found in open waters of the Great Lakes (Venier et al., 2014)(Andresen et
al. 2007). It is interesting to note that TBEP, the highest measured OPE in lake water actually has
the shortest half-life (704 hours) of all commonly measured OPEs (Zhang et al. 2016). This
suggests that despite its fast degradation in water, it is still measured in high concentrations
because of its pervasive use.
Exposure and potential for impacts to aquatic biota
It is important to put the levels reported here into the context of ecotoxicological impacts for
aquatic species. Past toxicology studies for the frequently detected OPEs in Toronto waters
focused on acute toxic effects, with thresholds for effects in the range of approximately 1-100
mg/L related to neurotoxicity (Verbruggen 2005)(Van der Veen & de Boer 2012). TPhP and
TDCPP are the most acutely toxic, with the lowest LC50 values of 0.4-1 mg/L. Cl-OPEs such as
TDCPP and TCEP have been shown to be developmental and carcinogenic toxicants (Van der
Veen & de Boer)(National Research Council 2000).
Recent toxicology testing has focused on more subtle endpoints related to endocrine disruption
and behaviour. For example, Liu et al. (2012) found that TCPP, TCEP, TPhP and TDCPP
exhibited endocrine disrupting potential with altering steroidogeneses and metabolism of
estrogen in zebra fish and MVLN cell lines at concentrations of 10-100 μg/L. These
concentrations can be within a factor of 10 of those reported here. Concentrations >625 µg/L
impaired zebra fish locomotor behaviour in free swimming and photomotor response (Sun et al.
2016)(Dishaw et al. 2014). Cristale et al. (2013) found that acute lethal toxicity of OPE
compounds was additive for Daphnia magna. This suggests that the current approach of
evaluating individual OPEs for their toxicity may be underestimating their toxicity. Therefore,
there is merit in further assessing the abundant OPEs (namely TCPP, TCEP and TDCPP) and
ΣOPE concentrations for their potential to impair aquatic ecosystem health.
OPE composition in urban waters
Average compound profiles in each of the waters are depicted in Figure 2.3. The profiles were
fairly consistent across streams and WWTPs. In particular, TCPP contributed, on average, 30-
22
51% of ΣOPEs, TBEP at 20-44%, and TCEP at 6-10% of ΣOPEs. TnBP contributed 8-11% to
ΣOPEs in Etobicoke Creek samples. On average, the three chlorinated OPEs TCPP, TCEP, and
TDCPP accounted for 47-62% of ΣOPEs in each of the urban waters.
The highest concentrations of individual OPEs in streams were measured in the Don River
during low and high flow samples. The highest concentration was for TBEP (5.2 µg/L), then
TCPP (4.9 µg/L), followed by TCEP (0.70 µg/L) and TDCPP (0.35 µg/L). As noted above, the
sampling site on the Don River was located downstream of a WWTP and the higher maximum
concentrations at this site were likely influenced by discharges from the plant. As discussed
below, the highest concentrations of OPEs are typically measured in WWTP effluent (Marklund
et al. 2005) and thus receiving waters with low dilution factors, such as the Don River, are
expected to have high levels (Cristale et al. 2013). However, the highest concentration of TnBP
was found at Etobicoke Creek (2.2 µg/L), which is not influenced by WWTP discharges.
The profiles of OPEs in rain and nearshore lake waters were more varied than stream and
WWTPs. Rain generally had fewer compounds detected but had higher proportions of TCEP
(20%), and was the only medium in which TPPP was detected (20%). The nearshore water
profile had a relatively greater proportion of TCEP of ΣOPEs (30%), which has the greatest
water solubility (794.3mg/L) of all OPEs studied except for TEP.
23
Figure 2.3 Average relative composition profile of OPEs measured in Toronto urban water.
PCA A principle components analysis was undertaken to identify the similar and differences
amongst OPEs in each water-type sampled and factors that accounted for the most variability
(Figure 2.4). Analysis was performed on log transformed concentrations for every sample type
for the 8 OPEs with greater than 30% detection frequency. Missing values were replaced with
the LOD. Principle components (PC) 1 (x-axis) and 2 (y-axis) accounted for 52.3% and 12.7% of
the variation, respectively, whereas other PCs each accounted for <10% of the variation (see
Table A1.12). PC1 appeared to represent concentrations (from low to high) in rain and nearshore
water (left side) to rivers then WWTP effluents (right side). Most samples did not separate along
PC2 suggesting similar patterns of abundance of the compounds, as discussed above. The one
exception here was for Etobicoke Creek samples.
TnBP was the distinguishing feature separating Etobicoke Creek from the rest of the samples in
the PCA space. Etobicoke Creek includes a very large international airport in the upper reaches
of the watershed. The elevated concentrations of TnBP in Etobicoke Creek are consistent with
releases from the use of TnBP in hydraulic fluids used in aircraft (Suhring et al 2016)(Marklund
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Perc
ent
Co
mp
osi
tio
n (
%) TPPP
TPPO
TEHP
EHDPP
TBEP
TPhP
TDCPP
TPP
TCPP
TCEP
TBPO
TnBP
TEP
24
et al. 2005). Etobicoke Creek has also been impacted by spills of perfluorinated surfactants from
firefighting foam from the same airport (Moody et al. 2001).
Figure 2.4 Principle Components Analysis (PCA) on concentrations the 8 OPE compounds
quantified in this study. Samples are grouped according to site and ellipses represent 70% of all
samples for a specific group. See Table A1.12 for more information.
Comparison of OPE Loadings to Nearshore Lake Ontario
Stream waters Loadings to nearshore Lake Ontario adjacent to Toronto were calculated as the
product of concentrations and flow were calculated for three pathways, rain, streams and
WWTP. The comparison was done on a daily basis due to the relatively few samples taken over
the course of the year.
25
During dry weather flows, the ranges of instantaneous loadings for Etobicoke Creek, Don River
and Highland River were 0.048-0.31, 0.21-1.5, and 0.018-0.10 kg/day, respectively. Wet
weather loadings were an order of magnitude higher than dry weather flows at 0.42-17, 0.36-31
and 0.071-13 kg/day, respectively (Table A1.13). Loadings did not differ significantly between
the three watersheds except during high and low flow periods (KWA-ANOVA, p<0.05) (Figure
2.5). This is because high variability of instantaneous discharges in both dry and wet conditions
reduces ability to detect statistically significant differences in the three watersheds. The Don
River had significantly greater loadings, particularly during dry weather, than Highland Creek
(Dunn’s Test, p<0.05), likely due to contributions from the upstream WWTP and its larger
watershed area. Additionally, loadings are a function of discharge, and since the stream
discharges at low flow are greatest for Don River (1.6 - 3.2m3/s), and lowest for Highland Creek
(0.39 - 0.59m3/s), comparing the two streams with the highest and lowest base flows likely
explain the higher loading observed in the Don river.
Spearman correlations (r) between ∑OPEs and chloride ion (Cl-), suspended solids (SS) and
turbidity were calculated for the three streams to explore other factors related to concentrations
and loadings measured in streams. ΣOPEs did not significantly correlate with the Cl- (p>0.5)
which is indicative of dissolved-phase constituents. However, a significant positive correlation
was observed between ΣOPEs and suspended solids and turbidity for Etobicoke Creek (r = 0.46,
0.46 respectively; p<0.05) and Highland Creek (r=0.42, 0.43 respectively; p<0.05) (Table
A1.14). Correlations with SS and turbidity were not significant for the Don River, likely due to
the influence of the effluent discharge from the upstream WWTP. These results, along with the
significantly higher stream concentrations and loadings during wet than dry conditions, and with
the lower concentrations found in rainwater itself, suggest that material including OPEs is
flushed from watersheds via stormwater run-off (Wei et al. 2015). The pathway from air to
deposition to urban surfaces followed by wash off was described in the multi-media modelling of
PCBs and PBDEs in Toronto (Csiszar et al. 2012, 2013, 2014), and has been shown for OPEs by
their detection in runoff and snow in the dissolved and particle phases (Marklund et al. 2005)
(Regnery & Püttmann 2009).
26
Rai
n
Eto
b( L
ow)
Eto
b (H
igh)
Don
(Low
)
Don
(Hig
h)
Hig
hlan
d Lo
w
Hig
hlan
d Hig
h
WW
TP(A
)
WW
TP(B
)
WW
TP(C
)
Insta
nta
ne
ous
OP
E L
oad
ing
s (
Kg
/day)
0
5
10
15
20
25
30
35
Figure 2.5. Estimated instantaneous ΣOPE loadings (kg/day) from sample locations at Etobicoke
Creek, Don River, and Highland Creek, and three WWTP. Boxplots show median with the IQR,
and the outliers represented as dots. For stream and WWTP, samples are displayed going from
west to east in the City of Toronto from left to right.
WWTP effluent Estimated loadings from the WWTPs ranged from 1.3-2.9 kg/day for Plant A,
2.0-7.8 kg/day for WWTP(B), and 0.21-1.9 kg/day for Plant C. Median WWTP(B) loadings
were significantly higher (3.7kg/day) than the other plants (KWA-ANOVA, p<0.05), with the
differences driven by mean daily flows and servicing of a larger portion of the population. The
magnitude of the WWTP loadings were similar to those for wet weather stream flows although
unlike sporadic wet weather events, WWTP the flows were more consistent day-to-day
throughout the year. As such, the WWTPs are expected to contribute greater loadings than these
streams to nearshore Lake Ontario waters.
Loading estimates were normalized on a per capita basis using watershed populations (streams),
and equivalent populations served (WWTPs). There were no significant differences among the
WWTPs or streams during high flows periods (KWA-ANOVA, p>>0.05) on a per capita basis
27
(Table A1.15); however they were statistically different than per capita loadings observed during
low flow periods. Per capita normalization reinforced the notion that OPE emissions are
widespread and diffuse across the city. The data show that different transport pathways drive
OPE loadings during wet and dry conditions in streams and that WWTP effluent and runoff from
cities influence the measured environmental concentrations of OPEs.
Rain water Loadings from rainfall ranged from 0.68 - 14 kg/day. This estimate assumed that rain
fell evenly across the area of Toronto at the same concentrations in one day. Similar to wet
weather stream flows, rainfall is sporadic, and concentrations and volumes are likely to vary
across the city, thus the load estimates are likely to be biased high. Comparing the watershed
area normalized loading for streams during wet periods and rain (Table A1.16), rain can
contribute 50-70% of watershed instantaneous wet loads. This suggests that rain contributes
substantially to loadings in streams during wet weather, but also that WWTP effluent discharge,
OPE accumulation on urban surfaces and its wash off into rivers is also important. The estimated
loadings suggest that OPE inputs from rainfall, and likely from stormwater runoff, are an
important pathway. Indeed, loadings from rain and streams could equal and surpass those from
WWTPs during storm events. However, WWTP inputs may dominate when scaled for annual
contributions because of the consistency of this source.
PBDE Comparison Median loadings of PBDEs from the same streams monitored in 2008-09
ranged from 0.004 -0.010 kg/day, with maximum estimated instantaneous loadings of 0.06-0.14
kg/day, approximately 2 or more orders of magnitude lower than ΣOPEs (Melymuk et al. 2014).
PBDE loading estimates were much lower at 0.010-0.020 kg/day in WWTP, and it was shown
that streams and WWTP contributed equal loadings on an annual basis to nearshore Lake Ontario
(Melymuk). While an order of magnitude difference in per capita discharge of PBDEs was
measured between WWTPs (Melymuk et al. 2011), this was not the case for the OPEs measured
in the same WWTPs in this study. This data shows that OPEs are measured at higher levels than
PBDEs.
28
Implications
The high levels of OPEs detected in urban waters in comparison to PBDEs and other FRs is
hypothesized to be due to their pattern of usage, higher additive levels in products, and their
physical-chemical properties. The relatively high octanol-air partitioning coefficients (KOA),
vapour pressures and higher solubility of OPEs is expected to facilitate air to surface transfer
followed by efficient wash-off by precipitation, to enter stormwater flows. The OPE levels
reported here have implications for aquatic ecosystem health and provide some insights on
approaches for reducing concentrations and loadings. These compounds can be measured at
maximum concentrations were within 10 orders-of-magnitude of sublethal effects on aquatic
organisms, and can have additive effects in organisms such as Daphnia (Cristale et al. 2013).
We hypothesize that there are two dominant pathways whereby OPEs migrate from their source
to the outdoor urban environment. First, OPEs are released from products and materials to indoor
and outdoor air. Evidence of their release from products to air comes from elevated indoor air
concentrations (Schreder et al. 2016)(Harrad et al. 2010) and from the observed decrease in
concentration the more removed from the source (see Chapter 4). The first pathway from indoor
air is to outdoor air via ventilation (Zhang et al. 2009). After release outdoors, it is likely that
some fraction of OPEs deposit to outdoor surfaces followed by washoff to stormwater and then
flows to streams. Chemical washoff from impervious surfaces is an efficient removal
mechanisms (Csiszar et al. 2012), but is expected to be particularly efficient for OPEs given their
high solubility. Furthermore, as shown in this study, rain water loadings could represent greater
than 50% of OPE instantaneous loadings in streams during wet events suggesting that wet
deposition in addition to washoff influence measured OPE concentrations in the urban aquatic
environment.
The second transport mechanism is “down-the-drain” transfer of OPEs from indoors to WWTPs.
This transport mechanism has been hypothesized to have major contributions from clothes
laundering (Schreder and La Guardia 2015). For example, Saini et al (2016) found that >80% of
OPEs that accumulated on fabrics deployed indoors were released into laundry wastewater. The
comparability of loadings from both streams and WWTP suggest that both pathways are
important
29
Consistent OPE compound profiles and loadings across the region and urban water samples
implies diffuse usage and release from products and materials into the environment. A reduction
in their environmental concentrations would require a broad strategy addressing use across many
areas, rather than a focused sector approach addressing a limited number of industrial or
commercial uses. For example, TBEP the OPE measured in highest concentrations, is used
primarily as a plasticizer and floor wax; perhaps the high concentrations of OPEs detected in the
environment are due to their diffuse use in many different products for purposes other than flame
retardancy. The implications of this are that to reduce the measured OPE concentrations, many
industrial sectors would be impacted, making emission reductions more difficult.
2.4 Conclusions
TBEP, TCPP, and TCEP were the most commonly detected and were most abundant of the
OPEs measured. Concentrations of OPEs were greatest in WWTP effluents, followed by wet
weather flows of streams, then dry weather flows of streams, then rain water, and lowest in
nearshore lake waters that receive the WWTP effluent and riverine inputs. OPE chemical profiles
were similar among all media and all sites, illustrating the diffuse nature of sources. This is
corroborated by, instantaneous load estimates as there were few significant differences between
watersheds even when normalized to area and population, and between WWTPs also when
normalized by population. The broad use and source emissions of these compounds has
implications for strategies to reduce their environmental concentrations. Evaluating the necessity
of their wide range of uses may be necessary rather than focusing on selected
commercial/industrial to reduce their emissions.
30
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33
Isomers of Tris(chloropropyl) Phosphate (TCPP), Replacement Flame Retardant in Technical Mixtures and Environmental Samples
Abstract
Tris(chloropropyl) phosphate (TCPP) is one of the most commonly reported organophosphate
esters (OPEs) in environmental samples. TCPP is comprised of four main isomers however
seven possible structures exist, eight CAS numbers, and even more common names have been
reported in the literature. A review of 42 studies reporting one or more of the TCPP isomers
confirmed that the most abundant and most often reported TCPP isomer is tris(2-chloro-1-
methylethyl) phosphate, also commonly known as tris(chloroisopropyl) phosphate (TCiPP or
named here TCPP1). The other three isomers are: bis(2-chloro-1-methylethyl) (2-chloropropyl)
phosphate (referred to here as TCPP2), bis(2-chloropropyl)(2-chloro-1-methylethyl) phosphate
(TCPP3), and tris(2-chloropropyl) phosphate (TCPP4). GC-FID was used to identify the relative
abundances of the isomers in two standards with unknown isomer composition. GC-MSD
response factors (RF) and GC-MSD RFs adjusted for the percent isomer composition are
significantly different (t-test, p<0.05) but the absolute differences indicate that the non-adjusted
RFs are sufficient for quantifying TCPP in environmental samples. Isomeric ratios can give
insight into sources, transport and fate of TCPP in the environment. Samples from urban
tributaries, effluent from waste water treatment plants and rain samples were taken in the
Toronto area and analyzed for TCPP. TCPP1/TCPP2 ratios in these samples were not
significantly different from technical TCPP except for rain (Mann-Whitney, p<0.05) which was
enriched in the lighter more volatile TCPP1 isomer, suggesting different transport pathways.
34
3.1 Introduction
Technical Tris(2-chloro-1-methylethyl) phosphate (TCPP) is an organophosphate ester (OPE)
commonly used as a flame retardant (FR) to comply with flammability standards for rigid
polyurethane foam used for building insulation and refrigerator casings (Sinoharvest 2015). It is
also added to flexible polyurethane foam used in furniture and automotive seats, and has minor
uses as a back-coating for textiles (Van der Veen & de Boer 2012). It is sold under a variety of
names in North America and Europe such as Antiblaze TMCP, Levagard PP, and Fyrol PCF
(Bester, 2005)(National Research Council 2005)(Van der Veen & de Boer, 2012). TCPP is added
but not chemically bonded to polymers, consequently it can be easily released into the
environment through direct contact with dust and surfaces, volatilization and abrasion (Rauert et
al. 2014).
TCPP technical mixtures can vary in the relative abundances of the four isomers depending on
conditions during the manufacturing process (National Research Council 2000)(Weis 2010). The
most commonly reported ratio of the three most abundant isomers is 9:3:1, with rare detection of
the fourth isomer (Bester 2005). Seven possible structures and eight CAS numbers have been
reported in the scientific literature for the four possible isomers of TCPP (Table A2.1). These
constitutional isomers differ in the number of (2-chloro-1-methylethyl, also referred to as 2-
chloroisopropyl) chains ranging from 0-3. The remaining chains are comprised of either (2-
chloropropyl groups), or (3-chloropropyl) groups, which is where the confusion and variation
arises in the literature. The possible isomers include: tris(2-chloro-1-methylethyl) phosphate, also
known as tris(chloroisopropyl) phosphate (TCiPP but referred to as TCPP1 here after); bis(2-
chloro-1-methylethyl)(2-chloropropyl) phosphate (henceforth referred to as TCPP2); bis(2-
chloropropyl)(2-chloro-1-methylethyl) phosphate (TCPP3); tris(2-chloropropyl) phosphate
(TCPP4); bis(2-chloro-1-methylethyl )(3-chloro-1-propyl) phosphate (TCPP5); bis(3-chloro-1-
propyl)(2-chloro-1-methylethyl) phosphate (TCPP6); and tris(3-chloropropyl) phosphate
(TCPP7).
Confusion regarding TCPP isomers is evident in the literature. Moreover, eight CAS numbers
representing different structures were found to reference TCPP and its isomers, a compound with
four possible isomers. Analytical standards prepared from a technical TCPP mixture of three to
35
four isomers were found to be often reported as a total or ΣTCPP, although this was typically not
stated. The relative composition of the isomers was not specified by suppliers nor by researchers
and quantification is difficult because mass spectrometry signal response is often not
proportional to the concentration of the isomer (Harder et al. 1983). A pure TCPP1 standard is
not available and, as such, one would have to infer the relative contribution of each isomer to the
total TCPP concentration, which could lead to uncertainty and potential errors in quantification.
This paper aimed to clarify inconsistencies and confusion with respect to the nomenclature of
TCPP isomers, their chromatographic elution order, and to recommend guidance for
quantification and reporting. We also summarize results from a literature review. Ratios of TCPP
isomers can be used to aid with distinguishing sources, transport and fate of TCPP. Finally, data
are presented on TCPP isomer ratios measured in rain, urban tributaries and waste water
treatment plant effluent sampled from Toronto, Canada, to illustrate the usefulness of isomeric
ratios as a diagnostic tool.
3.2 Methods
CAS numbers, common names, and structures for TCPP were compiled from an exhaustive
review of the literature. Structures and elution order of TCPP isomers were determined by
comparing previous studies and patents, including the NIST 2011 Mass Spectral Library Version
2.0, and literature reported MS spectra of TCPP. Additionally, technical TCPP isomeric
compositions were also experimentally determined in standards using GC-FID and GC-MSD
instruments.
Two standards of TCPP were obtained, 1) a technical standard from Sigma Aldrich (called
Sigma) and 2) a custom OPEs mix standard from Accustandard (called AccuSTD). See Table
A2.2 for further details. Both standards were separated on a non-polar capillary column (DB-5:
J&W, 30-m x 0.25mm x 0.25um film thickness capillary column) coupled with an Agilent 5975
gas chromatography-mass selective detection (GC-MSD) operating in electron impact mode (EI)
and a Perkin Elmer Clarus 680 Flame Ionization Detector (FID) using the same temperature
program (details are Appendix 2.1).
36
Environmental samples from Toronto, Canada, were collected in 2014/15 to determine the TCPP
concentrations and isomeric composition. The samples consisted of urban rain water samples
collected at the University of Toronto (n=8), surface samples from three urban tributaries (n=14)
and final effluent from three waste water treatment plants (WWTPs) (n=6) (see Appendix 2.2).
Details on sampling methods and handling are provided in Chapter 2.
3.3 Results and Discussion
Literature Review
A comparison of 42 studies listing TCPP in environmental samples revealed inconsistencies in
the nomenclature, reporting and quantification of these isomers. In terms of nomenclature, the
studies investigated showed considerable variation in which isomers were reported (see Table
A2.3 for full comparison). For example, 18 out of 42 studies measured TCPP concentrations
without mentioning which isomers were quantified. We found that most studies referred to TCPP
in the text using the common names tris(chloropropyl) phosphate or tris(chloroisopropyl)
phosphate, but with a variety of CAS numbers which referred to different isomeric compounds.
Four CAS numbers were found to be commonly referenced for all isomers or for TCPP1: CAS
13674-84-5, CAS 6145-73-9, CAS 1067-98-7, and CAS 26248-87-3, however three of these
refer to different constitutional isomers of TCPP each with unique triester sidechains, and not all
of these are possible if there are only two triester isomers and two intermediate diester isomers
(Table A2.1). This confusion could have arisen because the second and third most abundant
TCPP2 and TCPP3 intermediate diester compounds are rarely drawn or named in the literature.
Bergman et al. (2012) recommended the use of TCiPP (an acronym of the common name
tris(chloroisopropyl) phosphate), the most abundant isomer, defined here as TCPP1. Nine of the
42 studies used uncommon names for TCPP and its isomers including bis(2-chloro-1-
methylethyl)(3-chloro-1-propyl) phosphate (TCPP5), bis(3-chloro-1-propyl)( 2-chloro-1-
methylethyl) phosphate (TCPP6), and tris (3-chloropropyl) phosphate (TCPP7). Eighteen studies
did not state how many or which isomers were quantified and reported, four reported the first
isomer, TCPP1, whereas nine reported ∑TCPP composed of TCPP1 plus TCPP2 and sometimes
37
TCPP3. TCPP7 (CAS 1067-98-7) or tris(3-chloropropyl) phosphate, the rarest common name
and CAS number for TCPP, was listed as an isomer or as the main component in six studies
(Van der Veen & de Boer 2012)(Nakamura et al. 1979)(Badoil & Benanou 2009)(Ishikawa et al.
1984)(Galassi et al. 1990), whereas five studies cited TCPP5 and TCPP6 (Badoil & Benanou
2009)(Lehner et al. 2010)(Laniewski et al. 1998)(Serrano et al. 2011)(Thruston et al. 1991). Only
one study reported TCPP2-4 and explicitly stated the method of quantification (Nakamura et al.
1979). Several studies reported poor chromatography leading to the inability to quantify TCPP2-
4 and thus underestimating ΣTCPP.
It is likely that studies reporting ∑TCPP have summed the TCPP isomer peaks in the
chromatogram which can introduce error due to the assumption of one response factor (RF) for
all peaks and noise between the peaks if integrated as a one group. In addition, important
information is lost on individual isomers. Clearly there are inconsistencies in nomenclature and
reporting in the literature which leads to difficulties with comparability because TCPP 2-4 could
contribute up to 40% of ∑TCPP (Bester 2005).
Isomer Determination
Figure 3.1 shows the elution order of four TCPP isomers obtained from full scan GC-MSD
spectra of the four TCPP isomers in the AccuSTD mixture. Accustandard also supplied us with
chromatograms and area counts for two other technical TCPP standards they have commercially
available, each of which had a unique CAS number and are summarized in Table A2.2.
Figure 3.1. Chromatogram of the TCPP isomers from AccuSTD TCPP standard. The four
isomers 1) Tris(2-chloro-1-methylethyl) phosphate (TCPP1), 2) Bis(2-chloro-1-methylethyl) (2-
chloropropyl) phosphate (TCPP2), 3) Bis(2-chloropropyl)(2-chloro-1-methylethyl) phosphate
(TCPP3), and 4) Tris(2-chloropropyl) phosphate (TCPP4).
38
The elution order of the four isomers was determined by observing the relative abundances of the
277 ion to the base or highest ion, 99, and by the presence or absence of the (2-chloro-1-
methylethyl) group (see Figure 3.2). Ion 277 results from the cleavage of C-Cl (~50 amu with
isotopes, Figure 3.2 circled in red) from the “limbs” of the ester group. The first peak in the
chromatogram or TCPP1, has three limbs that can lose the C-Cl group, where TCPP2 has two
limbs, TCPP3 has only one limb, and TCPP4 has none of these limbs to lose, hence the 277 ion
is absent. With TCPP1 having the highest abundances of these ions, we were able to assign a
spectra to isomers TCPP2, TCPP3 and TCPP4. The elution order was also confirmed by
comparing the relative amounts of ion 201. Ion 201 results from the cleaving (P – O – 2-chloro-
1-methylethyl) groups (~126 amu with isotopes, see Figure 3.2 circled in blue), which is only
possibly when a (2-chloro-1-methylethyl) group is present in the isomer.
Figure 3.2. GC-MSD full scan of the AccuSTD mix. TCPP1-4 isomers, molecular weight
327.57 amu. 1) Tris(2-chloro-1-methylethyl) phosphate (TCPP1), 2) Bis(2-chloro-1-methylethyl)
(2-chloropropyl) phosphate (TCPP2), 3) Bis(2-chloropropyl)(2-chloro-1-methylethyl) phosphate
(TCPP3), 4) Tris(2-Chloropropyl) phosphate (TCPP4).
39
The elution order reported here is similar to that in three studies which published chromatograms
of TCPP containing (3-chloropropyl) chains (Lehner et al. 2010) (Laniewski et al. 1998)
(Thruston et al. 1991, Figures A2.1-3). However, the authors used different names and CAS
numbers to identify the isomers, as discussed above.
A comparison between the GC-MSD spectra of the Sigma and AccuSTD mixtures with those in
the NIST 2011 database, showed that the NIST database contained spectra for TCPP1 but did not
contain TCPP2, TCPP3, and TCPP4 labelled with the correct IUPAC names or CAS numbers.
The NIST 2011 database did contain spectra labelled TCPP7, or tris (3-chloropropyl) phosphate
(CAS-1067-98-7) and isomers with either one or two (3-chloropropyl) functional groups, TCPP5
(CAS 137909-40-1) and TCPP6 (CAS 137888-35-8). These spectra matched very closely with
the TCPP2-4 spectra obtained from Sigma. Discussions are on-going with NIST in regards to
this.
TCPP 5-7 are unlikely to exist in the technical TCPP mixtures. They are not known to be by-
products from the manufacturing process of TCPP (Weis 2010) and there can only be four
isomers judging from the chromatograms presented here (Figure 3.1) and in previous studies
(Figures A2.1-3). The AccuSTD reported here is listed as TCPP7 (CAS 1067-98-7) by the
supplier but has chromatograms that matched the Sigma technical TCPP chromatograms, where
we have identified the structure of the compounds under each peak (Table A2.2). Additionally,
NIST entries for TCPP5-7 were cited by one study where the nomenclature is in doubt (Thruston
et al. 1991) because these spectra match very closely with those obtained here for TCPP 2-4.
This suggests that the reports of TCPP5-7 in the literature are due to the mislabelling of TCPP
with different CAS numbers and/or common names.
Isomer Fraction
It is useful to determine the isomer fraction in technical mixtures to be able to compare it to
environmental samples to assess degradation, transport and ultimately fate in the environment.
The isomer fraction, f, is defined as:
40
where i is peak 1 to 4. Since industrially, TCPP is produced as a technical mixture with varying
compositions of each isomer, the actual composition of the individual isomers is unknown. To
determine isomer composition, the AccuSTD and Sigma standards were run by GC-FID. GC-
FID responds to the carbon skeleton of a chemical (Harder et al. 1983) so the mass contribution
from each isomer can be determined since all the isomers of TCPP have the same carbon
structure. This is similar to the Webb-McCall method used to determine the mass contribution
for PCBs (Webb et al. 1973). The mass contribution of individual isomer was obtained by:
M A
)(100)M A( = % Mass
ii
n
1=i
ii
where Ai is the area of peak i, Mi is the molecular weight of compound i (327.57 amu for TCPP),
and n is the number of peaks integrated.
The isomer fractions of the two standards differed significantly; AccuSTD was 37%, 40%, 18%
and 5% for TCPP1-4, respectively. In comparison, the Sigma was 71%, 26%, 3% and 0.1%,
TCPP1-4, respectively See Table A2.4 for more details and Table A2.2 for a comparison to other
published results. The Sigma standard is more similar to the other published technical TCPP
compositions, so we assume this standard is a technical standard, whereas the AccuSTD custom
standard is not.
The fraction of each isomer was also determined by GC-MSD for each mixture, assuming the
same response factor for each peak (see Table A2.4). The percentages based on FID and MSD
are significantly different (paired t-test, p<0.05), with a higher proportion of TCPP1 by FID
compared to TCPP2-4 for both Sigma (without TCPP4) and AccuSTD mixtures. GC-MSD mass
contributions of TCPP1 were 3-5% higher and for TCPP3 and 4, 1-6% lower compared to GC-
FID (Tukey Honesty Significance test (HSD), p<0.05, Table A2.4). Although the differences in
isomeric composition are small, they are significant. This emphasizes the importance of
accounting for the mass contribution of each peak using the FID method.
41
Two additional TCPP standards from Accustandard were quantified for their isomeric
composition using their mass contribution from chromatograms and peak area data from their
supplier (see Table A2.2). Comparing the percent contribution of the two standards with
literature values, this is further evidence that the Sigma standard is the technical mixture were the
AccuSTD is not.
Response Factor (RF)
The single response factor (RF) method using GC-MSD is typically used for mixtures of
unknown composition (Jantunen et al. 2000). This RF method assumes that the RF of each peak
is the same; however the GC-MSD RF of isomers can vary substantially (Jantunen & Bidleman
1998). After adjusting for the mass contribution for each peak as determined by GC-FID, the RF
for each of the isomers was determined for each standard mixture, where the RF is defined as:
RFi = Ai / Massi
where Ai is the area of peak i, and Massi is the total mass of isomer i in a sample. The individual
RFs for TCPP1-4 (Sigma) showed some significant differences: TCPP3 and TCPP4 were
significantly different from each other and from TCPP1 and TCPP2, but TCPP1 and TCPP2
were not significantly different from each other (Table A2.5). This suggests that the least
abundant isomers TCPP3 and 4 are not adequately estimated using the single GC-MSD RF
method because they do not give the same response factor as TCPP1 and TCPP2. This
emphasizes the importance of determining the mass contribution from each peak using FID and
using a multiple response factor method over the single RF method.
Isomeric Composition of TCPP in Environmental Samples
Samples were collected in the Toronto area during 2014-15, specifically rain, surface bulk water
from urban streams, and final WWTP effluent. The highest average ∑TCPP concentration was
found in WWTP effluent (13 ± 3.8 µg/L). It is well documented that WWTPs are a source of
∑TCPP to receiving waters (see Chapter 2), followed by urban tributaries (6.4 ± 2.1 µg/L). The
lowest concentrations was found in rain water (0.71 ± 0.78 µg/L, see Table 3.1). All samples had
42
the same relative abundance of isomers where TCPP1>TCPP2 with TCPP3 and TCPP4 below
detection limits in all samples (except WWTP, see Table 3.1). In Toronto tributaries, TCPP1
constituted on average 67-76% of ΣTCPP, followed by 23-25% of TCPP2, and the remaining 2-
8% was TCPP3 (Table A2.6). In WWTP effluent, TCPP ranged between 69-77%, TCPP2
between 22-31%, whereas TCPP3 was not found. In rain, TCPP1 ranged from 65-100% of the
ΣTCPP, although the lack of TCPP2 and TCPP3 in some samples was due to interferences in the
chromatogram rather than their absence, which were excluded from statistical analyses.
The TCPP1/2 ratios in stream water and WWTP effluent were not significantly different from
each other (Mann-Whitney Rank Sum Test, p<0.05, see Table A2.7), which suggests sources
with similar TCPP isomeric compositions. Both sets of samples were taken in urban
environments and for one stream site, final WWTP effluent was released directly upstream of the
sampling location. Although few samples were taken in each stream, there were no statistical
differences in TCPP1/2 ratios between the locations (see also Chapter 2)
Rain water had the highest average TCPP1/TCPP2 ratios (3.4 ± 0.04), which were also
significantly higher than TCPP1/2 in stream water (2.7 ± 0.36) (Mann-Whitney, p<0.05), but not
WWTP effluent (3.0 ± 0.41, see Table A2.8). The enrichment of TCPP1 in rain is consistent with
its higher vapour pressure. Although, the vapour pressures of individual TCPP isomers have not
been measured, we estimated them using SPARC (ARC 2013) based on their chemical
structures. The vapour pressures decrease from TCPP 1 (3.6x10-4 Tor) to TCPP 4 (3.0 x 10-4 Tor)
(Table A2.9). This is expected from their elution order on a non-polar gas chromatographic
column (Figure 3.1). The higher vapour pressure of TCPP1 would lead to a slightly higher
fraction of TCPP1 in air compared to water and hence the higher ratio of TCPP1/2 in rain than
surface waters.
43
Table 3.1. TCPP1-3 concentration average and ranges measured in Toronto stream, rain and
WWTPs: mean ± stdev (range) (µg/L).
TCPP1 TCPP2 TCPP3 ∑TCPP
Tributaries
(n=14)
6.7±5.5
(1.4-29)
2.4 ± 1.8
(0.31-9.0)
0.22 ± 0.36
(0 – 1.3)
6.4 ± 2.1
(3.1 – 10)
Rain (n=8) 0.50±0.61
(0.078-1.8)
0.10±0.19
(0-0.51)
- 0.71 ± 0.78
(0.078 -2.3)
WWTP
(n=6)
12±8.6
(6.6 – 29)
4.0 ± 2.7
(2. -9.0)
-
13 ± 3.8
(9.4 – 18)
The ratios of the three TCPP isomers in the environmental samples were compared to the Sigma
and AccuSTD mixtures. All TCPP isomeric fractions (TCCP1-4) in rain, tributaries and WWTP
samples were statistically different from the AccuSTD mixture whereas only rain samples
differed significantly from the Sigma mixture (Mann-Whitney, p<0.05). Since it was ascertained
that the Sigma standard is the technical mixture, TCPP retains the isomeric composition of the
technical mixture when transported from sources to urban tributaries and through WWTPs but do
not when partitioned into air as reflected in the rain.
44
Sigma AccuSTD Streams WWTP Rain
TC
PP
1/T
CP
P2
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Figure 3.3. Box plot showing TCPP1/TCPP2 ratios in the Sigma and AccuSTD standards, urban
tributaries, WWTP effluent and rain water. See SI for additional details (Table A2.7).
Quantification and comparison of TCPP isomers can be exploited as a tool to improve our
understanding of the environmental transport and fate of these compounds (Bester
2005)(Carlsson et al. 1997). Often isomers have different physical-chemical properties, and
degradation half-lives that can change the isomer ratios spatially and temporally (Sühring et al.
2016)(Cho et al. 1996)(Bidleman et al. 2002). Isomers can also differ in toxicity (Willett et al.
1998). Examples of compound for which isomer ratios have been used as a diagnostic tool
include hexabromocyclododecane (HBCDD) (Abdullah et al. 2008)(Newton, Sellström, & De
Wit, 2015), tricresyl phosphate (TCP) (Cho et al. 1996), and chlordane (Bidleman et al. 2002).
3.4 Conclusions
A review of 42 papers revealed considerable uncertainty and variability in nomenclature and
reporting practices for TCPP, noting that seven isomeric structures are possible and eight CAS
numbers have been used. We determined that the four isomers in technical TCPP in order of
elution on a DB-5 column are: tris(2-chloro-1-methylethyl) phosphate (TCPP1 or TCiPP); bis(2-
chloro-1-methylethyl) (2-chloropropyl) phosphate (TCPP2); bis(2-chloropropyl) (2-chloro-1-
45
methylethyl) phosphate (TCPP3); and tris(2-chloropropyl) phosphate (TCPP4). Individual
isomers can be quantified using both GC-FID and GC-MSD. However since GC-MSD results
can produce significantly different RF for isomers of the same compound, as was the case for
TCPP1-4, GC-FID is recommended for accurately determining fractions of isomers in technical
mixtures, but not for routine analysis. This accurate isomer determination is important because
RFs by GC-FID and GC-MSD are generally not the same and this can lead to over and
underestimation of the isomers. Furthermore we encourage the separate reporting of each TCPP
isomer because the relative abundance of each isomer could be a useful diagnostic tool for
tracing potential sources and transformation during environmental transport and fate processes.
Often isomers have distinct physical-chemical properties, hence transport, partitioning and
degradation characteristics. These properties have yet to be well characterized. We recommend
that future studies consistently name TCPP isomers with their CAS numbers as outlined here,
and that the quantification procedures be stated clearly and justified appropriately.
46
3.5 References
Abdallah, M.A. et al., 2008. Hexabromocyclododecanes in indoor dust from Canada, the United
Kingdom, and the United States. Environmental Science & Technology, 42(2), pp.459-464
Badoil, L. & Benanou, D., 2009. Characterization of volatile and semivolatile compounds in waste
landfill leachates using stir bar sorptive extraction-GC/MS. Analytical and bioanalytical
chemistry, 393(3), pp.1043–54.
Bergman, Å. et al., 2012. A novel abbreviation standard for organobromine, organochlorine and
organophosphorus flame retardants and some characteristics of the chemicals. Environment
International, 49, pp.57–82.
Bester, K., 2005. Comparison of TCPP concentrations in sludge and wastewater in a typical
German sewage treatment plant-comparison of sewage sludge from 20 plants. Journal of
environmental monitoring : JEM, 7, pp.509–513.
Bidleman, T.F. et al., 2002. Chlordane enantiomers and temporal trends of chlordane isomers in
arctic air. Environmental science & technology, 36(4), pp.539–44.
Carlsson, H. et al., 1997. Organophosphate ester flame retardants and plasticizers in the indoor
environment: Analytical methodology and occurrence. Environmental Science and
Technology, 31(10), pp.2931–2936.
Cho, K.J., Hirakwa, T. & Mukai, T., 1996. Origin and stormwater runoff of TCP (triscresyl
phosphate) isomers. Water Research, 30(6), pp.1–12.
Galassi, S., Provini, A. & De Paolis, A., 1990. Organic micropollutants in lakes: A
sedimentological approach. Ecotoxicology and Environmental Safety, 19(2), pp.150–159.
Harder, H., Carter, T. & Bidleman, T.F., 1983. Acute Effects of Toxaphene and Its sediment-
degraded products on estuarine fish. Can. J. Fish. Aquat. Sci., 40, pp.2119–2125.
Ishikawa, S., Taketomi, M. & Shinohara, R., 1984. Determination of trialkly and triaryl phosphates
in environmental samples. Water Research, 19(1), pp.119–125.
Jantunen, L.M. et al., 2000. Toxaphene, chlordane, and other organochlorine pesticides in Alabama
Air. Environmental Science & Technology, 34(24), pp.5097–5105.
Jantunen, M.L.M. & Bidleman, F.T., 1998. Organochlorine pesticides and enantiomers of chiral
pesticides in Arctic ocean water. Archives of Environmental Contamination and Toxicology,
35(2), pp.218–228.
Laniewski, K., Borén, H. & Grimvall, A., 1998. Identification of volatile and extractable
chloroorganics in rain and snow. Environmental Science & Technology, 32(24), pp.3935–
3940.
Lehner, A.F., Samsing, F. & Rumbeiha, W.K., 2010. Organophosphate ester flame retardant-
47
induced acute intoxications in dogs. Journal of Medical Toxicology, 6(4), pp.448–458.
Nakamura, A. et al., 1979. The mutagenicity of halogenated alkanols and their phosphoric acid
esters for Salmonella typhimurium. Mutation research, 66(4), pp.373–80.
National Research Council, 2000. Toxicological risks of selected flame-retardant chemicals,
National Academy Press, N.W. Washington D.C
Newton, S., Sellstrom, U. & De Wit, C., 2015. Emerging flame retardants, PBDEs, and HBCDDs
in indoor and outdoor media in Stockholm, Sweden. Environmental Science and
Technology, 49(5), pp.2912–2920.
Rauert, C. et al., 2014. A review of chamber experiments for determining specific emission rates
and investigating migration pathways of flame retardants. Atmospheric Environment, 82,
pp.44–55.
Serrano, R. et al., 2011. Non-target screening of organic contaminants in marine salts by gas
chromatography coupled to high-resolution time-of-flight mass spectrometry. Talanta,
85(2), pp.877–884.
Sühring, R. et al., 2016. Distribution of brominated flame retardants and dechloranes between
sediments and benthic fish — A comparison of a freshwater and marine habitat. Science of
the Total Environment, 542, pp.578–585.
Thruston, A.D. et al., 1991. Multispectral identification of alkyl and chloroalkyl phosphates from
an industrial effluent. Environmental Protection, 2 pp.419-426
Van der Veen, I. & de Boer, J., 2012. Phosphorus flame retardants: properties, production,
environmental occurrence, toxicity and analysis. Chemosphere, 88(10), pp.1119–53.
Webb, R.G., McCall, A.C., 1973. Quantitative PCB standards for electron capture gas
chromatography. Journal of Chromatographic Science, 11, pp.366–373.
Weis, T., Elbert, R. 2010. Preparation of phosphorus-containing propoxylation products by using
aluminium trichloride. US Patent 7820845 B2
Willett, K.L., Ulrich, E.M. & Hites, R.A., 1998. Differential toxicity and environmental fates of
hexachlorocyclohexane isomers. Environmental Science & Technology, 32(15), pp.2197–
2207.
48
Is Spray Polyurethane Foam (SPF) Insulation a source of Tris(chloropropyl) phosphate (TCPP) to the Indoor Environment?
Abstract
Energy consumption to heat and cool homes is the largest contributor to energy use in the
residential sector and as such, efforts have been directed toward minimizing consumption by
insulating homes. Flame retardants are added to building insulation to comply with flammability
standards set out in building codes. We report on concentrations of Tris(chloropropyl) phosphate
(TCPP) in the air, dust and insulation of a heritage house (Toronto) insulated with TCPP-treated
closed cell, medium density, spray polyurethane foam (SPF) insulation. The TCPP in the
insulation was 26 % by weight. Concentrations of ΣTCPP (sum of three isomers) in air and dust
were 23 ± 8.4 ng/m3 (7.3 – 37 ng/m3) and 85 ± 46 μg/g (3.0 - 230 μg/g), respectively, and were
higher compared to reports from other residential locations. As well, TCPP concentrations in
dust were higher in Vancouver homes reported to have polyurethane foam insulation compared
to homes without insulation. Ratios of isomers TCPP1/TCPP2 in the Toronto insulated home and
dust from Vancouver homes with insulation were significantly higher than those from Vancouver
homes without polyurethane foam insulation and a technical TCPP mixture (One-way ANOVA,
p<0.05). TCPP1/TCPP2 ratios were not significantly different between the SPF (4.1± 0.18), air
(4.8± 0.34) and dust (4.0± 0.20) in the insulated study house (ANOVA, p>>0.05), suggesting
that they came from a similar source. The elevated levels of TCPP in air and dust from this study
and similarity of TCPP1/TCPP2 ratios in the insulated house, and elevated TCPP concentrations
and higher TCPP1/TCPP2 ratio from Vancouver homes insulated with polyurethane foam
suggest that SPF insulation was the source of TCPP to these indoor environments.
49
4.1 Introduction
The heating and cooling of indoor spaces is the largest single contributor to residential energy
consumption in Canada, the EU and the US, accounting for 48-60% of total energy consumption
(Dixon et al. 2012) (Balaras et al. 2005). A common solution to reduce space heating is to tighten
building envelopes through the use of insulation to increase energy-efficiency in new and older
homes and buildings. One of the most common ways to insulate homes is to use Spray
Polyurethane Foam (SPF) and rigid polyurethane foam insulation. The other strategy to tighten
building envelopes is to reduce air infiltration with the attendant effect of increasing
concentrations of chemicals emitted indoors. In turn, this can increase risks for human exposure
to indoor chemicals (Zaatari et al. 2014). Flame retardants (FRs) are among those chemicals for
which indoor residues in air and dust can lead to human exposure (Schreder et al. 2016)(Harrad
et al. 2010).
Beginning in the early 1960s, flammability requirements were added to building codes to
regulate polymer insulations. Although the use of chemical flame retardants (FRs) is not
specified, several FRs have been added to polymer insulations to meet these flammability
requirements (Babrauskas et al. 2012). Prior to its restriction under the Stockholm Convention on
Persistent Organic Pollutants (POPs), hexabromocyclododecane (HBCDD) was used extensively
to flame retard expanded polystyrene (EPS) and extruded polystyrene (XPS) (I.O.M. 2008).
Currently, the FR commonly used in SPF and blown polyurethane foam insulation is
Tris(chloropropyl)phosphate or TCPP (see names below). TCPP is typically added at levels of 2-
25% (Babruskas et al., 2012). TCPP is also used to flame retardant flexible foam in upholstered
furniture and children’s products such as car seats and changing pads (Stapleton et al. 2011). As
50
with most FRs, TCPP is added to polymers not chemically bonded, and thus can migrate out of
the polymers (Rauert et al. 2014). A wide range of FRs including TCPP has been measured in
indoor air and dust where the origin of the TCPP was not identified (Fromme et al.
2014)(Brommer et al. 2012). Chamber studies have demonstrated temperature dependant release
of TCPP from newly-sprayed and older previously-installed SPF insulation (Poppendieck et al.
2014) (Salthammer et al. 2003) (Kemmlein et al. 2003). To date, no direct evidence has linked
the FRs in building insulation specifically to indoor concentrations since FR are used in multiple
applications.
Technical TCPP is comprised of four isomers with the IUPAC names: Tris(2-chloro-1-
methylethyl) phosphate (TCPP1 or TCiPP, CAS No. 13674-84-5 ), Bis(2-chloro-1-methylethyl)
(2-chloropropyl) phosphate (TCPP2, CAS No 76025-08-6), Bis(2-chloropropyl)(2-chloro-1-
methylethyl) phosphate (TCPP3, CAS No. 76649-15-5), and Tris(2-chloropropyl) phosphate
(TCPP4, CAS No. 6145-73-9) (See Chapter 3, Figure 3.1). Technical TCPP mixtures have
different ratios of the four isomers (National Research Council 2000)(Weis 2010)(Chapter 3),
where the most commonly reported ratio of the first three isomers is 9:3:1; TCPP4 is rarely
detected (Bester 2005, Chapter 3). Recently, Truong et al. (Chapter 3) showed differences among
measured ratios of the TCPP isomers in analytical standards and environmental samples. For
example, rain samples were enriched in TCPP1 and thus had a higher TCPP1/TCPP2 ratio than
that of surface waters sampled in Toronto, Canada. In turn, these ratios differed significantly
from technical TCPP standards. The use of isomer ratios has also been used to “fingerprint” or
distinguish sources and environmental samples of tricresyl phosphate (TCP) (Cho et al. 1996),
Hexabromocyclododecane (HBCDD) (Newton, Sellström, & De Wit, 2015), and Chlordanes
51
(Bidleman et al. 2002). This suggests that the TCPP1/TCPP2 ratios could be used to help
differentiate sources to environmental media.
Here we report indoor air and dust concentrations and ratios of TCPP1 and TCPP2 isomers from
a house designed to be highly energy efficient. We use the ratios of TCPP isomers to suggest that
TCPP added to SPF insulation was the likely source of indoor concentrations. The brick house
investigated was built in 1880s. In 2013, the house was renovated using an innovative Nested
Thermal Envelope Design using different thicknesses (from 100 or 193mm) of purple closed-cell
medium density SPF insulation containing TCPP to insulate all walls of the house. TCPP
concentrations and ratio were also examined from homes sampled in Vancouver (Shoeib et al.
2012).
4.2 Methods
Insulated House
The newly renovated historic 6-room house plus basement was treated with TCPP-containing
SPF insulation from June - July 2013, occupied by two people from January to November 2014
and unoccupied in December 2014. Sampling took place from January to December 2014. Three
rooms were sampled 1) sealed and unused with no furniture, 2) frequently used living room with
furniture, and 3) a bedroom with furniture and clothing. See Appendix 3.1 for more information.
Sampling Strategy
Full details are provided in Appendix 3.2.1. Briefly, dust samples (n=14) were collected from all
three rooms in February, April and September to December 2014 using polyester dust socks
52
attached to a vacuum hose (Abbasi et al. 2016). Air samples were collected in each room in
December 2014 (n=13) using a BGI 400S low volume pump at a sampling rate of 10L/min
through a sampling train of glass fibre filter (GF/F, Whatman, 47mm, cut off of 0.3um) followed
by a PUF-XAD-PUF cartridge (each PUF: L, 30 mm; Amberlite XAD-2, 1.5 g; O.D. x L, 22 mm
x 10 cm; Sigma-Aldrich)(Saini et al. 2015). Purple spray polyurethane foam (SPF) insulation
was sampled from two locations where it was exposed in the insulated house. This foam made up
more than >95% of the insulation used in this house. The remaining insulation, which was also
sampled, was white SPF which was used to seal minor cracks along ventilation ducts. For
comparison, insulation from two additional houses was analyzed, 7-year old foam board
insulation (FBI) and newly installed green SPF insulation. Additionally, TCPP concentrations
and ratios were compared to those in dust sampled from 71 homes with different types of
insulation in Vancouver, Canada. Details of dust sampling are provided by Shoeib et al. (2012).
Chemical and Statistical Analysis
SPF, GF/F filters and dust samples were sonicated three times in 3-mL of dichloromethane
(DCM) for 10 minutes. No cleanup was performed and quantitative analysis was done by GC-
MSD (See Appendix 3.2.2). TCPP concentrations were calculated as the sum of TCPP1-3
isomers (ΣTCPP) and ratios of TCPP1/TCPP were determined from the area of target ion. A one-
way ANOVA was used to compare TCPP1/TCPP2 ratios from the Insulated Home to a technical
TCPP mixture (Sigma Aldrich (Sigma) See Chapter 3), and to indoor dust from homes in
Vancouver.
53
4.3 Results and Discussion
TCPP Concentrations in Insulated House
The average TCPP concentration in the insulated house purple SPF insulation was 260 mg/g
(26%) (Table A3.1). In comparison, TCPP concentration in newly applied green SPF insulation
was 120 mg/g (12%). A sample of the 7-year old FBI contained 2.6% TCPP plus 14% Tris(2-
chloroethyl)phosphate (TCEP). The FR content of the white SPF from the Insulated House was
not measured.
Three sets of air samples from different locations in the house were taken twice in December
2014. Air concentrations measured during the two sampling events averaged 23 ± 8.4 ng/m3 (7.3
– 37 ng/m3, n=13, Table 4.2). The ventilation rate was increased during the second sampling
event which coincided with significantly lower air concentrations (t-test, p<0.05, Table A3.2);
unfortunately the ventilations rates were not measured. Air concentrations in the insulated house
were ~3-30 times higher compared to those reported in the literature for homes (Table 4.2). One
exception was TCPP concentrations measured in personal air samples by Schreder et al. (2016)
which exceeded those measured here by about 10-fold for inhalable particles (> 4 μm). However,
concentrations measured in the personal air samples represent the “personal cloud” that exceeds
those measured in stationary samples (Rodes et al. 1991)(Allen et al. 2007) reported that particle-
phase PBDE concentrations were up to ~70% higher compared to stationary samples (gas-phase
PBDE concentrations were comparable).
The overall average concentration of dust in the insulated house was 85 ± 47 μg/g (3.0 - 230
μg/g, n=14), which is ~10 times higher than literature values (Table 4.2). Dust concentrations did
not vary systematically over time in each room (Figure A3.1). Unlike air, TCPP dust
54
concentrations varied within the house: the average living room concentration of 160±53 μg/g
was significantly higher than the bedroom concentration of 50±72µg/g (Tukey Honesty
Significant Difference (HSD), p<0.05, Table A3.3) but neither were significantly different than
the empty room (95±47 μg/g). The living room contained two couches and several electronic
devices which could have been sources of TCPP whereas the bedroom contained only a mattress
and clothes in a closet, and the empty room was closed and empty during study duration. The
only significant source of TCPP in the empty room would have been the SPF insulation as there
was minimal transfer of dust from the occupied rooms.
The TCPP concentrations in dust samples from Vancouver homes with SPF insulation (65 ± 32
µg/g) were higher, although not significantly, than homes with other types of insulation (23±28)
(See Table A3.5).
TCPP Isomer Ratios
TCPP1/TCPP2 ratios differed in the samples of foam insulation. The ratio in the purples SPF
was4.1±0.18. In comparison, the ratio in FBI (4.7±0.13) was different from the green and white
SPF (Tukey HSD, p<0.05), and the green and white SPF were different from the purple SPF
(Tukey HSD, p<0.05,) (Table A3.4). In turn the ratio in the technical mixture (2.5±0.05) was
significantly different than the ratios in the foam.
55
Table 4.2. Comparison of ∑TCPP concentrations in insulated house dust and air to reported
literature values.
ΣTCPP Mean ΣTCPP Range Reference
Dust (μg/g)
Toronto home 85 ± 46 3.0 - 230 This study
Vancouver Homes Mean 22.8 0.46-120 (Shoeib et al., 2012)
Washington homes 4.82 (median) 82.7 (max) (Schreder et al. 2014)
Japanese Homes 0.74 (median) 0.56-390 (Tajima et al. 2014)
Canadian Homes (Fan et al. 2014) 1 ± 0.15 1.1-1.4 (Fan et al. 2014)
Amsterdam Homes 1.4 (median) 0.48-3.8 (Brandsma et al. 2014)
Boston Homes 0.57 (median) 0.14-5.5 (Stapleton et al. 2009)
Air (ng/m3)
Lower Ventilation Rate 29 ± 7.7 13-37 This study
Higher Ventilation Rate 18 ± 6.4 7.3-27 This study
German Indoor air 4.1 (median) <2.0-45 ng/m3 (Fromme et al. 2014)
Japanese Homes mean 1.9 (median) ND -1260 (Saito et al. 2007)
56
TCPP(S
igm
a)FB
I
Gre
en S
PF
IH W
hite
SPF
IH P
urple
SPF
IH A
ir
IH D
ust
VH D
ust
VH D
ust w
/ SPF
TC
PP
1/T
CP
P2
1
2
3
4
5
6
Figure 4.1. Box plots of TCPP1/TCPP2 isomer ratios from standards, insulation, insulated house
samples and dust. Technical TCPP standard (Sigma Aldrich, n=6); foam board insulation (FBI,
n=2); green (n=2) Spray Polyurethane Foam (SPF) insulation; Insulated House (IH) samples
(White SPF (n=4), Purple SPF (n=5), Air (n=13), and Dust(n=14)); dust from Vancouver homes
(VH) with different insulation material or without any (n=68) and dust from VH with SPF
insulation (n=3) (Shoeib et al., 2012)
Ratios of TCPP1/TCPP2 in samples of purple SPF, white SPF, dust and air from insulated house
were 4.1±0.18, 3.2±0.39, 4.0±0.20, and 4.8±0.34, respectively (Figure 4.1). The ratios in purple
and SPF, air, and dust were not significantly different (ANOVA, p=0.61), although the ratio in
air was slightly higher. This is consistent with the higher vapor pressure of TCPP1 (3.56x10-4 Pa)
versus TCPP2 (3.34x10-4 Pa) (ARC 2013). The white SPF, which was used minimally in the
57
house, was significantly different than the other insulated house samples (ANOVA, p<0.05). The
ratios in dust did not vary significantly over the time sampled (Figure A3.2, ANOVA, p=0.6).
This lack of spatial and temporal variability in the TCPP1/TCPP2 ratios in the insulated house
samples and the similarity to the purple SPF which was mainly used in the house support the
hypothesis that measured indoor concentrations of TCPP in the insulated house originated from
the insulation used.
The ratios from Vancouver homes in which owners confirmed the presence of SPF was 3.6±0.88
(2-4.4). These values were in the same range as the SPF insulation investigated here and were
not statistically different than insulated house samples ((Tukey HSD, p<0.05), Figure 4.1, Table
A3.4). These ratios were higher (One-way ANOVA, p=0.08) than ratios from Vancouver homes
with various types of insulation (none, SPF, fibre glass, polystyrene).
Figure 4.2. TCPP concentrations in dust from insulated/non-insulated Vancouver homes. No/DK
(No insulation or don’t know, 24.±32), Yes/DK (Yes insulation but don’t know what type,
19±18), Yes_FG(Yes fibre glass insulation, 20±26), Yes_PS(Yes polystyrene insulation, 12±14),
Yes_SPF(Yes SPF insulation, 65±32)
58
4.4 Conclusions
The results presented here for the insulated house suggest that TCPP migrated from TCPP-
treated SPF insulation into the indoor environment leading to high concentrations in dust and air.
These elevated concentrations could lead to increased TCPP exposure to occupants (Schreder et
al. 2016). Other potential sources of TCPP to the insulated house were minimal, but included
limited furnishings and electronics but rigid plastics and electronics components are not known
to be treated with TCPP. The TCPP1/TCPP2 ratio supported the hypothesis of TCPP migration
from the SPF into the house air and dust. A similar trend was found for homes sampled in
Vancouver. Since TCPP appears to be amongst if not the most abundant OPE in indoor air and
dust (REF), insulation as a source merits further investigation.
59
4.5 References
Abbasi, G. et al., 2016. Product screening for sources of halogenated flame retardants in Canadian
house and office dust. Science of The Total Environment, 545-546, pp.299–307.
Allen, J.G. et al., 2007. Personal exposure to Polybrominated Diphenyl Ethers ( PBDEs ) in
residential indoor air. Environ. Sci. Technol., 41(13), pp.4574–4579.
Arc, 2013. SPARC Performs Automated Reasoning in Chemistry. Autormating reasoning in
chemistry, Athens, USA.
Babrauskas, V. et al., 2012. Flame retardants in building insulation: a case for re-evaluating
building codes. Building Research & Information, 40(6), pp.738–755.
Balaras, C. a. et al., 2005. Heating energy consumption and resulting environmental impact of
European apartment buildings. Energy and Buildings, 37(5), pp.429–442.
Bester, K., 2005. Comparison of TCPP concentrations in sludge and wastewater in a typical
German sewage treatment plant-comparison of sewage sludge from 20 plants. Journal of
environmental monitoring : JEM, 7(5), pp.509–513.
Bidleman, T.F. et al., 2002. Chlordane enantiomers and temporal trends of chlordane isomers in
arctic air. Environmental science & technology, 36(4), pp.539–44.
Brandsma, S.H. et al., 2014. Organophosphorus flame retardants (PFRs) and plasticizers in house
and car dust and the influence of electronic equipment. Chemosphere, 116, pp.3–9.
Brommer, S. et al., 2012. Concentrations of organophosphate esters and brominated flame
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62
Conclusions
This thesis contributed to the overall goal of improving the understanding of the levels of OPEs
in the Toronto region and factors influencing their measured concentrations in the aquatic
environment. Results showed frequent detection of OPEs and at relatively high concentrations in
urban streams, rain and waste water treatment plant (WWTP) effluent. Toronto WWTPs were
found to contribute high loadings of OPEs into nearshore Lake Ontario. However, streams and
rain during wet periods had ΣOPE loadings approaching or surpassing that from WWTPs during
wet events, suggesting that OPEs are widespread and transported via a variety of mechanism into
Lake Ontario. One such pathway is the transport of TCPP, the OPE with the highest
concentrations measured in urban water, from its source in spray polyurethane foam (SPF) used
as insulation, into indoor residential air and dust followed by release to outdoor air and waste
water. Using a combination of concentrations and the unique TCPP isomer ratios observed in an
insulated study house, it was shown that TCPP measured in indoor air and dust has similar
abundances of the TCPP1 and TCPP2 isomers as the SPF insulation. These results are consistent
with the hypothesis that TCPP-treated SPF insulation was the source of the high TCPP
concentrations in dust and air in this house. We posit that this is one mechanism by which TCPP,
a highly detected OPE, can be released into air and thus be transferred into the waste water
stream or outdoor air resulting in the high concentrations of TCPP measured in urban water.
63
5.1 Future Work
To further this work, several recommendations are suggested:
1) WWTP effluent was shown to contribute high loadings of OPEs into Lake Ontario. Can
more effective technologies be developed and used to remove OPEs from WWTP
effluent as this important pathway into the aquatic environment?
2) Streams and rain during wet periods were found to have instantaneous daily loadings that
approached and even surpassed those coming from WWTPs. The pathways from the
urban environment to these media could be better characterized to determine factors
influencing the high concentrations measured during wet events. This could be done by
modelling the fate of OPE emissions from the stock in products and building materials in
the urban environment to determine their transport characteristics with respect to their
physical-chemical properties.
3) The variability in TCPP ratios found in the literature, analytical standards, and detected in
the environment should be further characterized to determine if relative isomer
composition can be used as a reliable fingerprint to link measured environmental
concentrations to insulation and other TCPP-containing products.
4) The relationship between SPF insulation and measured indoor TCPP air and dust
concentrations could be further strengthened by the use of models examining the
emissions rates of the TCPP isomers measured in SPF foam and by calculating expected
concentrations of the isomers with respect to their varying physical-chemical properties.
64
Appendices
Appendix 1 - Supporting information for: Organophosphate esters flame retardants and
plasticizers in urban rain, streams, and wastewater effluent entering into Lake Ontario .........67
Table A1.1. Details of 19 Organophosphate esters analyzed. ................................................67
Table A1.2. Average recovery for spike and recovery method validation experiment ...........69
Table A1.3. Average recoveries of surrogate standards in total sample set (n=152). .............70
Table A1.4. Average percent differences of measured concentrations of duplicate samples
for the 8 OPEs with detection frequencies greater than 30%. ..........................................71
1.1 Loadings equations .......................................................................................................72
Table A1.5 Summary data for Toronto rain samples (ng/L) ..................................................73
Table A1.6 Summary data for Etobicoke Creek (ng/L)..........................................................74
Table A1.7 Summary data table for Don River (ng/L) ..........................................................75
Table A1.8 Summary data table for Highland Creek (ng/L) ..................................................77
Table A1.9 Summary data table for WWTPs (ng/L) .............................................................78
Table A1.10 Summary data table for Lake Ontario nearshore water (ng/L) ..........................80
Table A1.11. Total OPE summary data (µg/L) .....................................................................81
Table A1.12. Principle Components Analysis (PCA) loadings for 8 log-transformed OPE
conger concentrations for all samples. ............................................................................82
Table A1.13. Estimated daily instantaneous ∑OPE loadings (kg/day) observed in urban
Toronto sampling locations. ...........................................................................................83
Table A1.14. Spearman correlation coefficients (R) of water quality parameters to OPE
compounds and Total OPEs (ΣOPEs) .............................................................................84
Table A1.15. Per capita loadings estimates for streams and WWTPs (mg/person/day). ........84
Table A1.16. Area normalized loadings estimates for streams and rain (g/km2/day). ............85
References ...........................................................................................................................86
Appendix 2 – Supporting Information for: Isomers of Tris(chloropropyl) Phosphate
(TCPP), Replacement Flame Retardant in Technical Mixtures and Environmental Samples ..87
65
Table A2.1. Common and chemical names used for TCPP obtained from SciFinder CAS
database. ........................................................................................................................87
Table A2.2 Literature reported and experimentally derived relative isomeric compositions
of TCPP mixtures. .........................................................................................................90
Table A2.3. Summary of TCPP isomers reported in the literature. ........................................92
Figure A2.1. TCPP chromatograms reproduced from Laniewski et al. (1998). .....................93
Figure A2.2. TCPP chromatograms reproduced from Lehner et al. (2010). ..........................94
Figure A2.3. TCPP chromatograms reprinted from Thruston et al. (1991). ...........................95
Table A2.4. Isomer fraction of the Sigma and AccuSTD mixtures by GC-FID and GC-
MS-EI. ...........................................................................................................................96
Table A2.5. Results of the paired t-test for GC-MSD response factors for TCPP1-4
(Sigma). .........................................................................................................................97
Table A2.6. Range and average of TCPP isomeric fractions measured in Toronto
Tributary, Rain and WWTPs ..........................................................................................98
Table A2.7 Mann-Whitney rank sum test results for TCPP1/TCPP2 ratios between
samples. N.S not significant ...........................................................................................99
Table A2.8 Data Summary of TCPP1/TCPP2 ratios in samples for Figure 3.3 .....................99
Table A2.9. Physical Chemical Properties of TCPP1-4 obtained from SPARC (Arc 2013) . 100
2.1 ANALYTICAL METHODS ....................................................................................... 100
2.2 Sampling Methods (See Chapter 2 and Appendix 1 for more detailed information) ..... 101
2.3 QA/QC ......................................................................................................................... 101
Table A2.9. Surrogate standards used in analysis ............................................................... 102
2.4 Sampling Methods (See Chapter 2 and Appendix 1 for more detailed information) ..... 102
References ......................................................................................................................... 103
Appendix 3 - Supporting information for: Is Spray Polyurethane Foam (SPF) Insulation a
source of Tris(chloropropyl) phosphate (TCPP) to the Indoor Environment? ...................... 106
3.1 Insulated House Background ..................................................................................... 106
3.2 Sample Collection ....................................................................................................... 106
66
3.3 Analytical Methods ..................................................................................................... 107
Table A3.1. Concentrations TCPP and TCEP in polyurethane foam insulation from IH
(purple SPF), 7-year old foam board insulation (FBI), and newly installed green SPF. . 109
Table A3.2. ΣTCPP (TCPP1-3) in air from the insulate house from two periods of normal
and increased ventilation. Concentrations are significantly different (T-test, P<0.05). .. 109
Table A3.3. Concentrations of ΣTCPP in IH dust sampled from three rooms from
February to November 2014. ....................................................................................... 110
Figure A3.1. ΣTCPP concentrations in dust from three rooms of IH sampled from
February to December 2014. ........................................................................................ 111
Figure A3.2. TCPP1:TCPP2 ratios from dust in IH sampled from February – December
2014. ........................................................................................................................... 112
Table A3.4. Significance tests across sample groups. One-Way ANOVA, with Tukey's
multiple comparisons test on each pairwise sample grouping. ...................................... 113
Table A3.5. TCPP concentrations in dust from Vancouver homes with different types of
insulation. .................................................................................................................... 114
Table A3.6 Significance tests of samples to technical standard. .......................................... 115
References ......................................................................................................................... 116
67
Appendix 1 - Supporting information for Chapter 2: Organophosphate esters
flame retardants and plasticizers in urban rain, streams, and wastewater effluent
entering into Lake Ontario
Table A1.1. Names, acronyms, CAS numbers of 19 organophosphate esters analyzed.
Acronym Full Name CAS MW
(g/mol)
Quantifier
Ion
Qualifier
Ions
TEP Triethyl phosphate 78-40-0 182 155 99, 127
TiPP Triisopropyl Phosphate 513-02-0 224 99 125
TPrP Tripropyl phosphate 513-08-6 224 99 141, 183
TnBP Tri n butyl phosphate 126-73-8 266 99 155
TNBPO Tributylphosphine oxide 814-29-9 218 92 189
TCEP Tris(2-chloroethyl) phosphate 115-96-8 285 249 251
TCPP *
Tris(chloroisopropyl) phosphate is
studied as a sum of two isomers
(TCPP1 and TCPP2, See Chapter 3)
See
Chapter 3 328 99 125
TPP Tripentyl phosphate 2528-38-3
50 308 99 169
TDCPP Tris(1,3-dichloro-2-propyl) phosphate 13674-87-
8 431 75 99, 191
TPhP Triphenyl phosphate 115-86-6 326 326 325
TBEP Tris(2-butoxyethyl) phosphate 78-51-3 398 57 85,125
68
EHDPP Ethylhexyldiphenyl phosphate 1241-94-7 362 251 250,249
TEHP Tris(2-ethylhexyl) phosphonate 78-42-2 435 94 113
TPPO Triphenylphosphine oxide 791-28-6 278 277 278
ToCP Tri-o-cresyl phosphate 78-30-8 368 368 165, 277
DOPP Dioctylphenyl phosphonate 1754-47-8 382 159 271
TmCP Tri-m-cresyl phosphate 563-04-2 368 368 367
TpCP Tri-p-tolyl phosphate 78-32-0 368 368 367
TPPP Tris(2-Isopropylphenyl)phosphate 64532-95-
2 453 118 452
69
Table A1.2. Average recoveries for spike and recovery method validation experiment (n=6).
Recoveries of spiked standards range from 70-110%; Instrumental detection limits (IDL) and
method detection limits (MDL). The IDL is the lowest concentration that can be measured from
the instrument (Signal to Noise 3:1), and the MDL is the average blank field blank + 3 times the
standard deviation of blanks.
Analytes
Spike
Recovery
(%)
IDL
(ng/L)
Avg Blank
(ng/L)
MDL
(ng/L)
TEP 69.9 ± 5.1 5.05 5.05 5.05
TiPP 77.6 ± 3.8 39.5 39.5 39.5
TPrP 82.8 ± 4.8 19.2 19.2 19.2
TnBP 86.8 ± 6.3 14.3 14.3 14.3
TNBPO 96.7 ± 3.7 71.1 71.1 71.1
TCEP 76.6 ± 12 37.0 37.6 44.4
TCPP 85.3 ± 7.5 26.6 30.4 50.3
TCPP-2 84.2 ± 7 28.6 28.6 28.6
TPP 89.9 ± 7.4 14.4 14.4 14.4
TDCPP 110 ± 8.9 64.9 64.9 64.9
TPhP 86.3 ± 5.5 13.9 13.9 13.9
TBEP 110 ± 4.6 37.1 37.1 37.1
EHDPP 92.7 ± 4.9 13.3 13.3 13.3
TEHP 98.4 ± 4.3 13.9 13.9 13.9
70
TPPO 93.4 ± 10.2 11.4 11.4 11.4
ToCP 84.4 ± 4.1 31.5 31.5 31.5
DOPP 96.1 ± 2.4 14.5 14.5 14.5
TmCP 84.4 ± 4.1 16.6 16.6 16.6
TpCP 83 ± 3.3 14.2 14.2 14.2
TPPP 104 ± 5.5 17.1 17.1 17.1
Table A1.3. Average recoveries of surrogate standards in complete sample set (n=152).
dTEP dTPrP dTNBP MTPhP
Mean 51 73 95 109
stdev 19 24 28 15
71
Table A1.4. Average percent differences of measured concentrations of duplicate samples for 8
OPEs with detection frequencies greater than 30%.
Analytes
WWTP
(n=6)
River
duplicates
(n=6)
TEP 21 45
TNBP 14 26
TCEP 13 22
TCPP-1 5 22
TCPP-2 20 13
TDCPP 29 8
TPhP 5 18
TBEP 17 42
TPPO 8 36
Mean Total 15 26
Stdev 14 24
72
1.1 Loading Calculations
Stream loadings to nearshore Lake Ontario were calculated as L = C x D, where L= loadings
(kg/day), D = discharge (m3/day) converted from m3/s, and C = concentration (ng/L) converted
to kg/m3. Stream discharge ranged from 1.6 – 46 (m3/s) for Etobicoke Creek, 0.38 – 42 (m3/s) for
the Don River, and 0.39 – 51(m3/s) for Highland Creek.
WWTP loadings were estimated as L = C x Da/ 365, where C= concentration, and Da = annual
average daily flows, assuming steady state conditions where effluent discharge equals annual
influent intake.
For Rain, the loading was estimated as L (kg/day) = C x At x Rm where C= concentration in
rain, At = 630 km2 area of Toronto and Rm = amount of rain fallen (m) in a sampling, assumed
to be a 24 hour period, and based on the volume collected over the area of the funnel.
For the WWTPs, the annual average daily flow rates for 2014 and 2015 were as follows:
WWTP(A) 269-280 (ML/day), WWTP(B) 585-638(ML/day), WWTP(C) 164-170 (ML/day).
Each WWTP had approximate catchment populations of 685,000, 1,524,000 and 509,000,
respectively.
73
Table A1.5. Summary data for Toronto rain samples (ng/L)
Rain
(n=16)
Freq of
Detection
(%)
RL
(MDL) Min Median Max
Mean Std
dev
TEP 6% 5.05 <LOD <LOD 9.60 5.30 1.10
TnBP 25% 14.3 <LOD <LOD 151 30.2 37.6
TCEP 75% 44.4 <LOD 159 1440 374 421
TCPP 75% 50.3 <LOD 109 743 182 215
TCPP-
2 19% 28.6 <LOD <LOD 180
43.9 40.0
TDCPP 0% 64.9 <LOD <LOD <LOD <LOD <LOD
TPhP 13% 13.9 <LOD <LOD 34.4 16.00 5.90
TBEP 69% 37.1 <LOD 211 2317 623 737
TPPO 10% 11.4 <LOD <LOD 93.9 19.5 23.1
74
Table A1.6. Summary data for Etobicoke Creek (ng/L)
Etobicoke
Creek
Freq of
Detection
(%)
RL
(MDL) Min Median Max Mean Stdev
Low Flow (n=7)
TEP 100% 5.05 15.3 32.0 105 41.2 30.1
TnBP 57% 14.3 <LOD 26.0 280 95.6 124
TCEP 100% 44.4 73.7 123 382 171 125
TCPP 100% 50.3 276 801 1063 727 293
TCPP-2 100% 28.6 66.3 197 365 188 99.3
TDCPP 0% 64.9 <LOD <LOD <LOD <LOD <LOD
TPhP 0% 13.9 <LOD <LOD <LOD <LOD <LOD
TBEP 86% 37.1 <LOD 499 1321 566 431
TPPO 43% 11.4 <LOD <LOD 111.9 43.1 43.6
High Flow (n=26)
TEP 88% 5.05 <LOD 36.4 101.1 38.1 21.6
TnBP 92% 14.3 <LOD 355 2241 465 487
TCEP 100% 44.4 85.3 280 523 302 125
TCPP 100% 50.3 427.4 1660 3850 1560 700
75
TCPP-2 92% 28.6 <LOD 611 1220 570 307
TDCPP 65% 64.9 <LOD 165 465 179 116
TPhP 50% 13.9 <LOD 21.5 110 29.3 22.7
TBEP 96% 37.1 <LOD 882 2340 912 486
TPPO 46% 11.4 <LOD <LOD 299 43.6 64.7
Table A1.7. Summary data for Don River (ng/L)
Don
River
Freq of
Detection
(%)
RL
(MDL) Min Median Max Mean Stdev
Low Flow (n=7)
TEP 71% 5.05 <LOD 11.2 52.3 18.2 17.4
TnBP 14% 14.3 <LOD <LOD 69.9 22.2 21
TCEP 86% 44.4 <LOD 152 747 263 262
TCPP 100% 50.3 402 881 3240 1190 1008
TCPP-
2 100% 28.6 114 243 1660 459 563
TDCPP 43% 64.9 <LOD <LOD 368 137 113
TPhP 14% 13.9 <LOD <LOD 33.7 16.8 7.51
TBEP 100% 37.1 243 1020 2310 1140 731
76
TPPO 29% 11.4 <LOD <LOD 147 34.7 50.5
High Flow (n=22)
TEP 59% 5.05 <LOD 12.7 52.8 17.7 13.7
TnBP 64% 14.3 <LOD 41.1 216 47.1 47
TCEP 95% 44.4 <LOD 373 696 382 158
TCPP 100% 50.3 794 1150 2810 1310 540
TCPP-
2 91% 28.6 <LOD 385 1418 494 348
TDCPP 64% 64.9 <LOD 162 365 163 91.4
TPhP 36% 13.9 <LOD <LOD 52.7 22.6 12.9
TBEP 100% 37.1 307 1238 5220 1500 1160
TPPO 41% 11.4 <LOD <LOD 129 30.7 35.8
77
Table A1.8. Summary data for Highland Creek (ng/L)
Highland
Creek
Freq of
Detection
(%)
RL
(MDL) Min Median Max Mean Stdev
Low Flow (n=7)
TEP 38% 5.05 <LOD <LOD 15.1 8.72 5.10
TCEP 63% 44.4 <LOD 110 179 106 59.1
TCPP 100% 50.3 92.8 567 1140 595 363
TCPP-2 75% 28.6 <LOD 215 348 192 129
TDCPP 0% 64.9 <LOD <LOD <LOD <LOD <LOD
TPhP 13% 13.9 <LOD <LOD 42.6 17.5 10.1
TBEP 100% 37.1 100 496 1650 657 543
TPPO 25% 11.4 <LOD <LOD 40 18.5 13.1
High Flow (n=24)
TEP 54% 5.05 <LOD 10.9 37.9 12.5 8.72
TnBP 54% 14.3 <LOD 30.6 246 42.1 52.9
TCEP 88% 44.4 <LOD 172 322 171 85.3
TCPP 100% 50.3 347.1 749 2000 850 473
TCPP-2 83% 28.6 <LOD 248 795 292 223
TDCPP 50% 64.9 <LOD 90.4 322 125 76.6
78
TPhP 38% 13.9 <LOD <LOD 239 33.7 46.8
TBEP 96% 37.1 <LOD 892 3180 1100 924
TPPO 38% 11.4 <LOD <LOD 176 31.2 39
Table A1.9. Summary data for WWTPs (ng/L)
WWTPs
Freq of
Detectio
n (%)
RL
(MDL) Min
Media
n Max Mean Stdev
WWTP(A) (n=8)
TEP 100% 5.05 39.4 72.9 122 79.9 26.1
TnBP 100% 14.3 77.7 139 281 164 78.7
TCEP 100% 44.4 396 804 1087 754 246
TCPP 100% 50.3 919 1700 3100 1830 828
TCPP-2 100% 28.6 274 648 1027 660 247
TDCPP 100% 64.9 650 1080 2260 1250 592
TPhP 75% 13.9 <LOD 51.1 97.5 51.6 29.2
TBEP 100% 37.1 861 3070 4890 3020 1440
TPPO 88% 11.4 <LOD 31.1 214 68.5 74.5
WWTP(B) (n=7)
79
TEP 100% 5.05 21 51.9 134 58.7 36.9
TnBP 86% 14.3 <LOD 82.6 98.8 67.7 33.2
TCEP 100% 44.4 443 585 1330 768 335
TCPP 100% 50.3 1180 1590 4551 2010 1164
TCPP-2 100% 28.6 375 558 2110 819 604
TDCPP 100% 64.9 401 702 1930 873 498
TPhP 86% 13.9 <LOD 58.8 724 148 256
TBEP 100% 37.1 453 1900 5560 2280 1620
TPPO 57% 11.4 <LOD 24.2 164 44.2 55.1
WWTP(C) (n=10)
TEP 100% 5.05 41.2 55.8 143 71.2 32.6
TnBP 60% 14.3 <LOD 32.3 124 38.7 33.6
TCEP 90% 44.4 <LOD 784 947 626 325
TCPP 100% 50.3 304.2 1182 2910 1470 845
TCPP-2 100% 28.6 71.3 634 947 548 286
TDCPP 90% 64.9 <LOD 876 2141 986 655
TPhP 10% 13.9 <LOD <LOD 27.9 15.3 4.4
TBEP 100% 37.1 398 3630 5450 3370 1590
TPPO 80% 11.4 <LOD 166 358 155 112
80
Table A1.10. Summary data for Lake Ontario nearshore water (ng/L)
Shore
Water
(n=18)
Freq of
Detection
(%)
RL
(MDL) Min Median Max Mean Stdev
TEP 11% 5.05 <LOD <LOD 14.6 6.00 2.90
TnBP 0% 14.3 <LOD <LOD <LOD <LOD <LOD
TCEP 11% 44.4 <LOD <LOD 215 59.2 44.8
TCPP 67% 50.3 <LOD 65.9 291 85.0 57.3
TCPP-
2 6% 28.6 <LOD <LOD 72.3 31.1 10.3
TDCPP 0% 64.9 <LOD <LOD <LOD <LOD <LOD
TPhP 0% 13.9 <LOD <LOD <LOD <LOD <LOD
TBEP 61% 37.1 <LOD 77.4 327 118 92.3
TPPO 11% 11.4 <LOD <LOD 36.7 13.4 6.37
81
Table A1.11. Total OPE summary data (µg/L)
Minimum Median Maximum Mean
Std.
Deviation
Etob Low
(n=7) 1.2 2.1 3.1 2.0 0.68
Etob High
(n=26) 1.4 4.1 6.0 4.0 1.3
Don Low (n=7) 1.3 1.8 4.9 2.4 1.4
Don High
(n=22) 2.3 3.4 8.2 4.1 1.7
Highland Low
(n=7) 0.49 2.0 2.3 1.7 0.65
Highland High
(n=24) 1.2 3.2 5.3 3.2 1.2
WWTP(A)
(n=8) 4.8 8.3 10 8.1 1.9
WWTP(B)
(n=7) 3.4 6.3 12 7.3 3.1
WWTP(C)
(n=10) 1.2 7.6 10 7.4 3.0
Rain (n=16) 0.18 1.0 4.7 1.3 1.2
Nearshore
Water (n=18) 0.19 0.27 0.69 0.33 0.15
82
Table A1.12. Principle Components Analysis (PCA) loadings for 8 log-transformed
concentrations of OPE concentrations for all samples.
PC1 PC2 PC3 PC4
TEP 0.37 0.02 0.44 -0.08
TNBP 0.37 -0.82 -0.04 0.18
TNBPO -0.004 0.001 0.01 0.01
TCEP 0.35 0.11 0.18 -0.20
TCPP 0.42 -0.09 0.005 -0.36
TDCPP 0.36 0.26 0.25 -0.15
TPhP 0.14 -0.13 -0.05 0.04
TBEP 0.47 0.34 -0.75 0.06
EHDPP 0.02 -0.18 -0.24 0.21
TEHP 0.04 -0.08 -0.10 0.19
TPPO 0.24 0.26 0.28 0.83
83
Table A1.13. Estimated daily instantaneous ∑OPE loadings (kg/day) for streams, WWTP and
rain. *ML/day. **meters of rain fallen.
Daily
Flow
range
(m3/s)
[OPE]
Range
(ug/L)
Minimum
(kg/day)
Median
(kg/day)
Maximum
(kg/day)
Mean
(kg/day)
Std.
Error
Etob Low
(n=6) 0.37 - 1.7
1.2 -
3.1 0.048 0.092 0.31 0.14 0.043
Etob High
(n=24) 0.99 - 42
1.3 -
8.1 0.42 2.8 17 4.1 0.85
Don Low
(n=6) 1.6 - 3.2
1.3 –
4.8 0.21 0.44 1.5 0.63 0.20
Don High
(n=20) 2.1 - 46 2 - 7.8 0.36 2.5 31 6.1 1.7
Highland
Low (n=7) 0.39 - 0.59
0.47 -
2.3 0.018 0.074 0.099 0.067 0.010
Highland
High
(n=22) 0.48 - 52
0.79 -
5.3
0.071 1.4 13 2.8 0.80
WWTP(A)
(n=8) 269-280* 4.8 - 11 1.3 2.3 2.9 2.2 0.19
WWTP(B)
(n=7) 585-638* 3.4 - 12 2.0 3.7 7.8 4.5 0.79
WWTP(C)
(n=10) 164-170* 1.2 - 11 0.21 1.2 1.9 1.2 0.16
Rain
(n=16)
0.001 -
0.034 **
0.39 -
4.7 0.68 3.5 14 5.3 4.0
84
Table A1.14. Spearman correlation coefficients (R) between water quality parameters and
ΣOPEs.. Yellow cells represent significant R values (p<0.05)
Discharge (m3/s) Suspended Solids Turbidity
Don River 0.28 0.12 0.080
Etobicoke
Creek 0.22 0.46* 0.46*
Highland
Creek 0.42* 0.42* 0.43*
Table A1.15. Per capita loadings estimates for streams and WWTPs (mg/person/day).
Don River
Etobicoke
Creek
Highland
Creek WWTP(A) WWTP(B) WWTP(C)
Population 796324 284091 294915 685000 1524000 509000
Condition Dry Wet Dry Wet Dry Wet n/a n/a n/a
Min 0.26 0.45 0.17 1.5 0.06 0.24 1.9 1.3 0.41
Max 1.9 39 1.1 59 0.34 43 4.3 5.1 3.7
Geomean 0.63 3.9 0.37 9.1 0.20 3.4 3.2 2.7 2.2
Mean 0.79 7.7 0.48 14 0.23 9.6 3.3 3.0 2.4
Stdev 0.60 9.8 0.37 15 0.09 13 0.79 1.4 1.0
85
Table A1.16. Area normalized loadings estimates for streams and rain water (g/km2/day).
Etobicoke Creek Don River Highland Creek
Area
(km2) 204 316 88.1
Sample
type Dry Wet Rain Dry Wet Rain Dry Wet Rain
Min 0.24 2.0 1.4 0.66 1.1 1.4 0.20 0.80 1.4
Max 1.5 82 31 4.7 99 31 1.1 140 31
Geomean 0.52 13 7.1 1.6 9.8 7.1 0.68 12 7.1
Mean 0.66 20 10 2.0 19 10 0.76 32 10
Stdev 0.52 21 8.1 1.5 25 8.1 0.30 42 8.1
86
References
Toronto Water, 2016. Humber Wastewater Treatment Plant 2015 Annual Report. City of
Toronto.
Toronto Water, 2015. Humber Wastewater Treatment Plant 2014 Annual Report. City of
Toronto.
Toronto Water, 2016. Highland Creek Wastewater Treatment Plant 2015 Annual Report. City of
Toronto.
Toronto Water, 2015. Highland Creek Wastewater Treatment Plant 2014 Annual Report. City of
Toronto.
Toronto Water, 2016. Ashbridges Bay Wastewater Treatment Plant 2015 Annual Report. City of
Toronto.
Toronto Water, 2015. Ashbridges Bay Wastewater Treatment Plant 2014 Annual Report. City of
Toronto.
87
Appendix 2 – Supporting Information for Chapter 3: Isomers of Tris(chloropropyl)
Phosphate (TCPP), Replacement Flame Retardant in Technical Mixtures and Environmental
Samples
Table A2.1. Common and chemical names used for TCPP obtained from SciFinder CAS
database.
Structure and Common Name CAS Number and Other Names
1) Tris(2-chloro-1-methylethyl) phosphate (TCPP1,
TCiPP)
CAS 13674-84-5
Tris(2-chloroisopropyl)
phosphate
Tris(1-chloro-2-propyl)
phosphate
Tris(1-methyl-2-
chloroethyl) phosphate
Tris(2-chloro-1-
methylethyl) phosphate
Tris(β-chloroisopropyl)
phosphate
2-Propanol, 1-chloro-,
2,2',2''-phosphate
2-Propanol, 1-chloro-,
phosphate
Amgard TMCP
Antiblaze 80
Antiblaze TMCP
Daltoguard F
Fyrol PCF
Hostaflam OP 820
Levagard PP
Levagard PP-Z
PUMA 4010
Tolgard TMCP
2) Bis(2-chloro-1-methylethyl) (2-chloropropyl)
phosphate (TCPP2)
CAS 76025-08-6
Phosphoric acid, bis(2-
chloro-1-methylethyl)
2-chloropropyl ester
88
3) Bis(2-chloropropyl) (2-Chloro-1-methylethyl)
phosphate (TCPP3)
CAS 76649-15-5
Phosphoric acid, 2-
chloro-1-methylethyl
bis(2-chloropropyl)
ester
4) Tris(2-Chloropropyl) phosphate (TCP4)
CAS 6145-73-9
AP 33
Antiblaze RX 35
Fyrol PCT
NSC 524664
Noinen R 921
Pelron 9338
Roflam P
1-Propanol, 2-chloro-,
phosphate
5) Bis(2-chloro-1-methylethyl)(3-chloro-1-propyl)
phosphate (TCPP5)
CAS 137909-40-1
Phosphoric acid, bis(2-
chloro-1-methylethyl)
3-chloropropyl
6) Bis(3-chloro-1-propyl)(2-chloro-1-methylethyl)
phosphate (TCPP6)
CAS 137888-35-8
Phosphoric acid, 2-
chloro-1-methylethyl
bis(3-chloropropyl)
ester
89
7) Tris(3-chloropropyl) phosphate (TCPP7)
CAS 1067-98-7
Tris(3-chloro-1-propyl)
phosphate
TCPP, TCMPP
1-Propanol, 3-chloro-,
phosphate
*Generic Formula with no structure
CAS 26248-87-3
Tri(chloropropyl)
phosphate
Tris(chloropropyl)
phosphate
Tris(monochloropropyl)
phosphate
Anfram 3PX
FG 8115,FG 8115S
Nissan Unflame 3PX
TMCPP
Unflame 3PX
1-Propanol, chloro-, 1,1',
1''-phosphate
1-Propanol, chloro-,
phosphate (3:1)
90
Table A2.2. Literature reported and experimentally derived relative isomeric compositions of
TCPP mixtures.
TCPP1 TCPP2 TCPP3 TCPP4 Comment Source
37% 40% 18% 6%
Determined by GC- FID
Had earlier eluting
impurity (7-8% impurity)
This study, also called ,
Accustandard
(AccuSTD)
CAS 26248-87-3
71% 26% 3% 0.11% Determined by GC-FID
This study,
Sigma Aldrich (Sigma)
CAS13674-84-5
68% 28% 4% 0%
Area data and
chromatograms supplied
by Accustandard
Accustandard
CAS 6145-73-9
67% 28% 4% 0%
Area data and
chromatograms supplied
by Accustandard
Accustandard
CAS 13674-84-5
TCiPP1 TCPP2 TCPP3 TCPP4 Comment Reference
90-95% - - - 10-5% others
NRC 2000
CAS13674-84-5
63% 27% 4% 0.5%
~5% of some other
impurity?
Bayer 1996
CAS 13674-84-5
98% - - Apparently "pure" TCPP NRC 2000, unstated
91
75% 16% 1% <0.1%
Albright and Wilson
1980, CAS Antiblaze
80 mix
<75% - - -
Albright and Wilson
1980, CAS6145-73-9
70% 27% 3% -
Carlsson 1997, Tri(2-
chloropropyl)
phosphate
(Akzo Nobel, Sweden)
75% 25% 8% -
* FYROL PCF industry
mixture
Bester 2005, Fyrol PCF
(Akzo Nobel, Sweden)
CAS
67% 28% 5%
Nakamura 1979, CAS
Tokyo Kasei Co
92
Table A2.3. Summary of TCPP isomers reported in the literature.
1Sum of three isomers 2 Measured both Tris(3-chloropropyl) phosphate and Tris(chloroisopropyl) phosphate using GC-MS to quantify all
three isomers
3 Uses NIST MS 02 database to identify leachate unknowns by matching experimentally derived spectra 4 States that the 3-chloropropyl and 2-chloropropyl chained isomers could produce similar chromatograms and
confound each other 5 Uses Chromalynx Application Manger software to search NIST 02 library to match unknowns
93
Figure A2.1. TCPP chromatograms reproduced from Laniewski et al. (1998). These show TCPP
and two possible structures for TCPP 2 isomers with either one (2-chloropropyl chain) or a (3-
chlorpropyl) chain. Laniewski et al. concluded that, “isomer II was the nonregistered compound
bis(1-chloro-2- propyl)(3-chloro-1-propyl)phosphate. However, the registered compound bis(1-
chloro-2-propyl)(2-chloro-1-propyl)- phosphate (CAS. 76025-08-6) may also produce a similar
mass spectrum.” This is one of the earlier studies that found in the literature that suggests that
TCPP could have two possible structures.
94
Figure A2.2. TCPP chromatograms reproduced from Lehner et al. (2010). TCPP isomers “with
3-chloropropyl” chains A) Tris(3-chloropropyl) phosphate, B) Bis(3-chloro-1-propyl)(1-chloro-
2-propyl) phosphate, C) Bis(1-chloro-2-propyl)(3-chloro-1-propyl) phosphate. Note the
similarity of these spectra to spectra for TCPP 2-4 isomers with (2-chloropropyl) chains. Lehner
et al. mention that TCPP isomers having the (2-chloropropyl) isomers are commonly
found/manufactured as impurities with TCPP1, however they quantified and labeled their
unknown isomers as having 3-chloropropyl chains, probably because the standard was labelled
as Tris(3-chloropropyl) phosphate (CAS 1067-98-7). D) The elution order of TCPP isomers of
Lehner et al. (2010) which correspond to the isomers determined here.
95
Figure A2.3. TCPP chromatograms reprinted from Thruston et al. (1991). They identified 3
TCPP peaks in waste water effluent. Peak 5 is TCPP1, while 6 and 7 were speculated “to have a
mix of (3-chloropropyl) groups because of the loss of CH2Cl ions, leaving an ion of 277”. This
chromatogram corresponds to TCPP chromatograms presented in this study suggesting Thruston
et al. named the three isomers by using CAS 1067-98-7 and chemical name (tris(3-chloropropyl)
phosphate), possibly because a TCPP standard having a rarer CAS number and common name
was purchased.
96
Table A2.4. Isomer Fraction of the Sigma and AccuSTD mixtures by GC-FID and GC-MS-EI.
Absolute differences were tested using Tukey’s Honesty Significant Difference (HSD) by
subtracting MS fractions from FID fractions
AccuSTD Sigma
n
(AccuSTD/Sigma)
P-values Tukey HSD
(FID – MS)
AccuSTD Sigma
TCPP1
FID 0.38 0.70 5/4 0.05(<0.05) 0.03(<0.5)
MS 0.34 0.67 4/6
.
TCPP2
FID 0.39 0.26 5/4 0.02(<0.5) -0.02(<0.5)
MS 0.37 0.28 4/6
TCPP3
FID 0.18 0.04 5/4 -0.01(<0.5) -0.01(<0.5)
MS 0.19 0.05 4/6
TCPP4
FID 0.05 - 5/- -0.06(<0.5) N/A
MS 0.11 - 4/-
97
Table A2.5. Results of the paired t-test for GC-MSD response factors for TCPP1-4 (Sigma).
TCPP3 and TCPP4 were found to be significantly different from each other and all other isomers
(t-test, p<0.05), where TCPP1 and TCPP2 were not significantly different from each other
RF1 RF2 RF3 RF4
RF mean 9.22 9.94 11.23 21.64
RF1 -
RF2 NS -
RF3 <0.05 <0.05 -
RF4 <0.05 <0.05 <0.05 -
98
Table A2.6. Range and average of TCPP isomeric fractions measured in Toronto Tributary, Rain
and WWTPs
Sample Type Isomer Range Average
Tributaries
TCPP1
TCPP2
TCPP3
0.67-0.76
0.23-.28
0.023-0.08
0.73±003
0.24±0.01
0.02±0.04
Rain TCPP1
TCPP2
TCPP3
0.65-1.0
0.35-0.19
0.11-0.02
0.79±0.11
0.19±0.1
0.02±0.04
WWTP TCPP1
TCPP2
TCPP3
0.69-0.77
0.22-0.31
<D.L.
0.74±0.04
0.25±0.04
<D.L.
99
Table A2.7. Mann-Whitney Rank Sum Test results for TCPP1/TCPP2 ratios between samples.
N.S not significant
Sigma AccuSTD Tributaries Rain
Sigma (n=6) -
AccuSTD (n=4) <0.05 -
Tributaries
(n=14) N.S. <0.05 -
Rain (n=8) <0.05 <0.05 <0.05 -
WWTP (n=6) N.S <0.05 N.S N.S
Table A2.8. Data Summary of TCPP1/TCPP2 ratios in samples for Figure 3.3
n Mean Std Dev
Sigma 6 2.5 0.05
AccuSTD 4 0.9 0.03
Streams 14 2.7 0.36
WWTP 6 3.0 0.41
Rain 8 3.4 0.04
100
Table A2.9. Physical Chemical Properties of TCPP1-4 obtained from SPARC (Arc 2013)
TCPP1 TCPP2 TCPP3 TCPP4
logKaw -1.53 -1.55 -1.57 -1.57
logKow 6.04 6.06 6.08 6.1
logKoa 7.6 7.61 7.65 7.67
VP (tor) 3.56E-
04
3.31E-
4
3.14E-
04
3.03E-
04
Solubility
(molefrac)
-7.93 -7.94 7.95 -7.96
2.1 ANALYTICAL METHODS
TCPP standards obtained from Accustandard (AccuSTD) and Sigma Aldrich (Sigma) were
analysed using an Agilent 5975 GC- MSD with an EI source with a DB-5 0.25um x 30m x
0.25mm column and a Perkin Elmer Clarus 680 GC-FID with a DB-5 0.25um x 30m x 0.25mm
column. Both instruments were run with the same temperature program: initial at 90°C hold for 1
minute, ramp 20°C/min until at 150°C, ramp again 5°C/min until 200°C hold for 5 minutes, then
ramp at 20°C until 310°C and hold for 10 minutes. Samples were injected splitless (2µL, split
opened after 1.0 min). For GC-MSD, additional parameters were as follows: injector temperature
of 200°C, transfer line temperature of 250°C, ion source at 230°C and quadrupole 150°C. MSD
ions monitored for TCPP isomers were: 99.0 (Quantifier), and 125.0, 157.0 (Qualifiers).
Tributary, rain and WWTP water samples were analyzed on the GC-MSD, using the above
parameters.
101
2.2 Sampling Methods (See Chapter 2 and Appendix 1 for more detailed information)
1 L grab samples were taken from three tributaries during high and low flow events in Toronto.
Final effluent was collected from three Toronto waste water treatment plants. Rain samples were
collected using a 1L amber bottle and a 9 inch steel funnel in downtown Toronto at the
University of Toronto Campus. Samples were extracted three times using liquid-liquid extraction
using DCM with a separatory funnel adapted from (Jantunen et al. 2013). The DCM fraction was
dried over fired granular sodium sulphate (Baker), the volume was reduced by Turbovap® II
Concentration Evaporator followed by a gentle stream of nitrogen to a final volume of 0.5 mL
for analysis. Mirex was added as the internal standard prior to analysis.
2.3 QA/QC
Organophosphate esters are ubiquitous especially in indoor environments, to prevent
contamination, all glassware was soaked in phosphate-free Decon75 concentrate, washed, rinsed
with deionized water and baked at 250°C for 12 hours. Analytical methods for TCPP
quantification were validated for their reproducibility using certified TCPP standards obtained
from Accustandard. The internal standard technique was used to quantify TCPP concentration
using Mirex as the internal standard (Jantunen et al. 2013). For a given peak to be identified as
detected, the signal to noise ratio of the peak must exceed 3:1. Mass labelled organophosphates:
dTEP, dTPrP, dTBP, MTPhP (Table A2.9) were used to assess recovery of TCPP isomers in
water samples (see Appendix 1.1). Recoveries of these surrogate standards ranged from 45 –
163%. Samples were not recovery corrected and only blank corrected when concentrations were
calculated according to Appendix (1.1) The method detection limit (MDL) was defined as the
average of the blanks plus three standard deviations were: 50.3, 28.6, 23.7 and 7.5 (ng/L) for
TCPP1-4, respectively. Samples were not blank corrected if the MDL was < 10% of total sample
concentration; blank corrected if the MDL between 10% - 35% of sample concentration; and
rejected if the MDL> 35% of sample concentration.
102
Table A2.9. Surrogate standards used in analysis
Acronyms Chemical Name
Amount
Added to
Sample MW
dTPrP Tri-n-propyl phosphate d21 100 ng 245.36
dTBP Tri-butyl phosphate-d27 100 ng 293.48
MTPP Triphenyl phosphate C18 100 ng 344.15
dTEP Tri-ethyl phosphate d15 100 ng 197.25
2.4 Sampling Methods (See Chapter 2 and Appendix 1 for more detailed information)
1 L grab samples were taken from three tributaries during high and low flow events in Toronto.
Final effluent was collected from three Toronto waste water treatment plants. Rain samples were
collected using a 1L amber bottle and a 9 inch steel funnel in downtown Toronto at the
University of Toronto Campus. Samples were extracted three times using liquid-liquid extraction
using DCM with a separatory funnel adapted from (Jantunen et al. 2013). The DCM fraction was
dried over fired granular sodium sulphate (Baker), the volume was reduced by Turbovap® II
Concentration Evaporator followed by a gentle stream of nitrogen to a final volume of 0.5 mL
for analysis. Mirex was added as the internal standard prior to analysis.
103
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106
Appendix 3 - Supporting information for Chapter 4: Is Spray Polyurethane Foam (SPF)
Insulation a source of Tris(chloropropyl) phosphate (TCPP) to the Indoor Environment?
3.1 Insulated House Background
In 2013, an uninsulated historic 1880s Second Empire-style masonry home was renovated using
a Nested Thermal Envelope Design where an insulated building is built inside the existing
structure. The building was insulated using purple closed-cell medium density spray foam
insulation (SPF). The building was doubly insulated with two thermal envelopes where both the
periphery and core spaces were insulated with this SPF. The house was divided into two separate
insulated envelopes that thermally isolate the house into two zones a core and a periphery space
where the core was comprised of rooms expected to be in daily use (kitchen, living room,
bedroom, and bathroom), and the periphery spaces (formal dining room, guest bedroom,
basement) were kept at a minimal level of heat, but could be warmed on demand. Renovation
began in June 2013 and was completed in January 2014. The house was occupied by two
residents from January to November 2014 where the house was unoccupied in December 2014.
Three rooms were chosen for this study: a sealed and unused room with no furniture that was
located in the periphery space; a frequently-used living room in the periphery space with two
couches, a dining table, and some electronics; and a bedroom in the core space with a bed, and a
closet full of clothing. All floors were hardwood, with no carpet.
3.2 Sample Collection
Dust sample collection, storage, sieving and were done following the method of Abbasi et al.
2016 (Abbasi et al. 2016). Dust samples were collected from hardwood floors using a
conventional vacuum cleaner. The hose was pre-cleaned with an isopropanol wipe between
samples. Dust was collected into pre-cleaned 25-µm mesh nylon socks (XUTRECHT03 Vacuum
Bag; Allied Filter Fabrics Ltd., Australia). An average area of 2×2m2 was vacuumed from the
easily accessible center area of the floor. Dust field blanks consisted of 1 g of Na2SO4 on baked
107
aluminium foil (250 °C overnight) placed on the floor of the IH and vacuumed using the same
method as for dust collection. Fourteen Dust samples were collected from the IH in February,
April, and from September –December 2014. Samples were sieved using a pre-baked 150 μm
sieve at 25oC overnight to produce a fine fraction. The sieved fine dust samples were stored in
pre-cleaned glass vials at 4 °C prior to chemical analysis.
72 hour air samples were collected with the method adapted from Saini et al 2015 (Saini et al.
2015). A BGI 400S (PacWill Environmental, Canada) low volume pump was used at a sampling
rate of 10L/min through a sampling train of a glass fibre filter (Whatman, 47mm, cut off of
0.3um), followed by a PUF-XAD-PUF cartridge (each PUF: L, 30 mm; Amberlite XAD-2, 1.5 g;
O.D. x L, 22 mm x 10 cm; Sigma-Aldrich). About 43200L of air was collected for each sample.
The sampling train was kept in-line, horizontal with the pump, on a wooden bench 1m above
ground and placed between two metal coat racks to prevent disturbance.
Thirteen samples were collected twice in each room at weekly intervals from December 8 – 19,
2014. Clean baked filters were brought on site and analyzed as field blanks. Only filters were
extracted to obtain particle-phase concentrations (Salamova et al. 2013), gas phase was checked
for TCPP levels and found very little. All the samples collected from were kept at 4°C until
extraction and analysis.
Purple and white SPF were sampled from IH one year followed its installation. Also sampled
were foam board insulation (FBI) installed approximately 7 years ago and newly installed green
SPF (day after installation in February 2015). These samples were obtained using an
isopropanol-cleaned penknife. Foam samples were wrapped in baked aluminum foil (250°C
overnight) before being placed into glass jars for storage at 4°C until extraction and analysis.
3.3 Analytical Methods
Extractions SPF (10mg), dust (45~75mg) and GF/F filters were sonicated in 5mL DCM x3. The
samples was filtered to remove particles through a pipet plugged with baked glass wool. The dust
and GF/F were volume reduction and exchanged into iso-octane with a gentle steam of GC
purity nitrogen. SPF was diluted prior to analysis as to be within the calibration range of the
instrument method.
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Instrument Parameters Samples were analysed using a GC-MSD (Agilent 6890-5975) EI
mode using a 9 point internal standard (IS) calibration, using Mirex (100 ng) as the internal
standard. The GC was equipped with a DB-5 0.25 μm × 30 m x 0.25 mm column run with the
temperature program: initial at 90°C hold for 1 minute, ramp 20°C/min until at 150°C, ramp
again 5°C/min until 200°C hold for 5 minutes, then ramp at 20°C until 310°C and hold for 10
minutes. Samples were injected splitless (2 µL, split opened after 1.0 min). Helium was used as a
carrier gas at 40 cm3/s. The injector temperature was 200°C, transfer line temperature 250°C, ion
source 230°C, and quadrupole at 150°C. MS ions monitored for TCPP isomers were: 99.0
(Target) and 125.0, 157.0 (Qualifiers). Full details of TCPP analysis is provided in (Chapter 3,
and Appendix 2.1).
QA/QC As organophosphate esters, including TCPP are ubiquitous compounds, contamination
was minimized by treating all glassware as follows: soaked in phosphate-free Decon75
concentrate, then washed, rinsed with water then DI water and baked at 250°C for 12 hours.
Solvents were analytical grade and gases were high purity (99.999%). Sample extraction
efficiency was assessed by adding mass labelled OPEs before extraction. Compounds added
were d15Tri-Ethyl Phosphate, d21Tri Propyl Phosphate, d27Tri Butyl Phosphate, 13C18Tri Phenyl
Phosphate. Recoveries of these surrogates ranged from 75-113% and the data were not recovery
corrected. The instrument detection limit (IDL) of TCPP was 0.5 ng/g based on a 100mg sample
of dust and 1pg/m3 based on a 100m3 air sample. No TCPP was found in the blanks for the
method detection limit (MDL) is the same as the IDL. (See Appendix 1)
Methods for Comparison Samples Full details of sampling and processing of the dust from the
Vancouver homes (n=71) has been published (Shoeib et al., 2012).
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Table A3.1. Concentrations TCPP and TCEP in polyurethane foam insulation from IH (purple
SPF), 7-year old foam board insulation (FBI), and newly installed green SPF.
Table A3.2. ΣTCPP (TCPP1-3) in air from the insulate house from two periods of normal and
increased ventilation. Concentrations are significantly different (t-test, p<0.05).
Air Sample Sample
Size
Mean
(ng/m3)
Std
Dev
Normal Ventilation 6 29 7.8
Increased Ventilation 7 19 6.4
Concentration Unit Purple IH
SPF
FBI Green SPF
∑TCPP mg/g 260 26 120
% 26 2.6 12
TCEP mg/g <DL 142 <DL
% <DL 14 <DL
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Table A3.3. Concentrations of ΣTCPP in IH dust sampled from three rooms from February to
November 2014. *Living room concentration is significantly higher than bedroom concentration
(ANOVA with Tukey HSD, p<0.05) but the empty room was not significantly different than
both the bedroom and living room.
Room Sample
Size
Mean Std Dev
Bedroom 6 50 72
Empty
Room
4 95 47
*Living
Room
5 160 53
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Figure A3.1. ΣTCPP concentrations in dust from three rooms of IH sampled from February to
December 2014.
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Figure A3.2. TCPP1:TCPP2 ratios from dust in IH sampled from February – December 2014.
Also included is mean ratio of all dust samples and IH purple SPF. *Indicates when IH was
unoccupied. IH dust and purple SPF are not statistically different (ANOVA, p=0.61).
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Table A3.4. Significance tests across sample groups. One-Way ANOVA, with Tukey's multiple
comparisons test on each pairwise sample grouping. *p<0.05, NS not significant, IH (insulated
house)
Insulation
Tests: FBI Green SPF White SPF
IH
Purple
SPF
FBI -
Green SPF * -
White SPF * NS -
IH Purple SPF NS * * -
IH tests: White SPF IH Purple SPF IH Air IH Dust
White SPF -
IH Purple SPF NS -
IH Air NS NS -
IH Dust NS NS NS -
Dust Tests: IH Dust
Vancouver
Homes
Vancouver Homes
w/ SPF
IH Dust -
Vancouver
Homes ** -
Vancouver
Homes w/ SPF NS NS -
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Table A3.5. TCPP concentrations in dust from Vancouver homes with different types of
insulation. No/DK (No insulation or don’t know, 24.±32), Yes/DK (Yes insulation but don’t
know what type, 19±18), Yes_FG(Yes fibre glass insulation, 20±26), Yes_PS(Yes polystyrene
insulation, 12±14), Yes_SPF(Yes SPF insulation, 65±32)
Mean Stdev
All Samples (no SPF) 23 28
No/DK 24 33
Yes/DK 19 18
Yes_FG 20 26
Yes_PS 12 14
Yes_SPF 65 32
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Table A3.6 Significance tests of samples to technical standard. One-Way ANOVA, with Tukey's
multiple comparisons test on each pairwise sample grouping. *<0.05 p<0.05, NS not significant,
IH (insulated house)
TCPP (SA)
Vancouver Homes Yes SPF n.s.
Vancouver Homes n.s.
IH Air <0.05
IH Dust <0.05
IH Purple SPF <0.05
White SPF n.s.
Green SPF n.s.
FBI <0.05
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References
Abbasi, G. et al., 2016. Product screening for sources of halogenated flame retardants in
Canadian house and office dust. Science of The Total Environment, 545-546, pp.299–307.
Saini, A. et al., 2015. Calibration of two passive air samplers for monitoring phthalates and
brominated flame-retardants in indoor air. Chemosphere, 137(January), pp.166–173.
Salamova, A. et al., 2013. High Levels of Organophosphate Flame Retardants in the Great Lakes
Atmosphere. Environment Science and Technology Letters, 1(1) pp. 8-14.
Shoeib, M. et al., 2014. Concentrations in air of organobromine, organochlorine and
organophosphate flame retardants in Toronto, Canada. Atmospheric Environment, 99,
pp.140–147.
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