Organophosphate Esters (OPEs) as Emerging Contaminants ......OPEs have been measured in indoor air...

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.

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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.

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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

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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


4.4 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

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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.

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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.


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




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,


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.



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



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


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.



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.



14(9), pp.2482–7.

Cho, K.J., Hirakwa, T. & Mukai, T., 1996. Origin and stormwater runoff of TCP (triscresyl

phosphate) isomers. Water Research, 30(6), pp.1–12.

I.O.M. Consulting,, 2008. Data on Manufacture, import, export, uses and releases of HBCDD as

well as information on potential alternatives to its use. Produced for European Chemical

Agency.

Dixon, E., Richman, R. & Pressnail, K., 2012. Nested Thermal Envelope Design construction:

Achieving significant reductions in heating energy use. Energy and Buildings, 54, pp.215–

224.

Fan, X. et al., 2014. Science of the Total Environment Simultaneous determination of thirteen

organophosphate esters in settled indoor house dust and a comparison between two

sampling techniques. Science of the Total Environment, The, 491-492, pp.80–86.

Fromme, H. et al., 2014. Organophosphate flame retardants and plasticizers in the air and dust in

German daycare centers and human biomonitoring in visiting children (LUPE 3).

60

Environment International, 71, pp.158–163.

Harrad, S. et al., 2010. Indoor contamination with hexabromocyclododecanes, polybrominated

diphenyl ethers, and perfluoroalkyl compounds: an important exposure pathway for people?

Environmental science & technology, 44(9), pp.3221–31.

Kemmlein, S., Hahn, O. & Jann, O., 2003. Emissions of organophosphate and brominated flame

retardants from selected consumer products and building materials. Atmospheric

Environment, 37, pp. 5485–5493

National Research Council, 2000. Toxicological risks of selected flame-retardant chemicals,


Newton, S., Sellstrom, U. & De Wit, C. A., 2015. Emerging flame retardants, PBDEs, and

HBCDDs in indoor and outdoor media in Stockholm, Sweden. Environmental Science and

Technology, 49(5), pp.2912–2920.

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

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pp.44–55.

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61

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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


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


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


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


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


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


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


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


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


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.

108

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).

109

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

110

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

111

Figure A3.1. ΣTCPP concentrations in dust from three rooms of IH sampled from February to

December 2014.

112

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).

113

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 -

114

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

115

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

116

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.



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