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Analysis and Relative Distribution of OPFR Compounds in Wastewater Treatment
Million B. Woudneh, Coreen Hamilton, Guanghui Wang, Richard Grace, John R. Cosgrove
Sidney B.C., Canada, V8L 5X2
OPFRs are commercial additives widely used to inhibit, suppress or delay the production of flames.
Trialkyl phosphates Halogenated phosphatesTriaryl phosphates
• Restrictions on polybrominated diphenyl ethers (PBDEs) has increased demand for OPFRs.
• Since they are not chemically bonded agents, OPFRs use as additives results in easy release to the environment.
Importance of Organophosphate Flame Retardants (OPFRs)
Alkyl phosphatesShort -hand
Halogenated alkyl phosphatesShort -hand
Triethyl phosphate TEP Tris(2-chloroethyl) phosphate TCEP
Tripropyl phosphate TPrP Tris(2-chloroisopropyl) phosphate TCPP
Tributyl phosphate TBP Tris(1,3-dichloro-2-propyl) phosphate TDCPP
Tris(2-ethylhexyl) phosphate TEHP Tris(2,3-dibromopropyl) phosphate TDBPP
Aryl phosphates Other phosphates
Triphenyl phosphate TPP Tris(2-butoxyethyl) phosphate TBEP
Tricresyl phosphate TCrP Tetrakis(2-chlorethyl) dichloroisopentyldiphosphate
V6
2-Ethylhexyl-diphenyl phosphate EHDPP
•Target compounds selected based on:CMP = Chemical management planTSCA = EPA's Toxic Substances Control ActSFEI = San Francisco Estuary InstituteCECBP = California Environmental Contaminant biomonitoring program listLeading researchers in the field
Target Analytes of Interest to Regulators & Scientists
Matrices: Influent, Effluent, Soil, Sediment, Biosolid
Solids+ surrogates
Extraction:Soxhlet, DCM:EtAOc
Cleanup: - NH2 SPE, Silica
Solvent exchange to MeOH
Analysis by LC-MS/MS
Aqueous+ surrogates
Extraction:L-L with DCM
Cleanup: -NH2 SPE
Surrogates
2H15-TEP
2H12-TCEP
2H21-TPrP
2H18-TCPP
2H15-TDCPP
13C15-TPP
2H27-TBP
Recovery
2H15-TPP
Initial and ongoing QCs: 5 replicates MS/MSD
QC samples: 1 Lab blank 1 Spiked sample 1 Duplicate
Isotope labeled surrogates: 7 Surrogates 1 Recovery
Method Makes Use of Eight Isotope-Labeled Standards
min6.0 10.0 14.0 18.0 22.0
327> 152
TPP
min
431> 99
TDCPP
min
583 >361
V6
min
329> 99
TCPP
min
225> 99
TPrP
min
285 > 223
TCEP
min
183 > 99
TEP 8.59
9.69
13.14
13.31
14.24
16.08
16.67
Rela
tive
resp
onse
min
17.0 21.0 25.0 29.0
435 >99
TEHP
27.07
min
363 > 251
EHDPP22.01
min
369> 165
TCrP
min
399 > 299
TBEP
18.85
min
267 > 99
TBP
17.98
min
716 >99
TDBPP
17.25
20.89
Rela
tive
resp
onse
Column: - Waters C18MS
Mobile phase: - 0.1% HCOONH4 + 0.1%
HCOOH MeOH
Two MRMs per compound
All Analytes Separated by Mass and Time
TEP TCEP TPrP TCPP V6 TDCPP TPP TDBPP TBP TBEP TCrP EHDPP TEHP0
20
40
60
80
100
120
140
Recovery from reagent water and sediment samples
Aqueous Solids
Perc
ent r
ecov
ery
TEP
TCEP
TP
rP
TCPP
V6
TDCPP
TPP
TDBPP
TBP
TBEP
TC
rP
EHDPP
TEHP
0
20
40
60
80
100
120
140
MS recovery from influent, effluent and biosolids
Effluent Influent Biosolid
Perc
ent r
ecov
ery
Reporting limits: - 0.1 to 5 ng/L for a 0.5 L sample - 0.01 to 0.5 ng/g for a 5 g wet sample
Quantitative measurement of OPFRs from aqueous samples, sediment and biosolids
PRIMARY EFFLUENT Surface
WatersPrimary Clarifier
Aeration Basin
Secondary Clarifier Disinfection
Bio-Gas Digestion Dewatering Land Application
PRIMARY
SLUDGE
WASTE ACTIVATED SLUDGE
TREATED BIOSOLIDS
RAWINFLUE
NT
SECONDARY EFFLUENT
Sampling Throughout the Process
= Sample points at the study site
TPrPTCEP
TBPTCrP
TEHP
TDCPPTBEP
0
200
400
600
800
4 6 52 61 69 75 92172181219
2,236Biosolids
Conc
. ng/
g, d
ry
TPrP
EHDPP TCrP
TPP
TDCPP TCPP
TBP 0
200
400
600
800
1 1 26 27133
227344
440547581
Final Effluent
Conc
. ng/
L
3292
3807
ND ND ND
TPrP
TEHP
EHDPP TPP
TEP TCEP
TBEP 0
200
400
600
800
16 33 40 41 90
227299
380
598
7473,293Raw Influent
Conc
. ng/
L
ND
ND
ND
ND
TPrP V6TEHP
TCrP TEPTBP
TBEP0
200
400
600
800
8 2172 76 98 106139168174196
1,069Primary Sludge
Conc
. ng/
g, d
ry
ND ND
1069
OPFRs survive secondary wastewater treatment
Distribution of OPFRs
BDE influent and effluent data from Kim, et al., Water Research 47, no. 7: 2213–21. BDE influent and effluent data from Kim, et al., Water Research 47, no. 17: 6496–6505. BTBPE and DBDPE data from Grace et al. BFR 2011, Boston.
Influent Effluent Biosolid0
1000
2000
3000
4000
5000
6000
7000
5763
2328
3167
210 12
1,900
46 19 268
Comparison of ∑OPFR conc. vs. other FRs in sec-ondary wastewater treatment
∑ OPFRs ∑ BDE BTBPE DBDPE
Tota
l con
c. ng
/L, o
r ng/
g, d
ry
• Final effluent and biosolid from secondary wastewater treatment are significant sources of OPFRs.
• Relative to brominated diphenyl ethers, OPFRs have a much higher affinity for the aqueous phase.
OPFR Concentrations Significantly Higher than Other FRs
AXYS OPFR MethodSummary and Conclusions
A reliable method for quantitative measurement of OPFRs from aqueous, sediment and biosolid samples.
The method makes use of eight isotope-labeled surrogates. OPFRs survive secondary wastewater treatment. Final effluent and biosolids from secondary wastewater treatment are
significant sources of OPFRs. OPFRs have much more affinity for the aqueous phase relative to BDEs OPFRs are present at significantly higher concentrations than BDEs and
other FRs.
For Follow-up: mwoudneh@axys.com
Acknowledgements
Dr. Shirley Anne Smyth and her research group at Environment Canada are thanked for their assistance in sample collection and water quality data analysis.
Dr. Heather M. Stapleton is thanked for providing ‘V6’ technical standard for the initial method development.
Supplemental Information
NH2 1 g SPE - Condition: - with 2 x col. vol of HXN and 2 x col. Vol of DCM - Load: 1 mL extract in Hexane - Wash: 5 mL 20:80 DCM:Hexane (DISCARD) - Elute: 12 mL of 1:9 EtOAc:DCM (COLLECT)
Silica, 8 g, 5% deactivated - Pack column in hexane - Load: 1 mL DCM extract - Wash: 20 mL 15: 85 DCM:Hexane (DISCARD) - Elute : 100 mL of 1:2 DCM:ETOAc (COLLECT)
Before cleanup
Aftercleanup
Clean extracts were achieved with NH2 and silica columns
SeaStar Water Effluent Influent Soil Bio-solid0
50
100
150
200
Matrix effects for 0.5 L reagent water, 0.5 L effluent and in-fluent, 10 g soil and biosolid samples
TEP TCEP TPrP TCPP V6 TDCPP TPP TDBPP TCrP EHDPP TEHP
Perc
ent r
ecov
ery * *
Samples sizes:• 0.25 L for influent • 0.50 L for effluent and • 2.5 g wet for biosolid • 10 g for biosolid
These samples sizes were demonstrated to have no matrix effects.
No significant matrix effects
Reagent
0 20 40 60 80 100 120 140 1600
20
40
60
80
100
120
Stability of TEP, TCEP, TPrP
TEP TCEP TPrP
Number of Days in storage
Perc
ent r
ecov
ery
0 20 40 60 80 100 120 140 1600
20
40
60
80
100
120
Stability of TPP, TDBPP, TBP
TPP TDBPP TBP
Number of Days in storage
Perc
ent r
ecov
ery
0 20 40 60 80 100 120 140 1600
20
40
60
80
100
120
Stability of TCPP, V6, TDCPP
TCPP V6 TDCPP
Number of Days in storage
Perc
ent r
ecov
ery
0 20 40 60 80 100 120 140 1600
20
40
60
80
100
120
Stability of TBEP, TCrP, EHDPP, TEHP
TBEP TCrP EHDPP TEHP
Number of Days in storage
Perc
ent r
ecov
ery
OPFR Standard Stability in Methanol
OPFR Extract Stability
TEP
TCEP
TP
rP
TCPP
V6
TDCPP
TPP
TDBPP
TBP
TCrP
EHDPP
TEHP
020406080
100120140
Reagent water extracts after 4 months in storage
SeaStar Water
Perc
ent r
ecov
ery
TEP
TCEP
TP
rP
TCPP
V6
TDCPP
TPP
TDBPP
TBP
TCrP
EHDPP
TEHP
0
20
40
60
80
100
120
140
Effluent extracts after 4 months in storage
Effluent
Perc
ent r
ecov
ery
TEP
TCEP
TP
rP
TCPP
V6
TDCPP
TPP
TDBPP
TBP
TCrP
EHDPP
TEHP
020406080
100120
Influent extracts after 4 months in storage
Influent
Perc
ent r
ecov
ery
TEP
TCEP
TP
rP
TCPP
V6
TDCPP
TPP
TDBPP
TBP
TBEP
TC
rP
EHDPP
TEHP
020406080
100120
Sediment and bio-solid extracts after 4 months in storage
Sediment Biosolid
Perc
ent r
ecov
ery
MRM transitionsTarget Analyte Typical Retention
Time (minutes)Parent Ion
Mass 1DaughterIon Mass 1 Quantified Against
TEP 8.68 183 99.0 (127) d15-TEPTCEP 9.79 284.9 222.9 (63.1) d12-TCEPTPrP 13.32 225.1 99.0 (140.9) d21-TPrPTCPP 13.50 329.1 (327.1) 99.0 (99.0) d18-TCPPV6 14.38 582.8 360.8 (99.0) d15-TDCPPTDCPP 16.28 430.9 99.0 (208.9) d15-TDCPP TPP 16.86 327.1 152.0 (77.1) 13C18-TPPTDBPP 17.44 715.5 (698.6) 99.0 (99.0) d15-TDCPPTBP 18.17 267.1 99.0 (155.0) d27-TBP
TBEP 19.09 399.1 299.0 (199.0) d27-TBP
TCrP 21.08 369.1 165.0 (91.0) 13C18-TPP
EHDPP 22.20 363.1 250.9 (77.1) 13C18-TPP
TEHP 27.21 435.3 99.0 (211.0) d27-TBP
Surrogate Standard
d15-TEP 8.55 198.0 102 (134) d15-TPPd12-TCEP 9.70 297.0 231.9 (67.1) d15-TPPd21-TPrP 13.10 246.2 102 (150.1) d15-TPPd18-TCPP 13.41 347.0 (345) 102 d15-TPPd15-TDCPP 16.18 446.0 102 (216) d15-TPP13C18-TPP 16.86 345.0 164.1 (83.1) d15-TPPd27-TBP 17.93 294.2 102 (166.1) d15-TPP
Recovery Standard
d15-TPP 16.67 342.1 160.1 (82.1) d15-TPP
LC Gradient
Time (min) Flow mixture 1 LC Flow Rate Program
GradientCurve
0.015% solvent A
85% solvent B0.2 mL/min 1
3.050% solvent A
50% solvent B0.2 mL/min 6
1070% solvent A
30% solvent B0.2 mL/min 6
1885% solvent A15% solvent B
0.2 mL/min 6
2195% solvent A5% solvent B
0.2 mL/min 4
3095% solvent A
5% solvent B0.25 mL/min 6
3115% solvent A
85% solvent B0.2 mL/min 1
3515% solvent A
85% solvent B0.2 mL/min 1
Calculated Log KD vs Log Kow for OPFRs
TCEP
TB
P TE
P V6
TCPP
TDCPP
TPrP
TDBPP
TPP
TBEP
TE
HP
EHDPP
TCrP
0.01.02.03.04.05.06.07.08.09.0
10.0
Log Kd log Kow log Koc
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