1
Novel Active Sampling Device for Determination of Pollutants in Surface Water and Porewater – the In Situ Sampler for
Bioavailability Assessment (IS2B)
Samuel D. Supowit1, Isaac B. Roll1, Viet D. Dang2, Kevin J. Kroll2, Nancy D. Denslow2, Rolf U. Halden1 1The Biodesign Institute, Center for Environmental Security, Security and Defense Systems Initiative, Arizona State University, Tempe, AZ
852872Department of Physiological Sciences and Center for Environmental and Human Toxicology, University of Florida, Gainesville, FL 32611
Corresponding author: Rolf U. Halden; (P): 480-727-0893; email: [email protected]
Presenting author: Sam D Supowit; (P): 520-245-6576; email: [email protected]
2
Rationale for sampler developmentAssumption• What a sampler “sees” is
representative of what organisms will see.
Challenge• Many contaminants are
often at trace concentrations in water and difficult to detect/quantify.
Solution• Preconcentration
Figure 1. Typical deployment of samplers for assessing bioavailability.
3
RationaleAdvantages Disadvantages
Discrete grab sampling
• Fast• Easy• Temporal trends
• Large volumes of water• Porewater is difficult• Sample handling losses
Passive sampling(SPME, LDPE)
• Time-weighted averages• Easy to deploy • Porewater • Bioavailability
• Method development • Long sampling periods• Short term trends??• Calibration
4
Objectives• Automatic in situ sampling vs grab
sampling
• Quantify at trace levels
• Short sampling period
• Dual phase sampling
5
Approach1. Design and build a
sorptive active sampler for dual-phase sampling across the sediment-water interface.
2. Develop an analytical method incorporating active sorptive sampling using SPE as a sample preparation step.
3. Compare discrete grab sample data with the time-averaged data derived using the active SPE sampler.
SPE cartridges
Dis
char
ge in
to b
ulk
wat
er
Pore- Water
Bulk water
Qtotal ≤ 0.5 mL/min
Bench extraction of grab sample
sulfide
Fipronil
sulfone desulfinyl
amideTargets
Compound Procambarusa Hyalella aztecab Diphetor hagenib 27 OC urban
water conc. (µg/L) 25 LC50 (µg/L)
24 LC50 (µg/L)
24 EC50 (µg/L)
24 LC50 (µg/L)
24 EC50 (µg/L)
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
-desulfinyl 68.6 - - - - 0.05-0.13
-sulfide 15.5 1.1-1.7 0.007-0.003 - - ND
-sulfone 11.2 0.35-0.92 0.12-0.31 0.19-0.54 0.055-0.13 0.05-0.19 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
1
7
<5 ng/bee
Colony Collapse Disorder?
8
Deployment LocationEngineered Wetland
9
Deployment LocationEngineered Wetland
.
10
Deployment LocationEngineered Wetland
.
11
Deployment LocationEngineered Wetland
.
13
Results
ConceptDesignFabrication
Results• Analytical QAMatrix water:3 L MilliQ water (0.2 L/ch x8)33 ppm K-citrate(~ 8 ppm DOC)300 ppm Kathon ICP-CG10 ng/L spike
Matrix control signal (x2) ~ 1-10% of matrix spike signal
No isotopically-labeled standards available.
Fipronil Fipronil sulfide Fipronil sulfone Fipronil amide Fipronil desulfinyl
0
20
40
60
80
100
120
10 ng/L spike (1 ng/L for fipronil-desulfinyl)
Abso
lute
Rec
over
y (%
)
15
ResultsTable 1. Calculated fiprole MDLs and LOQs using the IS2B for preconcentration (n = 7).
Chemical MDL (ng/L) LOQ (ng/L) Recovery Stdev Spike (ng/L)
Fipronil 0.74 2.37 92% 24% 1-sulfide 0.69 2.20 93% 22% 1-sulfone 0.41 1.21 86% 9% 1-amide 0.84 2.69 77% 12% 1-desulfinyl 0.041 0.13 95% 13% 0.1
• Analytical QA
Chemical MDL (ng/L) LOQ (ng/L) Recovery Stdev Spike (ng/L)
Fipronil 0.85 2.69 72% 27% 1
-sulfide 0.72 2.30 87% 23% 1
-sulfone 0.98 3.13 87% 31% 1
-amide 0.77 2.45 93% 25% 1
-desulfinyl 0.048 0.15 74% 15% 0.1
Table 2. Calculated fiprole MDLs and LOQs using the Autotrace for preconcentration (n = 7).
16
Results
A B C0
5
10
15
20
25Bulk water
Tota
l fipr
ole
conc
entr
ation
(ng/
L)
A B C
Porewater
IS2B (time averaged 48 hr composite)
Autotrace (discrete grab sample)
vs
17
ResultsBulk water concentrations
0
2
4
6
8
10
12
14
16
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0
1
2
3
4
5
0
1
2
3
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Conc
entr
ation
(ng/
L)
IS2B (48 h avg) Autotrace (Single grab sample)
A B C A B C A B C A B C
Fipronil -Sulfide -Sulfone -Amide -Desulfinyl A B C
MDL
18
A B C 0
2
4
6
8
A B C A B C A B C A B C
Results
0.0
0.5
1.0
1.5
0
1
2
3
4
0
1
2
3
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Conc
entr
ation
(ng/
L)
Fipronil -Sulfide -Sulfone -Amide -Desulfinyl
Porewater concentrations (IS2B)
19
Points to Take HomeSampler capabilities and performance• Dual phase sampling• Good recovery• pg/L LODs• Potential bioavailability assessment• No large volume sample transport• Data produced comparable to conventional methods• Time averaged data• Short sampling periods
Wetland demonstration• High contaminant mobility• Little partitioning (~1% TOC in sediment)
20
Acknowledgments• Principal Investigator Dr. Rolf Halden, PE
• Isaac Roll, EIT, MSE (designs)
• Dr. Benny Pycke
• Tengfei Chen
• Dr. Nancy Denslow
• Dr. Viet Dang
• Kevin Kroll
• National Institutes of Health
Top Related