POCIS – Current Applications, On-going Research and Future Needs

D.A. Alvarez

USGS, BRD, Columbia Environmental Research Center, Columbia, MOU.S. Department of the Interior U.S. Geological Survey

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OUTLINE

State of technology

What types of information can you get

Current/recent application

Calibration

PRCs

Bioindicator tests

Future needs

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Polar Organic Chemical Integrative Sampler (POCIS)

The POCIS was designed to sequester and concentrate waterborne polar organic chemicals.

It consists of a microporous polyethersulfone membrane enveloping various solid phase sorbents and/or mixtures of sorbents.

Its versatility allows for the sequestering medium and membranes to be tailored to specific applications.

Exploded POCIS

Recommend using the “pharmaceutical” configuration containing Oasis HLB for most applications.

Alvarez et al. 2004 Environ Toxicol Chem 23:1640-1648

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Exploded view of the uptake process in POCIS

Wat

er

Water

Pore Size

0.1 μm

Sorbent particles

Contaminant molecule

Membrane

~ 130 μm thick

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General Processing Scheme for POCIS

Exterior Cleaning

Solvent Extraction & Chemical Recovery

EnrichmentTransport to

andlab sealed

Fractionationin airtight can

Deployed POCIS

Chemical Analysis Bioassay/Toxicity testing

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Log KOW

Sam

pli

ng

Rat

es i

n L

/d (

@ <

1 c

m/s

ec, 2

6-28

°C

) N

orm

aliz

ed t

o a

Sta

nd

ard

SP

MD

(46

0 c

m2 )

POCIS

SPMD

Sampling Characteristics of POCIS and SPMDs

Alvarez et al. 2007 Ch. 8 in Passive Sampling Techniques. Comprehensive Analytical Chemistry, vol 48, Elsevier

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SPMDs POCIS

Priority Pollutant PAHs Pharmaceuticals including (also, some alkylated PAHs) Acetaminophen, Carbamazepine, Azithromycin,

Erythromycin, Sulfa drugs (antibiotics) Certain heterocyclic aromatics Tetracycline antibiotics

Organochlorine Pesticides Illicit drugs (methamphetamine, MDMA)

Several Current-Use Pesticides including Several natural and synthetic hormones Pyrethroids and Endosulfan 17β-estradiol, 17α-ethynylestradiol

metabolites: estrone and estriol PCB Congeners

Triazine herbicides including Chlorinated dibenzodioxins including Atrazine and its metabolites

2,3,7,8-TCDD Various polar pesticides including

Chlorinated dibenzofurans including Acetochlor, Alachlor, Chlorpyrifos, Diazinon, 2,3,7,8-TCDF Dichlorvos, Diuron, Isoproturon, Metolachlor

Perfluorinated Compounds Various household and industrial products and PFOS, telomer alcohols degradation products including

Alkyl phenols (nonyl phenol), Benzophenone, Flame Retardants Caffeine, DEET, Indole, Triclosan

PBDEs Perfluorinated Compounds

Tributyl Tin PFOS, PFOA

Nonyl phenol Urobilin (fecal contamination marker)

Essentially, compounds with log Kow ≥ 3.0 Essentially, compounds with log Kow ≤ 3.0

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What type of information can you get from the POCIS?

With sampling rate data –

• Quantitative measurements of contaminant water concentrations

• Plus everything under the “Without sampling rate data” list

Without sampling rate data –

• Qualitative measures of contaminant water concentrations

• Relative differences between sites

• Identification of chemicals (is it there? YES / NO )

• Bio-mimic assessment of an organism’s exposure to chemicals

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Current / Recent Applications – Wastewater Monitoring

Tinkers Creek, OH

Las Vegas / Lake Mead, NV

Potomac River Basin, MD and VA

Assunpink Creek, NJ

Fourmile Creek, IA Boulder Creek, CO

Ozark Caves, MO

Santa Ana River, CA

Eagle Bluffs, MO

Golden Gate National Park, CA

Mad River, OH

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Current / Recent Applications - Drugs from WWTPs

Summer – 15 ng/L

Winter – 66 ng/L Summer – 36 ng/L

Summer – 19 ng/L

Methamphetamine Summer – 2.5 ng/L

MDMA

Winter – 0.8 ng/L Summer – 0.5 ng/L

Summer – ND

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Azithromycin (antibiotic)

Illegal Drugs

Jones-Lepp et al. 2004 Arch Environ Contam Toxicol 47, 427-439

Also Detected:

nonylphenol polyethoxylate and alcohol polyethoxylate surfactants

PFOA and PFOS

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Current / Recent Applications - Agricultural Monitoring

POCIS were deployed Summer 2004 in the drainage basins of 3 agricultural areas.

Pesticides and degradates which were commonly found included:

Acetochlor

Alachlor

Atrazine Desethylatrazine

Desisopropylatrazine

Fipronil

Metochlor

Simazine Trifluralin

Alvarez et al. 2007 J. Environ. Qual. IN PRESS

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Current / Recent Applications - CAFO Activities

1. Prime Hook National Wildlife Refuge

2. Blackwater National Wildlife Refuge

Delmarva Peninsula

- 600 million chickens worth more than 2 billion dollars annually (USDA, 1992)

- 1.6 billion pounds of manure per year

- SPMDs and POCIS were deployed during spring/summer 2000 at 3 locations in each refuge

- 17β-estradiol and tetracycline found at sites impacted by poultry litter field application and runoff

- Several pesticides associated with agriculture were also found

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Current / Recent Applications – Comparison to Grab Sampling

Assunpink Creek near Trenton, NJ

Site 1 – 100 yards downstream from WWTP discharge

Site 2 – 2 miles further downstream

POCIS deployed for 54 days

Water samples taken every 14 days

Samples analyzed by LC/MS and GC/MS for selected pharmaceuticals and wastewater-related contaminants

Alvarez et al. 2005 Chemosphere 61:610-622

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Current / Recent Applications – Comparison to Grab Sampling

Pharmaceuticals

acetaminophen

carbamazepine

dehydronifedipine

diphenhydramine

sulfamethoxazole

thiabendazole

Pesticides

atrazine

DEET

diazinon

metolachlor

pentachlorophenol

prometon

Fire Retardants

Fryol CEF

Fryol FR2

tri(2-butoxyethyl)phosphate

Nonionic Detergent Metabolites

4-cumylphenol

4-tert-octylphenol

nonylphenol, diethoxy

Fragrances

3-methyl-1H-indole

HHCB

indole

methyl salicylate

tonalide

Plasticizers

diethylhexylphthalate

triphenyl phosphate

Miscellaneous

5-methyl-1H-benzotriazole

anthraquinone

benzophenone

caffeine

cotinine

tributyl phosphate

triclosan

triethyl citrate

Chemicals highlighted in green identified in POCIS extracts only Alvarez et al. 2005 Chemosphere 61:610-622 14

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Current / Recent Applications – Pharmaceuticals in UK

A range of therapeutic drug classes were selected based on their prevalent usage and potential risk to the aquatic environment in the United Kingdom.

3 sites located near STWs were sampled over three successive 30 day periods.

7 out of 10 targeted pharmaceuticals were detected including sulfamethoxazole, trimethoprim, propranolol, erythromycin, dextropropoxyphene, diclofenac, and mefenamic acid.

Alvarez et al. 2007 Ch. 8 in Passive Sampling Techniques. Comprehensive Analytical Chemistry, vol 48, Elsevier 15

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Current / Recent Applications - Regulatory Applications

For more details on this project, see the poster by Akin Babatola.

Most emerging contaminants for which POCIS is ideally suited are not currently regulated.

A pilot study by the City of Santa Cruz, CA, using POCIS and SPMDs to monitor effluent from a WWTP has demonstrated the usefulness of this technique once new regulations are made.

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Determination of Sampling Rates (Calibration Studies)

Initial tank studies –

Static renewal under stirred and non-stirred conditions

Pharmaceuticals, pesticides, hormones

Current field calibration –

Treated WW effluent under controlled flow, temperature, and light

Wastewater chemicals, pharmaceuticals

Current diluter –

Flow-through system

Agricultural pesticides

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Performance Reference Compounds (PRCs)

PRCs are chemicals added to the sampler prior to deployment. PRC loss rate can be used to account for site-specific environmental factors (i.e., flow and temperature)

POCIS sorbents have a high sorptive capacity making selection of PRC with sufficient fugacity problematic.

Alternatives –

Mini PRC-SPMD mounted in POCIS rings can act as a surrogate for chemicals which are under water boundary layer control

Use of other chemical reservoirs placed between the PES membranes which are less sorptive (i.e., C18, silicone)

Alvarez et al. 2007 Ch. 8 in Passive Sampling Techniques. Comprehensive Analytical Chemistry, vol 48, Elsevier 18

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5g S ca Ge

1 65432 7

SPMD o POC S extract

Fract onat on Scheme

1) 20 mL 25% D ch orome hane/Hexane

2) 20 mL 40% D ch orome hane/Hexane

3) 20 mL 60% D ch orome hane/Hexane

4) 20 mL 80% D ch orome hane/Hexane

5) 40 mL 100% D ch orome hane

6 30 mL 30% Ace one D chlorome hane

7) 30 mL 100% Ace one

Top row 17β Estrad ol positive con o(serial dilution

Fractions tested in duplicate w h ema ning wells serving as negative cont ols

GC MS Total on Ch omatogram

Spect um o selected peak

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Combination with Bioindicator/Toxicity tests

Extracts have been screened using the Microtox acute toxicity assay and the YES. In general, POCIS extracts can be used in conjunction with almost any assay or exposure test.

0

0.5

1

1.5

2

2.5

3

0.001 0.01 0.1 1 10 100

sample concentration (% POCIS)

ad

jus

ted

ab

so

rban

ce

at

54

0 n

m

04-793B

negative control

upper 99% confidence interval

lower 99% confidence interval

ili l

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i l t

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) t / i t

t

- - i tr l )

it r i r

/ I r

r f

5g Silica Gel

1 65432 71 65432 7

SPMD or POCIS extract

Fractionation Scheme

1) 20 mL 25% Dichloromethane/Hexane

2) 20 mL 40% Dichloromethane/Hexane

3) 20 mL 60% Dichloromethane/Hexane

4) 20 mL 80% Dichloromethane/Hexane

5) 40 mL 100% Dichloromethane

6) 30 mL 30% Acetone/Dichloromethane

7) 30 mL 100% Acetone

Top row - 17β-Estradiol positive control(serial dilution)

Fractions tested in duplicate with remaining wells serving as negative controls

GC/MS Total Ion Chromatogram

Spectrum of selected peak

Silica gel fractionation/YES/GC-MS identification Standard serial dilution YES assay

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Future Research Needs

Optimization of extraction schemes/methods

Different custom configurations for specific chemical classes not easily sampled and/or recovered from the current design

Modeling of the uptake curve

effects of flow and temperature

measurement of partition coefficients

Continued determination of sampling rates

Finalization of the PRC approach

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Acknowledgements

Jim Petty, Jim Huckins, Walter Cranor, Stephanie Perkins, Vickie Schroeder, Randal Clark, Jon Lebo – USGS CERC

Tammy Jones-Lepp – US EPA

Dominic Getting, Jon Goddard, Anthony Gravell – Environment Agency UK

Andrew Rastall – University of Heidelberg, Germany

Steve Goodbred, John Tertuliani, Dana Kolpin, Paul Stackelberg, Ed Furlong, Mike Meyer, Steve Zaugg, Larry Barber, James Gray, Roger Hothem – USGS

Chris Guy, Fred Pinkney, Beth McGee, Scott Sobiech – US FWS

Roger Stewart – Virginia DEQ

John Holmes – Friends of the North Fork of the Shenandoah River

Doug Novinger – Missouri Department of Conservation

Akin Babatola – City of Santa Cruz, CA

And Many More That I’m Forgetting, Sorry.

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