usepa/usgs research on pfas and other contaminants of

USEPA/USGS Research on PFAS and other Contaminants of Emerging Concern in Drinking WaterPresenter- Susan T. Glassmeyer, US Environmental Protection Agency

The views expressed in this presentation are those of the authors and do not necessarily represent the views or policies of the U.S. Environmental Protection AgencyOffice of Research and Development

National Exposure Research Laboratory

Office of Research and DevelopmentNational Exposure Research Laboratory

What I hope you leave with…

• Background understanding of contaminants of emerging concern (CECs) and their relation to the water cycle

• Information on our research on CECs in source and treated drinking water

• PFAS results–PFAS occurrence patterns in two river systems–Source investigation via de facto reuse modelling–Removal during drinking water treatment–Role of granular activated carbon (GAC) during treatment–Examination of data in relation to the third round of the

unregulated contaminant monitoring rule (UCMR 3)

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Office of Research and DevelopmentNational Exposure Research Laboratory2

What are Contaminants of Emerging Concern?

• Term that has come to encompass many contaminants–Pharmaceuticals and personal care products (PPCPs)–Per- and polyfluoroalkyl substances (PFAS)–Surfactants and fluorescent whitening agents–Other household chemicals–Nanomaterials, microplastics–Microorganisms

• Not currently regulated in wastewater effluents and/or drinking water• Unknown or incomplete knowledge of environmental toxicity and fate• Endocrine Disrupting Chemicals (EDCs)

CECs EDCs


Public Awareness of CECs

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Public Awareness and Concern


Bottled Water Sales

5International Bottled Water Association www.bottledwater.org

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Public Drinking Water Treatment Costs 34 billon gallons/ day * $2/ 1000 gallons* 365 days/ year= $24.8 billon/ year

2003


CECs and the Water Cycle

Office of Research and DevelopmentNational Exposure Research Laboratory7 7

CECs in Untreated and Treated Drinking Water

• Two phase study- PFAS in Phase II only.• Source and treated drinking water paired grab samples from 25 locations

• 247 chemical and microbial analytes• ~ 70% of analyses were quality assurance/ quality control samples• Bioassay for estrogenic activity• Human health margin of exposure assessment• Ecological hazard quotient assessment

Office of Research and Development8 National Exposure Research Laboratory8


Location Information

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432

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Number of Phase II sampling sites in each USEPA Region

Population


247 Analytes

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• 112 prescription and nonprescription pharmaceuticals and their metabolites

• 9 hormones

• 40 metallic and nonmetallic trace elements

• 17 per- and polyfluoroalkyl substances (PFAS)

• 5 viruses• 4 bacteria • 3 fungi• 2 protozoa

• 10 industrial chemicals• 10 fragrances • 9 polycyclic aromatic hydrocarbons• 7 pesticides• 7 detergent-related chemicals• 5 household chemicals• 4 plant and animal sterols• 3 phosphorus-based flame

retardants


QA/QC Samples-Organic Chemical Analyses

• Every location had 7-8 samples collected:–Primary sample for both source and treated samples

–Duplicate sample for both source and treated samples

–Laboratory Fortified Matrix (LFM aka matrix spike) for both source and treated samples

–Field Blank- 1 or 2 depending on method

• Laboratory Blank- every batch of 6-10 samples• Laboratory Fortified Blank (LFB aka lab spike)- every batch of 6-10 samples

• Lowest Concentration Minimum Reporting Level (LCMRL)

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What did we do with the QA/QC data?

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Qualitative Detections• Analyte was considered as a QUALITATIVE detection if

– Detection was above the instrument detection limit but below the lowest concentration minimal reporting limit (LCMRL) or reporting limit (RL)

– Associated laboratory fortified matrix (LFM aka matrix spike) was > 150% recovery, suggesting matrix enhancement

– Analyst expertise not confident in quantified detection

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QuantitativeDetection

QualitativeDetection

QuantitativeDetection

QualitativeDetection


Qualitative Detections

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< LCMRL

Quantitative Detections

<RL

Positives

>150 % Recovery


Censored Detections

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• Analyte was CENSORED if– Individual detection censored if concentration not greater than

three times associated laboratory and field blanks–All analyte detections censored if LFMs and laboratory fortified

blanks (LFB; aka lab spikes) did not have a median recovery greater than 50 %


QA/QC Impacts

Performance Measure Action

Number of Affected

MeasurementsSource Treated

Concentration less than LCMRL or RL Qualitative detection 216 123

Non-quantifiable detection “positive” Qualitative detection 18 13

Matrix spike associated with sample > 150% recovery Qualitative detection 59 35

Sample concentration does not exceed 3 × field and/or laboratory blank concentration

Detection censored 179 215

Median recovery < 50% for the LFB, Source LFM and/or Treated LFM

Analyte censored(48 analytes) 15 6

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Qualified detections 293 171Censored detection 179 215Quantified detections 1082 854Non-detects (includes censored) 4698 4931


Products

• Introduction- STOTEN 2017 579 1608• Overview- STOTEN 2017 581 909-922• QA/QC- STOTEN 2017 579 1618-1628• Pharmaceuticals- STOTEN 2017 579 1629-1642• Estrogen Bioassay- STOTEN 2017 579 1610-1617• Bacteria and Protozoa- STOTEN 2016 562 987-995• Viruses- STOTEN 2018 619 1330-1339 • Human Health- STOTEN 2017 579 1643-1648• Aquatic Health- STOTEN 2017 579 1649-1657• PFAS- STOTEN 2019 653 359-369

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Qualitative Frequency of Detection

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Qualitative Frequency

of Detectionby Analyte

Class

Presenter

Presentation Notes

Frequencies on previous slide broken out by analyte class. Pharms and AWIs show decreases from moving to still waters, but PFCs and inorganics show fairly consistent frequencies. Microorganisms all over the place (the viruses show slight tendency to occur more frequently in samples collected in the winter over the summer)


Commonly Detected in Source Water

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Pharmaceuticals•sulfamethoxazole•lithium•carbamazepine•metoprolol•estrone•aciclovir•metformin•methocarbamol•tramadol•caffeine•meprobamate

PFAS•PFOA•PFBS•PFOS•PFHxA•PFHpA•PFNA•PFBA•PFPeA•PFHxS•PFDA•PFUnDA

AWIs•triclocarban•triclosan•benzotriazole methyl-1H•DEET•atrazine•metolachlor•galaxolide •tri(2-butoxyethyl) phosphate•tri(2-chloroethyl) phosphate

•strontium•barium•calcium•sodium•sulfur•magnesium•silicon•potassium•total dissolved nitrogen•fluoride•nitrate •aluminum •zinc•sulfate

•chloride•iron•manganese•phosphorus•copper•phosphate •bromide•lead•uranium•ammonia •arsenic•nitrite•nickel•vanadium•tin

Inorganics•Aspergillus fumigatus•Giardia•Adenovirus•Norovirus G2

Microorganisms

•148 out of the 247 analytes detected at least once in source water

Presenter

Presentation Notes

Compounds in each class found at least 8 locations. In order in each class from most frequent at top to least at bottom


Commonly Detected in Treated Water

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Pharmaceuticals•lithium•metoprolol

PFAS•PFOA•PFBS•PFHxA•PFPeA•PFOS•PFHpA•PFNA•PFBA•PFHxS•PFDA•PFUnDA

AWIs•bromoform•triclosan•benzotriazole methyl-1H•isophorone•atrazine•metolachlor•tri(2-chloroethyl) phosphate

•strontium•calcium•barium•sodium•sulfur•magnesium•potassium•silicon•total dissolved nitrogen•fluoride•aluminum •nitrate •sulfate •chloride

•iron•zinc•phosphate •phosphorus•copper•manganese•arsenic•chlorate •uranium•bromide•ammonia •tin

Inorganics Microorganisms

•121 out of the 247 analytes detected at least once in source water

Presenter

Presentation Notes

Again detected in at least 8 locations. Pharms and microorganisms show lower frequencies. Addition of bromoform to AWIs as DBP


Summed Concentration

by Analyte Class

Presenter

Presentation Notes

Look at concentration trends across classes, if compare/contrast to the frequencies, there is more variability in concentration between locations than frequency. Also, no one location is high in all classes


Estrogen Assay

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Source Water

LC/M

S/M

S

Treated Drinking Water

T47D

-Kbl

uc A

ssay

No quantified detections

Presenter

Presentation Notes

Only estrone was quantifiably measured and then only in the source waters. The estrogen assay and estrone measurements agree in general pattern, The assay may also include the qualified detections of things we looked for, as well as chemicals we did not look for


Deep dive into the PFAS data

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PFAS Methodology

• Boone et al., J. Chrom. A, 2014• 250 mL unfiltered sample for both source and treated drinking water

• Buffered with Trizma ® pre-set crystals to pH of approximately 7.0 and then buffered using citric acid buffer to approximately pH 4

• Solid Phase Extraction-Oasis® Wax• Analyzed by liquid chromatography tandem mass spectrometry (LC/MS-MS)

• Lowest Concentration Minimum Reporting Level (LCMRL) 0.032-0.56 ng/L

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Laboratory Fortified Matrix (Matrix Spike) Recoveries

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Source Water

Treated Drinking Water


Concentrations

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PFAS Patterns in Source Water

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DRINCS Model

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Median De Facto Reuse (DFR)Sorted by Stream Order

30 Nguyen et al., JAWWA, 2018


De Facto Reuse (DFR)and Concentration

31 Nguyen et al., JAWWA, 2018


Treatment

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DW

TP1

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TP2

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TP3

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TP5

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TP10

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TP12

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TP21

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TP22

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TP23

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TP24

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TP28

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TP29


Granular Activated Carbon

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Wilcoxon 0.00 0.02 0.53 0.94 0.73 0.99 0.00 0.85 0.37 0.32 0.04P


Health Advisory Comparison


UCMR v. Phase IIPFAS Methods

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Criteria UCMR Phase II

Intended Use Potentially Regulatory Research

Analytes PFBS, PFHpA, PFHxS, PFNA, PFOS, PFOA

UCMR list + PFBA, PFPeA, PFHxA, PFDA, PFUnDA, PFDoDA, PFTrDa, PFTeDA, PFHxDA, PFOcDA. PFDS

Detection Limit MRL 10-90 ng/L LCMRL 0.032-0.56 ng/L


Comparing UCMR to Phase II Data

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AnalyteUCMR* Phase II

# DWTPs Sampled

# Detections > MRL

# > Reference

Conc**.

# DWTPs Sampled

# Detections > LCMRL

# > Reference

Conc.**

PFOS 4920 95 46 25 20 0

PFOA 4920 117 13 25 19 1

PFNA --

PFHxS --

PFHpA 4920 86 -- 25 23 --

PFBS 4920 8 -- 25 24 --

Lower detection limits lead to higher frequencies of detection.

DWTP 22 did not exceed health reference level in UCMR 3 samples.

*UCMR 3 data from https://www.epa.gov/sites/production/files/2017-02/documents/ucmr3-data-summary-january-2017.pdf** Reference Concentrations 70 ng/L for PFOS, PFOA, or PFOS + PFOA


Take Home Messages

• Twenty-five paired source and treated drinking waters were sampled.

• All 50 samples had detectable PFAS; one treated drinking water sample exceeded health advisory guidelines.

• Distinctive PFAS patterns were observed for two large river systems.

• PFAS not as strongly linked to de facto reuse percentage as other organic CECs. Non-wastewater sources?

• Minimal removal during drinking water treatment; GAC depth and recharge rate may play a role in removal.

• Detection frequencies higher in Phase II relative to UCMR 3.


Co-Authors

• Susan Glassmeyer • Edward Furlong• Dana Kolpin• Angela Batt• Bob Benson• Scott Boone• Octavia Conerly• Maura Donohue• Dawn King• Mitch Kostich• Heath Mash• Stacy Pfaller

• Kathleen Schenck• Jane Ellen Simmons• Eunice Varughese• Stephen Vesper• Eric Villegas• Vickie Wilson

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