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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: Rolf.Halden@asu.edu

Presenting author: Sam D Supowit; (P): 520-245-6576; email: Samuel.Supowit@asu.edu

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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.

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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

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Objectives• Automatic in situ sampling vs grab

sampling

• Quantify at trace levels

• Short sampling period

• Dual phase sampling

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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

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7

<5 ng/bee

Colony Collapse Disorder?

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Deployment LocationEngineered Wetland

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Deployment LocationEngineered Wetland

.

10

Deployment LocationEngineered Wetland

.

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Deployment LocationEngineered Wetland

.

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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 (%

)

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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).

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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

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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

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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)

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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)

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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