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Transcript of thesis defense 4
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Methods and devices for assessment of fiprole pesticides in engineered waterways
Sam Supowit, environmental engineeringPhD thesis defense9/25/2015
Committee: Rolf Halden, chair; Paul Westerhoff; Paul C. Johnson
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Importance
Methods• Sampling• Analysis
Identify contributing contaminants
DATA
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Major contributions• Method for quantifying fipronil and byproducts in
wastewater/sludge• Time-integrating sampler that samples trace level
contaminants (e.g., fipronil) across the sediment-water interface
• Data on occurrence of fipronil in the environment• Fate of fipronil in a wastewater treatment plant
and wetland via a mass balance approach
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IntroductionFipronil• Highly toxic to invertebrates• Occurs at trace levels (ng/L)• Lipophilic• Emerging contaminant• Byproducts equally/more toxic
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Fipronil Sulfide Sulfone Amide Desulfinyl
Fiproles
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Introduction – Rationale
Waterway
WWTP
Fish
Aquatic insects
Angiosperms
Pollinators
Birds
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Introduction – Rationale • Only two prior studies assessed fiproles in
wastewater matrices
• Fiproles may be resistant to degradation in WWTPs (Heidler & Halden, 2009)
• Improved precision/sensitivity necessary to assess fate of fiproles in WWTPs and downstream waters
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Introduction – Hypotheses
1.
2.
3.
Total fiprole mass balance
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Introduction – Hypotheses
1.
2.
3.
≤
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Introduction – Hypotheses
1.
2.
3. WWTP mass balance
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• Fiproles are largely resistant to degradation in treatment.Hypothesis
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• Fiproles are largely resistant to degradation in treatment.Hypothesis
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• Fipronil implicated in colony collapse disorder
• Highly toxic to bees LD50 = 1-6 ng/bee
Introduction – Rationale
Compound Procambarusa Hyalella aztecab Diphetor hagenib 33 OC urban
water conc. (µg/L)
Half-life
31 LC50 (µg/L) 30 LC50 (µg/L)
30 EC50 (µg/L)
30 LC50 (µg/L)
30 EC50 (µg/L)
34 Silt loam (d)
35 Facultative conditions (d)
Fipronil 14.3-19.5 1.3-2.0 0.65-0.83 0.20-0.57 0.11-0.21 0.05-0.39 21±0.15 -
-desulfinyl 68.6 - - - - 0.05-0.13 - 217-497
-sulfide 15.5 1.1-1.7 0.007-0.003 - - ND >200 195-352
-sulfone 11.2 0.35-0.92 0.12-0.31 0.19-0.54 0.055-0.13 0.05-0.19 >200 502-589 aProcambarus species were clarkii and zonangulus. bValues for H. azteca and D. hageni are the 95% confidence interval. OC – Orange County, California ND – non detect
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Introduction – Rationale
http://www.actbeyondtrust.org/wp-content/uploads/2013/07/IUCN2013sympo03_sluijs.pdf
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≠
Introduction – Rationale
=
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Methods1. Review active sampling plans– Identify and critique various means of sampling for
ascertaining fate of trace level HOCs 2. Optimize sampling, extraction, and analysis for precise,
trace-level detection of fiproles3. Design, develop, and deploy a sampler to assess fiproles
in pore water and surface water4. Assess the mass of fiproles in wastewater process
streams and wetland– Apply appropriate sampling strategy, and analysis method
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1. Review of “active” sampling strategies
Snapshot in time
Volume sampled proportional to flow
Constant sample rate Average concentrations
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1. Review of “active” sampling strategies: pore water sampling
SPE
Automatic water collection
Discrete grab sampling
In situ extraction
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Feature
Grab Water collection In situ extraction
Bottle/bailer
Kemmerer sampler
MINI-POINT Rhizon
Thin layer film
sampler
Syringe In situ SPE
Active GFF/PUF sampling
ISCO/Sigma
Gulper samplers
Osmo-Sampler CFIS CSS Automatic
SPE units* CLAM PROFEXS SAMOS
Sampling specification
Time integration None0
None0
Potentiala
0 Potentiala
0None
0 Potentiala
0 None
0Excellent
0 None
0Good294,95
Good159
Good159
Potential196
Good17
Potential0
Potential0
Flow-weighting None0
None0
None0
None0
None0
None0
None0
Excellent13097-99
None0
None0
Potential0
None0
Potential0
None0
Potential0
Potential0
Time discrete Yes12100,101
Yes70102
Yes3284
Yes70102
Yes3989,103
Yes262,104
Yes187
Yes1105
Yes1106
No0
No0
No0
Yes30107,108
No0
Yes4769
Yes3989,103
Sample handlingVolatile loss reduction
Poor0
Poor0
Potential0
Potential0
Potential0
Potential0
Potential0
Very poor0
Potential0
Potential0
Potential0
Potential0
Potential0
Fair17
Potential0
Potential0
Adsorption loss reduction (HOCs)
Fair0
Potential0
Potential0
Poor0
Potential0
Potential0
Potential0
Fair0
Potential0
Potential0
Potential0
Potential0
Potential0
Good17
Potential0
Potential0
Applications
Mass balances Fair3900109-111
Potential0
N/A0
N/A0
N/A0
Potential0
Potential0
Excellent13997,112
N/A0
Potential0
Potential0
Potential0
Potential0
Potential0
Potential0
Potential0
Spacial characterization
Fair50113,114
Good12115
Good0
Good12115
Potential0
Good0
Good0
Good10116
Good1117
Potential0
Potential0
Potential0
Good0
Excellent2118
Good0
Good0
MatricesSediment pore water
Difficult860119,120
No0
Yes3284,121
Yes130102,122
No0
Potential0
No0
No0
No0
No0
No0
No0
Potential0
No0
No0
No0
Wastewater Yes1990123,124
Yes50125,126
No0
No0
Yes0
Yes0
Yes0
Yes273127,128
No0
No0
Yes0
Yes0
Yes0
Yes0
Yes0
Yes0
Cost range $ $$ $$ $$ $$ $ $ $$$ $$$ $$$ $$ $$ $$$ $$$ $$$ $$$$
Automation N/A Potentiala Potentiala Potentiala None Potentiala None High High Moderate Moderate Moderate Moderate Moderate High High
Commercially available Y N N Y N Y Y Y N Y Y N N Y N N
a – If an automatic pump were to be integrated (not present in current design)
*Any device aside from the CLAM that automatically extracts water using a pump and SPE resin.
WWTPMass balance + =
New wetland sampler
1. Review of “active” sampling strategies: comparisons
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2. Water analysis method1000 mL
RAS & PS
500 mg/3 mL Strata XL 4 mL eluate x 2
Concentrations calculated by both standard addition and isotope dilution
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2. Sludge analysis method
Surrogate addition
Acetone extraction Shake Centrifuge
Solvent switch to hexane
Cleanup on Florisil
Analyze by LC-MS/MS
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3. New sampling device testingFiproles in a wetland• Sample across the sediment-water interface
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4. Fiproles in a WWTP
PP
Wetland
River
==
Primary sedimentatio
n basins
Secondary sedimentatio
n basinsHeadworks Aeration
basins
PS Thickening Centrifuge
WAS Thickening Centrifuge
Acid Phase
Methane Phase
DS Thickening Centrifuge
Centrate Treatment
Disinfection
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SamplingWWTP assessment• Sample all process streams
using most appropriate sampling method
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Results – Analytical method
MRM chromatograms for spiked and unspiked biosolids
• 20 ppb spike• High intensities (> 106 cps)• High S/N
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Table 3. Method detection limits for fiproles from various studies in water and sludge matrices.
Water (ng/L) Sludge (pg/g)
Source Schlenck et al, 2001
Heidler & Halden, 2009 Hladik et al, 2008 Weston &
Lydy, 2014b This study Heidler & Halden, 2009 This study
Matrix Surface water Wastewater inf/eff River water Wastewater
influentSurrogate
wastewater Sludge Surrogate sludge
ExtractionLLE (pentane) +
normal phase SPE (Florisil)
Reversed phase SPE
(HLB)
Reversed phase SPE (HLB)
LLE (DCM) + filtration
+ GPC
Reversed phase SPE
(StrataTM-X)
SLE (MeOH/acetone)
SLE (acetone) + normal phase SPE
(Florisil)
Analysis GC-ECD LC-MS/MS GC-ion trap MS GC-MS LC-MS/MS & GC-MS/MS LC-MS/MS LC-MS/MS &
GC-MS/MS
Fipronil 500 10-20 2-2.9 0.88-1.49 0.045 400 20
-sulfide 1000 N/A 1.8-2.2 0.88-1.49 0.16 N/A 140
-sulfone 2000 N/A 3.5-7.0 0.88-1.49 0.07 N/A 100
-amide N/A N/A N/A 0.88-1.49 0.3 N/A 90
-desulfinyl 500 N/A 1.6-2.7 0.88-1.49 0.77 N/A 240
a The range shown (0.88-1.49) was given for all fiproles, and no individual MDLs are published
HLB, hydrophilic-lipophilic balance; DCM, dichloromethane; MeOH, methanol; GPC, gel permeation chromatography; SPE, solid phase extraction; LLE, liquid-liquid extraction; SLE, solid-liquid extraction
Results – Analytical method
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Applying the method• Use modified method to validate new biphasic
sampling device
• Use method to perform WWTP mass balance
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Sampler development–the in situ sampler for biphasic water sampling (IS2B)
1. Designed and built an “active” biphasic sampler (IS2B)
2. Applied analytical method involving in situ SPE using IS2B
3. Validated method using fiproles as targets– Deployed device and demonstrated utility
End cap Shell Peristaltic pump
Porewater inlet manifold
SPE cartridges
Outlet manifold
InletsBulk water inlet manifold End cap
Inlets/outlet
B - Offline
A - Online
Organic Eluent Non-volatile &semi-volatile organics0.2 µm Filter
LC-MS/MS
Bulk water
Pore- Water
Discharge into bulk water
× 3 SPE cartridges
Manifolds
× 3
Results – sampler
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Features
• Time-integrated pore water sampling
• Biphasic sampling
• In situ SPE
• Enables low detection limits
Results – sampler
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• Results similar to conventional method
• Successful deployments of 48 hrs
• Yielded time-integrated values
• Precision lower than grab sample field replicates
ResultsIS2B sampler – wetland test
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ResultsIS2B sampler – wetland test
Chemical Fipronil -Sulfide -Sulfone -Amide -Desulfinyl Total fiproles
I
BWIS2B 14.1 ± 3.3 ND (<0.7) 4.0 ± 1.3 ND (<0.8) 0.04 ± 0.14a 18.1 ± 4.6
LEA 10.0 ± 0.8 ND (<0.7) 3.4 ± 0.5 ND (<0.8) ND (<0.05) 13.4 ± 1.3
PWIS2B** 7.5 ± 1.0 1.4 ± 0.4a 3.7 ± 0.7 ND (<0.8) ND (<0.04) 12.6 ± 2.1
LEA 5.3 ± 0.2 1.4 ± 0.5a 1.9 ± 0.7 ND (<0.8) ND (<0.05) 8.6 ± 1.4
IIBW
IS2B 5.0 ± 2.5 0.8 ± 0.5a 2.3 ± 0.9 1.4 ± 0.7a 0.35 ± 0.16a 9.9 ± 4.6
LEA 3.0 ± 0.1 2.8 ± 1.1 2.2 ± 0.1 2.3 ± 0.2a ND (<0.05) 10.3 ± 1.5
PW IS2B* 5.6 0.94a 2.9 2.0a 0.3 11.6
IIIBW
IS2B 5.4 ± 0.8 0.8 ± 0.1a 3.7 ± 0.9 2.4 ± 0.4a 0.06 ± 0.11a 12.4 ± 2.3
LEA 4.6 ± 0.2 0.8 ± 0.1a 3.3 ± 0.1 2.0 ± 0.1a ND (<0.05) 10.7 ± 0.5
PW IS2B 4.2 ± 1.4 ND (<0.7) 2.9 ± 1.0 1.9 ± 0.5a 0.09 ± 0.08a 9.1 ± 3.0
• Pore water and bulk water concentrations similar in 2/3 of locations• Low sediment OC (~1%) low adsorption of fiproles• Pore water grab sample results similar to IS2B pore water results
a - values are below the limit of quantitation, and are therefore estimatedSampling locations I, II, and III are those referenced in Figure 2BW, bulk water; PW, pore water; LEA, laboratory extraction apparatus (large volume)Standard deviations shown are calculated from n=3, except where indicated*n=1 field replicate (2-day, time-averaged composite)**n=2 field replicates (2-day, time-averaged composite; ± values provided represent maximum/minimum)
Anchor
Porewater inlet
Bulk water inlet
Water outlet
Anchor
Porewater inlet
Bulk water inlet
Water outlet
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IS2BRedesign
Figure 5-2. Pictures showing the internal components (panel a), including the syringes, pump motor, battery, and pore water extraction cartridges. Panel b shows the completed construction with a clear PVC shell. Panel c shows several individual components, including (from bottom to top) the stainless steel bottom cap, acrylic top cap, step motor, interior chassis, O-rings, battery, and shell. Panel d shows the constructed top tap with Swagelok fittings (for bulk water intake).
Figure 5-1. Diagram of the mIS2B.
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PP
Wetland
River
==
Primary sedimentatio
n basins
Secondary sedimentatio
n basinsHeadworks Aeration
basins
PS Thickening Centrifuge
WAS Thickening Centrifuge
Acid Phase
Methane Phase
DS Thickening Centrifuge
Centrate Treatment
Disinfection
Results – WWTP mass balance
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Results – WWTP mass balanceConcentrations of fiproles in wastewater streams• Fipronil (parent) is dominant congener in most streams• Sulfone is higher in RAS, indicating probable aerobic degradation of parent• Sulfide is highest in DWS, indicating probably anaerobic degradation of parent
Stream Fipronil -sulfide -sulfone -amide -desulfinyl 1 Total fiproles (as fipronil)
Influent 22.5 ± 4.5 NP 6.7 ± 1.8 NP 0.5 ± 0.8 29.5 ± 4.8
Primary effluent 21.4 ± 3.4 0.9 ± 2.9 5.2 ± 2.6 NP 0.2 ± 0.2 27.6 ± 5.8
Primary sludge 99.7 ± 53.0 3.0 ± 6.7 13.8 ± 9.3 NP NP 107.0 ± 54.5
Return activated sludge 33.7 ± 8.7 7.8 ± 0.8 25.0 ± 3.8 3.0 ± 0.3 0.01 ± 0.02 76.9 ± 25.6
Secondary effluent 16.4 ± 2.6 2.0 ± 1.4 12.4 ± 11.9 NP 0.1 ± 0.1 30.5 ± 12.9
Chlorination basin effluent 16.2 ± 2.3 0.8 ± 0.6 7.3 ± 5.1 0.7 ± 0.9 0.1 ± 0.1 24.9 ± 5.6
Plant effluent 20.1 ± 3.7 0.6 ± 0.3 5.9 ± 3.9 1.1 ± 1.0 0.1 ± 0.2 27.6 ± 5.6
Wetland effluent 14.7 ± 2.7 0.8 ± 0.4 4.4 ± 2.9 1.1 ± 0.6 0.1 ± 0.2 21.0 ± 4.2
Dewatered sludge* 2.0 ± 0.6 8.4 ± 4.2 1.3 ± 0.9 0.1 ± 0.0 1.2 ± 1.8 3.2 ± 1.5
NP, no peaks detected
* concentrations expressed as ng/g dry weight sludge1 detected concentrations near the MDL, estimated
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Results – WWTP mass balance
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Individual fiprole mass loads
• Reduction in fipronil coincides with increase in byproducts.
• Total fiprole mass from primary influent through disinfection effluent is not discernably different.
Results – WWTP mass balance
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• No attenuation of total fiproles in WWTP
• About half the fiprole mass is attenuated in wetland
47 ± 13% total fiprole reduction
No discernable changeResults – WWTP mass balance
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WWTP fate study – take home points•Conventional wastewater treatment is not efficient at removing fiproles.•Reduction in parent compound mass may coincide with degradate formation (sulfone, in particular).•Total fiprole levels re-entering the environment from wastewater treatment are toxicologically relevant and may impact biota (bees?). •Fiproles are “lost” in the wetland at a rate of about 50%
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Hypotheses revisited1. Assessing fipronil and its byproducts in wastewater and surface water
will generate data precise enough to perform total fiprole mass balances in engineered waterways. – Most streams %RPD (concentration) < 20 %
2. An automatic biphasic sampling tool capable of time-integrated sampling and in situ solid phase extraction (SPE) can produce quantitative data comparable to conventional methods. – Grab sample and IS2B data was similar– %RSD for IS2B was greater
3. Since fipronil is resistant to degradation, a mass balance conducted over a WWTP and wetland will show fiproles to be highly conserved.– True in WWTP– Not true in wetland
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Research implications and recommendations
Sam Supowit, environmental engineeringPhD thesis defense9/25/2015
Committee: Rolf Halden, chair; Paul Westerhoff; Paul C. Johnson
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Implications• Total fiprole mass discharge = 7.9 Σf g/day (0.017 lb/day)
into wetland = 6.3 lb/yr
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ImplicationsThe entire volume of AG fipronil in the U.K. during peak use was about 124 kg/yr (273 lb/yr)
In Japan, it’s about 50,000 kg/yr
In California, it’s about20,000 kg/yr
The estimated, extrapolated discharge by US WWTPs is ~ 500 – 700 kg/yr (1100 lb/yr)
ExtrapolationEstimated ~0.4% of market volumedischarged by WWTPs
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Implications & Recommendations
IS2B data to model contaminant availability
Determine where fiproles in wetland are going
Environmental impacts
pore water
bulk waterwater
column biota
benthic biota
Passive exchange
Passive exchange + particulate ingestion
Passive exchange + food ingestion
Waterway
WWTP
Fish
Aquatic insects
Angiosperms
Pollinators
Birds
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Recommendation: expansion of the search
• Apply sampling/analysis methods to other emerging and legacy contaminants fill data gaps.– Triclosan– Triclocarban– Neonicotinoids– Metolachlor– Trifluralin– Pyrethroids
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Acknowledgments
Committee:Rolf HaldenPaul JohnsonPaul Westerhoff
Team members:Akash SadariaIsaac RollArjun VenkatesanEdward Reyes
Collaborators:
Nancy DenslowViet DangKevin KrollTop secret logistics aids
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QUESTIONS