Occurrence, Removal, and Environmental Emission of

Article

Occurrence, Removal and Environmental Emission of Organophosphate Flame Retardants/Plasticizers in a Wastewater Treatment Plant in New York State, USA Un-Jung Kim, Jung Keun Oh, and Kurunthachalam Kannan Environ. Sci. Technol., Just Accepted Manuscript • Publication Date (Web): 12 Jun 2017 Downloaded from http://pubs.acs.org on June 12, 2017

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Environmental Science & Technology

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Occurrence, Removal and Environmental Emission

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of Organophosphate Flame Retardants/Plasticizers in

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a Wastewater Treatment Plant in New York State,

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USA

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Un-Jung Kima, Jung Keun Oha, Kurunthachalam Kannana,b*

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a

Wadsworth Center, New York State Department of Health, and Department of Environmental

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Health Sciences, School of Public Health, State University of New York at Albany, Empire State

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Plaza, P.O. Box 509, Albany, New York 12201-0509, United States

9 10

b

Biochemistry Department, Faculty of Science and Experimental Biochemistry Unit, King Fahd Medical Research Center, King Abdulaziz University, Jeddah 21589, Saudi Arabia

11 12 13

*Corresponding author: [email protected]

14 15

For submission to : ES&T

ACS Paragon Plus Environment

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16

ABSTRACT

17

The occurrence and fate of 14 triester organophosphate flame retardants (OPFRs) and

18

plasticizers and their two diester metabolites were investigated in a wastewater treatment plant

19

(WWTP) in the Albany area of New York State. All target OPFRs were found in wastewater,

20

with average concentrations that ranged from 20.1 ng/L for tris(methylphenyl) phosphate

21

(TMPP) to 30100 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in influents and from 7.68

22

ng/L for TMPP to 12600 ng/L for TBOEP in final effluents. TBOEP was the dominant

23

compound in influents (max: 69500 ng/L) followed in decreasing order by tris(1-chloro-2-

24

propyl)phosphate (TCIPP; max: 14500 ng/L), bis(1,3-dichloro-2-propyl)phosphate (BDCIPP;

25

max: 4550 ng/L), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP; max: 3150 ng/L) and tris(2-

26

chloroethyl)phosphate (TCEP; max: 8450 ng/L). The fraction of TMPP sorbed to suspended

27

particulate matter (SPM) was 56.4% of the total mass in wastewater, which was the highest

28

among the target chemicals analyzed. The average concentrations of OPFRs in sludge were

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between 4.14 ng/g dw for tripropyl phosphate (TPP) and 7290 ng/g dw for TBOEP; for ash, they

30

were between 2.17 ng/g dw for TMPP and 427 ng/g dw for triphenyl phosphate (TPhP). The

31

mass loadings of OPFRs into the WWTP ranged from 0.02 mg/day/person for TPP to 28.7

32

mg/day/person for TBOEP, whereas the emission from the WWTP ranged from 0.01

33

mg/day/person for 2-ethylhexyl diphenyl phosphate (EHDPP) to 5.12 mg/day/person for TCIPP.

34

The removal efficiencies for OPFRs were slightly above 60% for TMPP, TBOEP and tris(2-

35

ethylhexyl)phosphate (TEHP) whereas those for other OPFRs were 0.995. Internal standards (mixture of eight deuterated OPEs) were

165

spiked into each calibration standard and sample at 20 ng/mL (for sludge and ash, 40 ng/mL).

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The limits of quantitation (LOQs) were set at a signal to noise ratio of 10 in sample extracts.

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These were determined to be 1–100 ng/L for wastewater (200 ng/L for TDBPP, 500 ng/L for

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BDCIPP and 1000 ng/L for EHDPP), and 0.05–10 ng/g dry weight for SPM and other solid

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matrices (Table S3). Procedural blank, field blank, laboratory blank, duplicate samples, and

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matrix spike samples were analyzed. To check for potential degradation of OPEs during sample

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storage, randomly chosen wastewater samples (n=3) were extracted at different time points at a

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monthly interval (for details see supporting information). Because background contamination is a

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critical issue in the analysis of OPEs, all containers and laboratory wares were thoroughly

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checked.1,24 The filter papers and plastic containers contained trace amounts of TnBP, TPhP,


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TBOEP, TCIPP and TMPP, but after rinsing with solvents, the background levels decreased

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below the LOQ. Randomly selected wastewater, SPM and sludge/cake/ash samples were

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fortified with known concentrations of OPEs (20–50 ng) for the determination of matrix effects

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(for details see supporting information). Eight deuterated internal standards were used to account

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for the matrix effects. Accuracy and precision were determined by fortification of samples with

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native and internal standards, and analysis of those samples through the entire procedure.

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Average recoveries ranged 85.5–110% for wastewater (n=8), 83.7–109% for SPM (n=8) and

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82.7–101% for other solid wastes (n=4). HPLC grade water was injected after every 25 samples

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and no carryover was observed. A mid-point calibration standard was injected after every 10 h to

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monitor for drift in instrumental sensitivity. The detailed information with regard to method

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performance and background contamination is presented in the supporting information.

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Data Analysis. The fraction of the total mass of target chemicals sorbed to SPM,

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removal efficiency in wastewater treatment processes, and mass loading to and emission from

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WWTPs were calculated by the equations Eqs. (1) and (2) as reported by Wang and Kannan (25)

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and Eqs. (3) and (4) as reported by Subedi and Kannan (26) 25–26

190 191

=

×

×

× 100 … (1)

192 193

%" =

&'' &'' )* +#, ×% )* &''(

&''(

&'' )* #$ ×% &''(

#$ ×%

× 100 … (2)

194 195

899

-./ 00 1/340 = 56 × 7 × 899+

8

8

× 89: × ;?@6;A … (3)


9


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196 197

B00/340 = CD 5E × 7" ×

899

899+

F + 5H × IJ"K ×

8

;?@6;A

×

8

89:

… (4)

198 199

Where, PSPM is the fraction of the total mass of OPFRs sorbed to SPM (%), CSPM is the

200

concentration of OPFRs in SPM (ng/g wet wt), MSPM is the weight of SPM (g), VW is the volume

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of wastewater (L) used to obtain the corresponding MSPM, CW is the concentration of OPFRs in

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wastewater (ng/L), Ci and Ce are the concentrations of OPFRs in influent (ng/L) and effluent

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(ng/L), respectively. Mass loading is the amount of individual OPFR introduced into WWTP

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(mg/day/person), F is the daily flow of wastewater (L/d), Cs is the concentration of OPFRs

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measured in sludge (ng/g wet weight), TSP is the total sludge production rate (g/day wet weight),

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population is the number of inhabitants served by the WWTP, and emission is the quantity of

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OPFRs discharged through wastewater effluent, SPM, and sludge (mg/day/person).

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RESULTS AND DISCUSSION

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Occurrence and Distribution in Dissolved Phase of Wastewater. Among 16 OPEs

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measured, TEP, TBOEP, TCEP, TCIPP, TiBP and TnBP were found in all wastewater samples

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(n=48). Conversely, EHDPP was not detected in any of the wastewater samples (Table 1).

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Occurrence of TPP, TDBPP, PBDPP, DPhP and BDCIPP is reported for the first time in

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wastewater. The total (sum) concentrations of the 16 OPEs in wastewater ranged between 2230

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ng/L and 117000 ng/L. TBOEP was the dominant compound in influents (mean: 30100 ng/L)

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followed by TCIPP (5120 ng/L), BDCIPP (2900 ng/L), TDCIPP (1720 ng/L) and TCEP (1430

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ng/L). In effluents, TBOEP was the predominant compound (12600 ng/L), followed by TCIPP


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(5950 ng/L) and TDCIPP (3110 ng/L). There was no significant day-to-day or monthly

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variations in the concentrations of target chemicals in samples analyzed in this study.

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Concentrations of TCIPP, TDCIPP, TCEP, TBP, TPhP and TBOEP have been reported in

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wastewater from various countries, including China, Norway, Sweden, Spain, Germany,

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Australia and Austria (Table S4).10–15,17 The mean concentrations of TPhP and TCEP in our

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study were lower than those reported from Norway, but higher than those reported from the other

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countries listed above. TBOEP and TCIPP concentrations were similar to those reported from

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Sweden, but higher than those reported from the other countries. The concentrations of TDCIPP

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were striking, occurring at 2–10 times higher than the mean values reported for European

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countries and 50 times higher than those reported for China. It is worth noting that 60–70% of

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the global production and consumption of OPFRs was in Europe and America from 1995 to

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2008.1,27,29 The measured concentrations of chlorinated OPFRs, except for TDCIPP, were up to 4

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times higher in our study than those previously reported for wastewater samples collected during

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2011-2012 in the state of Washington.20 Another explanation for high levels of TDCIPP found

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in this study is the flammability standard (California Technical Bulletin 117) for residential

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upholstered furniture that was implemented in 1975, which was expanded throughout the USA

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until 2013. In New York State, a law restricting the use of TDCIPP and TCEP in children’s

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products was in place during 2015 and 2013, respectively, but this does not include residential

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upholstered furniture (supporting information).28 Additionally, the phase out of PBDEs in the

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USA in 2005 has led to increased usage of TDCIPP, TCIPP and Firemaster 550 in household

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products.22-23

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OPFRs in Suspended Particulate Matter. Similar to that in dissolved phase, TEP, TBOEP,

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TiBP and TnBP were found in all SPM samples. TMPP, TPhP, TCEP, TCIPP, TDCIPP and


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TEHP were found in >80% of the SPM samples. TBOEP was predominant in the SPM of

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influents (mean: 1480 ng/g dry wt) followed by BDCIPP (352 ng/g dry wt), TDCIPP (134 ng/g

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dry wt) and TCIPP (94.9 ng/g dry wt). Except for a study from China, no earlier studies have

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reported OPFR concentrations in SPM (Table S5). EHDPP was not found in the dissolved phase,

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although it was found in the SPM of influent (Table 1). EHDPP can be hydrolytically degraded

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in aqueous solution (half-life: 110 days at pH 7),30 which might explain its absence in the

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dissolved phase in our study.

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OPFRs in Solid Matrices. OPFRs were measured in combined sludge, dewatered sludge cake

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(after belt press treatment of the combined sludge), and ash. TPhP, TBOEP, TCIPP, PBDPP and

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TnBP were detected in these three types of solid matrices. TBOEP was predominant in combined

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sludge (mean: 7290 ng/g dry wt), followed by TEHP (1190 ng/g dry wt), TDCIPP (783 ng/g dry

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wt), TCIPP (411 ng/g dry wt) and TPhP (373 ng/g dry wt). Similarly, TBOEP (8360 ng/g dry wt)

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was the dominant compound in sludge cake, followed by TEHP (1450 ng/g dry wt), TDCIPP

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(852 ng/g dry wt) and TPhP (426 ng/g dry wt). There was no significant difference in the

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concentrations of OPEs between combined sludge and sludge cake. However, the concentrations

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of OPEs decreased dramatically following the incineration of sludge, as evidenced from the

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concentrations in ash that were an order of magnitude lower than those in sludge. In ash, the

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concentrations of TPhP were the highest (427 ng/g dry wt), followed by EHDPP (288 ng/g dry

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wt), TDCIPP (205 ng/g dry wt) and TBOEP (181 ng/g dry wt). To the best of our knowledge,

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this is the first study to measure OPFRs in ash samples from WWTPs.

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The measured concentrations of OPEs in sludge were compared with those reported previously

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from Germany, Sweden and China (Table S6).10,14,16–19 There was a country-specific difference

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in the distribution of OPFRs in sludge, which is likely related to the consumption pattern of


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OPFRs. Nevertheless, TCIPP, TBOEP and EHDPP were the dominant compounds. Thus far,

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only one study reported the occurrence of diester OPFRs in sludge collected from China.19 The

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reported concentration of DPhP in sludge from China (18 ng/g dry wt) was approximately two-

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fold lower than in our study (41.1 ng/g dry wt).

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Partitioning of OPFRs and Removal Efficiency. The fraction of OPEs sorbed to SPM was

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calculated based on the concentrations measured in dissolved phase and SPM. The fraction of

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OPEs sorbed to SPM (normalized to sampling volume) was the highest for TMPP (56.4%),

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followed in decreasing order by TEHP (39.9%), TBOEP (21.9%), DPhP (17.7%), TiBP (14.8%),

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TPhP (14.8%), TDCIPP (14.7%), TPP (9.77%), TnBP (9.76%), TEP (5.73%), TCEP (5.68%),

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TCIPP (4.45%), and PBDPP (1.57%). These sorption coefficients are in accordance with their

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corresponding logKoc values (Fig. S2).1 These results suggest that the analysis of OPFRs in

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particulate fraction is important, especially for TEHP, which were found sorbed to particulates at

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> 40% of the total mass in wastewater (Fig. S2).

277

Removal efficiencies for OPEs in WWTPs were calculated based on the total concentrations

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(i.e., concentrations in both dissolved phase and SPM of wastewater) in influents and effluents.

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Due to the low detection frequencies, TDBPP and EHDPP were not included in this calculation.

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The average removal efficiencies for OPEs (Fig. 1) following the primary treatment ranged from

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-87% (PBDPP) to 46% (TMPP) whereas those after the secondary treatment were from -101%

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(PBDPP) to 70% (TMPP). Among the 16 OPEs investigated, only TMPP, TBOEP and TEHP

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were removed at >60% (Table S7). Similarly, in a WWTP in China, negative removal was

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reported for TCEP and TCIPP at -30.1% and -50.6%, respectively, while TMPP, TBOEP,

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EHDPP, and TPhP were removed at >80%.17 In two WWTPs in Washington State (USA), a

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negative removal for TCEP, TCIPP and TDCIPP was reported.20


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The observed differences in removal efficiencies among several OPEs may be related to their

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physicochemical properties (Table S7).31 For example, linear alkyl compounds (e.g., TnBP) were

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expected to degrade more quickly than branched compounds (e.g., TiBP) by microorganisms.17

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Similarly, chlorinated alkyl OPFRs were reported to be more resistant to degradation than non-

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chlorinated hydrocarbons.17 All three chlorinated triester OPFRs analyzed in this study showed a

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negative removal efficiency, which may be related to their resistance to biotransformation and

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formation from precursor compounds.32

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Composition Profiles and Mass Loadings of OPFRs.

We found that chlorinated-alkyl

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OPFRs and TBOEP were the major OPEs found in wastewater and solid matrices (Fig. 2). In

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particular, TBOEP, TCIPP and TDCIPP were the predominant OPFRs in wastewater. A similar

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composition of OPFRs was found in SPM, except that BDCIPP was found at relatively higher

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proportion in SPM. TBOEP was the dominant compound in sludge, and the proportions of

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TEHP, EHDPP and PBDPP in sludge were higher than in wastewater. The composition of OPEs

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in ash samples was remarkably different from that found in sludge, which suggests that

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incineration decomposes certain types of OPEs (Fig. 2). One of the suspected sources of OPFRs

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in WWTPs is the discharge from laundry.20,33

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Calculation of the average daily mass loading of OPEs into the WWTP was based on the

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concentrations measured in influents and the daily flow of wastewater (Fig. 3A). The estimated

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average daily mass loadings per capita ranged from 0.02 mg/day/person (TPP) to 28.7

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mg/day/person (TBOEP). Except for TBOEP (which had the highest mass loading), chlorinated

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alkyl OPFRs showed higher mass loadings per capita (ranging between 1.2 and 4.5

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mg/day/person) than non-chlorinated alkyl or aryl OPEs.


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The calculated mass loading of OPEs into the WWTP seemed to be related to the production

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volume of these chemicals, which is in the decreasing order of TCIPP > TDCIPP ≈ TPhP >

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TMPP > TCEP > PBDPP.1 According to the U.S. Environmental Protection Agency (EPA;

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2010/2011), the annual production volume of TCIPP (19,600 tons) was the highest, followed by

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TDCIPP (7200 tons), TPhP (3800 tons), TBOEP (2000 tons), TnBP (1000 tons), EHDPP (145

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tons) and DPhP (60 tons). The global production volumes of TBOEP and TEHP in the 1990s

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were 5000–6000 tons and 1000–5000 tons, respectively.29

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The estimated mass loadings of OPEs in our study were 5 to 50 times higher than those

317

reported from Australia.15 This difference may be related to higher production and consumption

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of OPEs in the USA than in Asia-Pacific countries.1,17,27,29 The estimated daily mass loading per

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capita was extrapolated to annual loadings in the USA, based on the assumption that the volume

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of wastewater generated in the USA was approximately 85 trillion liters per day.20 The national

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loadings of OPEs into WWTPs were compared with the reported production volume. It was

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found that the mass loadings of TPhP, TCIPP, TDCIPP, and TnBP into WWTPs were 1.3–2.8%

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of the annual production, which is consistent with those reported previously.14,20 This further

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suggests that large proportions of OPEs are still present in products, and may eventually reach

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landfills.

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Environmental Emission and Fate. Average daily per capita emission of OPEs from the

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WWTP was calculated based on the measured concentrations in effluent, SPM and sludge (Fig

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3B). The average daily emission of TCIPP was the highest at 5.12 mg/day/person, followed by

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TBOEP (3.72 mg/day/person), TDCIPP (2.89 mg/day/person), BDCIPP (1.58 mg/day/person)

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and TCEP (0.96 mg/day/person). Although considerable amounts of OPFRs were removed

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during the treatment processes (e.g., TBOEP at 25.0 mg/day/person, BDCIPP at 1.23


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mg/day/person and TEHP at 0.34 mg/day/person), appreciable amounts of chlorinated OPFRs

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were still discharged into the aquatic environment. The possibility of formation of two diester

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metabolites (i.e., DPhP and BDCIPP) from their corresponding triester parent OPFRs (i.e., TPhP

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and TDCIPP) was examined by calculating the concentration ratios between dister and triester

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OPFRs and described in the supporting information. Some of the OPEs are expected to be

337

rapidly hydrolyzed in water and hydrolytic metabolites need to be examined in future studies.

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Furthermore, the bioconcentration factors (BCF) of EHDPP, PBDPP, TnBP, TMPP, TBOEP,

339

and TEHP have been reported to be above 1000.1 Considering elevated levels of TBOEP and

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TDCIPP found in wastewater and low removal efficiencies, further studies are needed to assess

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the environmental occurrence of fate of OPEs in the aquatic environment.

342 343 344 345 346 347 348 349 350 351 352 353 354


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355 356 357 358 359 360 361

FIGURES

362 363

364 365

Fig. 1. Average removal efficiency (± standard deviation, %) of organophosphorus flame

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retardants (OPFRs) after primary and secondary treatments in wastewater treatment plants (both

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wastewater and SPM were included in the calculation of the removal efficiency)


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369 370

Fig. 2. Composition of 16 organophosphorus flame retardants in various types of samples

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analyzed from a wastewater treatment plant in the Albany area of New York (categorized as aryl,

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non-chlorinated alkyl, chlorinated-alkyl and others)

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375 376

Fig. 3. Average daily per capita mass loadings (A) and emission (B) of organophosphate flame

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retardants in a wastewater treatment plant in the Albany area of New York

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Table 1. Concentrations of organophosphate flame retardants in wastewater, suspended

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particulate matter (SPM), sludge, dewatered sludge cake and ash samples

Compound

TMPP

TEP

TPhP

TPP

TBOEP

TCEP

TCIPP

TDBPP

TDCIPP

TEHP

EHDPP

PBDPP

TiBP

TnBP

DPhP

BDCIPP

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MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F. MEAN MIN MAX D.F.

Influent 20.1 3.60 40.5 38% 501 184 775 100% 491 187 845 94% 21.2 5.65 45.8 75% 30100 129 69500 100% 1430 195 8450 100% 5120 820 14500 100% 449 370 530 19% 1720 259 3150 94% 392 13.1 1850 94% 0% 462 99.0 1530 81% 57.9 0.425 102 100% 291 50.8 649 100% 263 30.0 1290 88% 2900 1830 4550 56%

Wastewater (ng/L) Secondary Primary effluent effluent 7.68 47.9 6.11 7.26 10.6 206 19% 38% 442 473 265 295 630 665 100% 100% 293 390 147 178 595 680 81% 94% 18.9 23.5 6.60 12.3 39.1 44.8 88% 81% 12600 38700 35.8 73.3 101000 82400 100% 100% 1100 1090 552 326 2270 2280 100% 100% 5950 6580 965 3750 9350 23400 100% 100% 472 409 316 245 565 585 25% 31% 3100 2380 565 1480 8200 4420 100% 100% 50.5 328 4.43 21.0 169 910 50% 100% 0% 0% 764 547 188 191 2660 1630 100% 88% 95.4 56.1 17.2 24.4 255 92.4 100% 100% 301 321 69.8 150 769 614 100% 100% 252 188 22.2 25.0 505 458 69% 94% 1700 2690 610 1760 3630 4100 44% 56%

Influent 8.30 2.10 20.6 100% 9.90 4.32 23.9 100% 33.8 8.27 76.5 88% 0.731 0.277 1.85 75% 1480 46.9 3990 100% 22.5 7.95 54.4 100% 94.9 29.7 216 100% 21.2 19.5 22.8 13% 134 29.1 229 94% 66.5 14.3 121 100% 71.5 50.6 104 31% 3.99 1.17 7.52 69% 3.47 1.72 6.32 100% 12.4 1.74 28.6 100% 24.8 4.68 122 44% 352 105 765 44%

SPM (ng/g dry wt) Secondary Primary effluent effluent 3.41 5.66 0.699 1.43 23.4 14.8 81% 100% 8.06 11.4 1.48 2.40 16.7 25.7 100% 100% 14.6 29.5 6.96 13.4 38.5 67.2 94% 100% 0.758 0.687 0.185 0.254 1.52 1.80 81% 69% 471 1700 3.36 26.0 2480 4380 100% 100% 17.9 20.4 4.11 7.41 35.1 40.4 100% 94% 71.9 101 24.3 17.1 130 233 94% 100% 26.3 2.22 61.8 19% 0% 125 143 46.5 45.3 252 302 94% 94% 5.24 37.2 0.231 7.24 14.2 107 94% 100% 0% 0% 0.892 1.14 0.092 0.112 1.48 3.03 69% 38% 2.71 3.61 1.41 0.953 4.61 5.81 100% 100% 8.57 12.1 2.71 3.06 18.2 26.2 100% 100% 31.6 9.37 2.07 3.75 153 21.4 38% 50% 259 224 216 135 315 277 31% 31%

Combined sludge (ng/g dry wt)

Ash (ng/g dry wt)

Sludge cake (ng/g dry wt)

81.7 5.62 124 100% 36.8 2.77 121 92% 373 158 589 100% 4.14 1.60 10.4 77% 7290 3700 11500 100% 40.1 13.6 82.5 62% 411 64.4 1670 100% 195 122 333 23% 783 541 1340 100% 1190 737 1830 100% 225 145 450 54% 152 33.1 314 100% 19.9 5.46 94.7 100% 41.7 26.7 64.9 100% 40.5 17.7 132 92% 397 8%

2.17 0.293 4.53 25% 10.9 1.97 34.9 100% 427 90.1 1480 100% 11.3 3.20 25.3 100% 181 35.0 545 100% 47.7 14.1 198 75% 60.2 10.0 158 100% 19.4 6.05 59.5 33% 205 98.7 479 100% 21.4 0.740 67.6 67% 288 136 562 50% 83.0 30.1 254 100% 10.3 4.82 21.4 92% 11.7 3.78 27.6 100% 33.6 14.8 81.6 83% 0%

65.3 35.2 100 100% 49.1 2.99 189 100% 425 223 688 100% 6.45 3.07 10.3 92% 8360 2490 13500 100% 78.9 48.6 109 15% 290 132 661 100% 335 288 397 38% 852 431 1700 85% 1450 607 2750 100% 224 121 427 54% 174 54.1 555 100% 26.5 0.608 131 100% 44.8 13.8 106 100% 41.7 10.9 210 69% 331 62.4 595 23%

(D.F.: detection frequency)

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TOC ART

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ASSOCIATED CONTENT

387

Supporting Information.

388

Additional information with regard to instrumental parameters used in the analysis of

389

organophosphate esters (OPEs), QA/QC details, sample and WWTP parameters, detailed OPE

390

concentrations and comparison to the values found in the literature are given in the supporting

391

information (SI 1–5, Table S1–S7, Fig. S1–S2). The Supporting Information is available free of

392

charge on the ACS Publications website.

393 394

AUTHOR INFORMATION

395

Corresponding Author

396

*Phone:

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[email protected].

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Author Contributions

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The manuscript was written through contributions of all authors. All authors have given approval

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to the final version of the manuscript.

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Notes

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The authors declare no competing financial interest.

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ACKNOWLEDGMENTS

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+1-518-474-0015;

fax:

+1-518-473-2895;

e-mail:

We thank individuals at the WWTP and Mr. Jingchuan Xue (Wadsworth center) for assistance with the collection of samples.


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