What are Emerging Contaminants and why are we Concerned · individual compounds. • No minimum detection levels were specified. • No standardized methods for collecting, preserving,

www.eatonanalytical.com

What are Emerging Contaminants and why are we Concerned

William Lipps CSO

Monrovia South Bend

www.EurofinsUS.com/Env

William Lipps

• Chief Science Officer – Eurofins Eaton Analytical

• Monrovia CA

• South Bend Indiana

• ASTM D19 Chair, Fellow

• Standard Methods AWWA Editor and Part 4000 Coordinator

• Incoming SME ED Chair

• ANSI representative to ISO TC147 (water) SC2 (chemistry)


Some History

Water testing before the EPA

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Burning Barge On The Ohio River, May 1972William Strode / EPA

Outflow Pipe 6 of the Oxford Paper Company Will at Rumford

on the Androscoggin River 06/1973

Charles Steinhacker / EPA

Mills of the Brown Paper Company in Berlin, on the

Androscoggin River 06/1973

Charles Steinhacker / EPA

Prior to EPA – Conventional Pollutants such as BOD, COD, metals, pH, turbidity

No real trace organics testing at all

Pre-EPA organics analysis involved solving mysteries – took weeks

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Fish Kills

Taste and Odor

Credit to Larry H Keith for this and photos on

next few slides

Large volumes of samples collected and extracted

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Data manually analyzed – no QA/QC

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Ron Webb – capillary columnsPlotting and interpreting mass spectra by hand

1975 report – 66 chemicals found in New Orleans water supply

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• Newly formed EPA got sued

• Consent Decree 1976 – required EPA to:

• Develop methods• Develop sampling procedures• 65 pollutants• 21 industrial categories• In 15 months

Some overlooked aspects of the consent decree

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• “65 pollutants” – really thousands since some were classes rather than individual compounds.

• No minimum detection levels were specified.

• No standardized methods for collecting, preserving, or analyzing for thousands of chemicals at low levels in complex industrial waste waters were available.

• How do labs estimate costs for sampling and analysis for no defined list of analytes, no methods, or no defined limits?

Now 1912

Priority Pollutants are born

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• EPA made methods:• GCMS for organics• GC-ECD for pesticides• ICP or AA for metals• 10 ppb detection limit

• Specific compounds made list• Metals = “total”• Classes became – “total

phenolics”, “total cyanide”, aroclors

We got 129 Priority Pollutants with defined methods

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1. Metals2. Asbestos3. Total Cyanide4. Organochlorine Pesticides and PCBs5. Base Neutral and Acid Extractable Organics6. Purgeable Organics7. Total Phenols

“In the beginning there was water, and it got dirty” Bill Telliard, USEPA

These 129 pollutants are still with us today

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Different US EPA programs = same pollutants plus more

• SDWA = Primary, Secondary, UCMR, DBP, Radionuclides, Bacteria

• CWA = Priority Pollutants, radionuclides, nutrients, bacteria/viruses

• RCRA = Priority Pollutants, BTEX/GRO, explosives


Emerging Contaminants

Other compounds that are not on a list are = Emerging Contaminants

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• No regulation, maybe no method• Have been found in environment• May pass through drinking or wastewater

treatment

• Very similar to New Orleans study:• Classes with no fixed list• No “standardized methods”• No analytical standards (for many)

Over years, talk of emerging contaminants but not much action

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• Pharmaceutical and Personal Care Products (PPCP)

• Perchlorate, • Chromium VI, • 1,4-Dioxane• Dioxin• Microplastics• Unknown organics• The compounds that shall not be named (aka

PFAS)

So what is the difference between now and then?

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No consent decree


Pharmaceuticals and Personal Care Products

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Pharmaceutical and Personal Care Products (PPCP)

• Very diverse = thousands of compounds• Antibiotics• Hormones• Laundry and cleaning products• Cosmetics and sunscreen• Dietary supplements• Prescription and over the counter drugs• Illegal drugs

• Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water)

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How can PPCP get into our water supplies?

IWMI 2017

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Example- Antibiotics affect bacteria in WWTP and ambient

• Antibiotics used -- Human and animal use• Not regulated for NPDES or SDWA

• Purpose of WWTP • Decrease organic waste• Remove nutrients

• WWTP uses bacteria

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Bacteria in the WWTP can develop into antibiotic resistant strains

https://www.sciencedirect.com/science/journal/00431354

Antibiotic resistant strains can be released

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Fish don’t need pills

https://aispantherpaper.wordpress.com/2018/04/30/what-are-superbugs-and-how-are-they-affecting-us/

Resistant bacteria

Food and/or drinking water

Antibiotics in water


What are the “approved” methods for PPCP?

• Method 539 – LCMSMS, finished drinking water, UCMR• Method 542 – LCMSMS, finished drinking water, UCMR• Standard Methods 6810

• Not regulated by SDWA – no official methods

• EPA 1694 – LCMSMS, non-potable water, bio-solids• Standard Methods 6810

• Not listed in 40 CFR Part 136

Proprietary methods

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Unlike the priority pollutant solution, PPCP analysis lacks:

• A specific list of analytes

• Approved methods

• Regulations requiring monitoring

• Clear adverse health risk (SDWA)


Perchlorate

Perchlorate, another big boom

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• Highly oxidized polyatomic anion• Naturally occurring – arid • Man-made• Soluble and mobile

First measured in UCMR1

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• 164 of 3865 systems > 4 ppb

• 26 States and 2 Territories

• Mean = 9.85 ppb• Median = 6.40 ppb

Perchlorate regulations by States

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• California proposed 1 ppb

• Now at 6 ppb with 4 ppb action level

• Most States 1 – 6 ppb

Perchlorate difficult to remove by traditional treatment

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• Ion Exchange

• Reverse Osmosis

• Biological Reduction

• Biological Activated Carbon

• Granular Activated Carbon

Analyze Perchlorate to verify removal from Drinking water

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EPA method 314.0 Ion Chromatography (2-4 ppb MRL)

EPA Method 331 LCMSMS (0.5 – 2 ppb MRL)

No federal MCL as of 2019, however, regulation is proposed

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A consent decree entered by the U.S. District Court for the Southern District of New York states that EPA shall propose a national primary drinking water regulation (NPDWR) with a proposed Maximum Contaminant Level Goal (MCLG) for perchlorate in drinking water no later than 10/31/18 and finalize a MCLG and NPDWR for perchlorate in drinking water no later than 12/19/19.


Micro-Plastics

Microplastics in water, and what it could mean

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• Plastics debris and microplastics occur worldwide• Beaches• Surface water• Wastewater• Drinking water• Food• Inside fish, birds, mammals

Where do micro-plastics come from

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• Primary• Health and beauty products• Toothpaste• Spills

• Secondary• Larger products become smaller

• Bottles• Bags• Carpet

• Size < 5 mm

There is about 322 million tons plastic manufactured per year

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Polypropylene (PP)

Low Density Polyethylene

(LDPE)

High Density Polyethylene

(HDPE)Polyvinyl

Chloride (PVC)

Polyethylene Terephthalate

(PET)

Polystyrene (PS)

Polyurethane (PUR)

Other

How much plastic is released into the environment?

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Degradation fragmentation into smaller particles

Do not dissolve

Are not biodegradable

No one really knows how much of the 322 Million tons per year is released

Once plastic is released it weathers to micro-plastic

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• Wave activity• Abrasion• UV irradiation• Microbes

• Systematically break down into smaller particles• Higher surface area• Greater sorption capacity• Different shapes

Microplastics in the POTW

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• Effluent ~ 1000 particles/L

• Removal ~ 90%• < 10 µm not removed• 80 % of fibers NOT removed (shape matters)

• Most end up in bio-solids (land farmed?)

Microplastics in ambient water and source water

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• Higher in coastal and industrialized areas• Vertical distribution counterintuitive

• Larger, more buoyant, on top• Smaller (< 100 µm) particles deeper• Varies on stream conditions, particle shape

Efforts to standardize methods for Microplastics

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As always – there are proprietary methods

How to sample varies per sample type, so does processing

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In our own study - Everyone Used Their Own Bottles

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The whole sample as received filtered Special filtration setup in

polymer dust free lab facility.

Specially designed stainless steel filtration apparatus

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Even drinking water needs prep!

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total samples samples coloring filters

21% of samples resulted in colored filters. Occurred in most countries.

Most challenging aspect of micro-plastic analysis is preparation

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• Sample preparation “breaks” particles

Sampling

Extraction

Selective Digestion

Isolation

Analysis

Once preparation is complete, ID plastics using FTIR microscope

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Analysis of Micro-plastics, using an IR-Microscope

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80010001200140016001800200024002800320036004000cm-1

AbsMeasurement samplePolystyrene (PS)

Count particles, determine ID, Size and shape

Can only estimate mass

Alternatively - Analysis of Micro-plastics, using Pyrolysis GCMS

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https://doi.org/10.1016/B978-0-08-100116-5.00017-X

Mass / Volume measurement

ID polymer

Don’t know:• # particles• Size• Shape

Efforts to standardize methods for Microplastics

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WK67563 Collection of Wastewater Samples for the Identification and Quantification of Microplastic Particles

WK67564 Preparation of Wastewater Samples Allowing the Identification and Quantification of Microplastic Particles using Raman and FTIR Microscopy

WK67565 Spectroscopic Identification and Quantification of Microplastic Particles in Water Using Raman and FTIR Spectroscopy

WK67788 Identification of Microplastic Particles and Fibers in Water using Pyrolysis‐GC/MS


That other stuff

The compounds that shall not be named (aka – the other plastics)

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Per and polyfluorinated Alkyl Substances - PFAS

What are PFAS, really?

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• Man-made• Surfactant or “fatty acid”• Carbon backbone – fluorine instead of

hydrogen• Very inert• Residual and persistent• Still in use – thousands of products

Let’s compare PFAS to hydrocarbons - surfactants

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Anionic detergent(Linear octyl sulfonate)

PerfluoroOctyl Sulfonate (PFOS)

Let’s compare PFAS to hydrocarbons – fatty acids

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Fatty Acid(Octanoic Acid)

PerfluoroOctanoic acid (PFOA)

Definition of what PFAS really is

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• Linear or branched chain organic compounds• Chain terminated with polar “head”• Negative charged “head” = anion• Carbon – Hydrogen replaced by Carbon – Fluorine• C-F bond VERY stable• Oil/water resistant “tail” and polar “head”• Fewer carbons = more water soluble• Long chains = stick to stuff (soil, GAC, surfaces)• Buoyant (like plastics)

The magical carbon-fluorine bond

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• C-F bond = one of strongest in organic chemistry• High thermal stability• Fluorine “shields” carbon from oxygen, etc.

• Think Teflon™

The difference between per and poly

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• Perfluorinated – every carbon (except head) surrounded by a fluorine

• Polyfluorinated – one or more carbon not surrounded by fluorine, or a break in the chain

Naming conventions of PFAS

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• Perfluorinated Functional groups (heads)

• Carboxylic acids (R-COOH) Surfactants (A)• Sulfonic Acids (RSO3H) Surfactants (S)• Sulfonamides (R-SO2NH2) Raw material or

intermediate

• Polyfluorinated Functional Groups• Fluorotelemer alcohols (R-CH2CH2OH) Raw

material• Fluorotelemer sulfonic acid (R-CH2CH2SO3H)

Surfactant• Fluorotelemer carboxylic acid (R-CH2COOH)

Intermediate

• 4 carbons – Buta (B)• 5 carbons - Penta (Pe)• 6 carbons - Hexa (Hx)• 7 carbons – Hepta (Hp)• 8 carbons – Octa (O)

Perfluorooctanoic acid (PFOA)

Perfluorooctane sulfonate (PFOS)

Treating PFAS out of your water, not your average kind of bear

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• Surfactants and grease do not behave like pesticides, normal organics

• Grease traps, oil/water separators

• Bugs – BOD removal

Fatty Acid = food

PFAS behaves like oil and surfactants, but are inert

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Micelles Float on surface

They are not “dissolved” in water, either coagulate, float, or stick to sides

Bugs cannot eat PFAS

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The smaller chains are water soluble

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https://www.researchgate.net/figure/Structures-of-major-perfluoralkyl-substances-PFBA-perfluorobutanoic-acid-PFPeA_fig1_316313698

Carbon will clean some, but not all

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PFBA about same PFOS about 90% removal

The laboratory/regulatory predicament = which ones to test?

• 2 (PFOA & PFOS)?

• 6 UCMR3 compounds?

• 12 or all 14 EPA 537 compounds or 18 537.1 compounds?

• 21 compounds (NYDEC, etc.)?

• 24 or more compounds (DOD, NHDES, MIDEQ, EPA, ASTM, etc.)?

• GenX, ADONA, etc.?

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Should we look at all EPA 537, UCMR list, or just PFOA and PFOS?

Compound Acronym CarbonPerfluorobutanesulfonic acid (UCMR3) PFBS C4

Perfluorohexanesulfonic acid (UCMR3) PFHxS C6

Perfluorooctanesulfonic acid (UCMR3 and HA) PFOS C8

Perfluorohexanoic acid PFHxA C6

Perfluoroheptanoic acid (UCMR3) PFHpA C7

Perfluorooctanoic acid (UCMR3 and HA) PFOA C8

Perfluorononanoic acid (UCMR3) PFNA C9

Perfluorodecanoic acid PFDA C10

Perfluoroundecanoic acid PFUnA C11

Perfluorododecanoic acid PFDoA C12

Perfluorotridecanoic acid PFTrDA C13

Perfluorotetradecanoic acid PFTeDA C14

N-methyl Perfluorooctanesulfonamidoacetic acid NMeFOSAA C11

N-ethyl Perfluorooctanesulfonamidoacetic acid NEtFOSAA C1265

Should we add the 537.1 analytes?

Compound Acronym Carbonhexafluoropropylene oxide dimer acid (HFPO-DA) GenX C3

11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS C10

9-chlorohexadecafluoro-3-oxanone-1-sulfonic acid 9Cl-PF3ONS C8

4,8-dioxa-3H-perfluorononanoic acid ADONA C7

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Or our In-house Test that includes all EPA 537 compounds

Compound Acronym MRL (n/L)

Perfluorobutanesulfonic acid PFBS 2.0

Perfluorohexanesulfonic acid PFHxS 2.0

Perfluorooctanesulfonic acid PFOS 2.0

Perfluorohexanoic acid PFHxA 2.0

Perfluoroheptanoic acid PFHpA 2.0

Perfluorooctanoic acid PFOA 2.0

Perfluorononanoic acid PFNA 2.0

Perfluorodecanoic acid PFDA 2.0

Perfluoroundecanoic acid PFUnA 2.0

Perfluorododecanoic acid PFDoA 2.0

Perfluorotridecanoic acid PFTrDA 2.0

Perfluorotetradecanoic acid PFTeDA 2.0

N-methyl Perfluorooctanesulfonamidoacetic acid NMeFOSAA 2.0

N-ethyl Perfluorooctanesulfonamidoacetic acid NEtFOSAA 2.067

Plus some extra for a total of 31


3 More Perfluoroalkylcarboxylic Acids

Perfluorobutanoic acid (C4) PFBA 5.0

Perfluoropentanoic acid (C5) PFPeA 2.0

Perfluorohexadecanoic acid (C16) PFHxDA 2.0

5 More Perfluoroalkylsulfonic Acids

Perfluoropentanesulfonic acid (C5) PFPeS 2.0

Perfluoroheptanesulfonic acid (C7) PFHpS 2.0

Perfluorononanesulfonic acid (C9) PFNS 2.0

Perfluorodecanesulfonic acid (C10) PFDS 2.0

Perfluorododecanesulfonic acid (C12) PFDoS 2.0

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In-house Test: 31 Extra (Cont’d)


5 More Perfluoroalkylsulfonamides

Perfluorooctane sulfonamide PFOSA 2.0

N-methylperfluorooctane sulfonamide NMeFOSA 2.0

N-ethylperfluorooctane sulfonamide NEtFOSA 2.0

N-methylperfluorooctane sulfonamidoethanol NMeFOSE 2.0

N-ethylperfluorooctane sulfonamidoethanol NEtFOSE 2.0

4 Fluorotelomer Sulfonic Acids

4:2 Fluorotelomer sulfonic acid 4:2 FTS 2.0






8 Perfluoroalkyl Ether Carboxylic Acids and Others

GenX --- 5.0

ADONA --- 2.0

F-53B Major --- 2.0

F-53B Minor --- 2.0

Perfluoro-4-methoxybutanoic acid PFMOBA 5.0

Perfluoro-3-methoxypropanoic acid PFMOPrA 5.0

Perfluoro-2-methoxyethoxyacetic acid PFMOEOAA 5.0

Perfluoro-4-isopropoxybutanoic acid PFIpOBA 5.0

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6 Non-Target Perfluoroalkyl Ether Carboxylic Acids and Others

Perfluoro-2-methoxyacetic acid PFMOAA ~ 5

Perfluoro (3,5-dioxahexanoic) acid PFO2HxA ~ 5

Perfluoro (3,5,7-trioxaoctanoic) acid PFO3OA ~ 5

Perfluoro (3,5,7,9-tetraoxadecanoic) acid PFO4DA ~ 5

Nafion Byproduct 1 Nafion BP1 ~ 5

Nafion Byproduct 2 Nafion BP2 ~ 5

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In Absence of PFAS “regulation” Eurofins Eaton does-

EPA 537 and 537.1 for Drinking Water

• Stick to our guns on following methods

In-House methods for non-potable water

• Additional compounds and different SPE

In-House methods for Soil and DoD (LLE and/or TA)

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New and coming PFAS methods

ASTM D7979 (water) to SW846 method 8327

• Method 3512 for Extraction

ASTM D7968 (soil) to SW846 method 8329

• Method 3551 for Extraction

SW846 (soil and tissue) as method 8328

• Isotope dilution

• Carbon Cleanup (DoD)

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Potential existing PFAS methods

Total Oxidizable Precursor

Measures before and after oxidation

Increase assumes pieces “broken off” larger chains

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LC/MS/MS is targeted analysis, but we can look for unknowns

• Use EPA 537.1 for SDWA monitoring - Eaton

• Targeted list

• Use Eurofins Eaton High Resolution in house method for discovery of unknowns

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Cautions on existing PFAS data

• Only EPA 537.1 and ASTM/New EPA methods are “standardized”

• Lab modified methods may not compare between labs

• What were the modifications?

• Are peaks chromatographically resolved?

• Is the whole bottle extracted?

• “Hits” could be sampling contamination

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Recommendations• Use a Method 537.1 certified lab for drinking water

analysis.

• Use their bottles/preservatives

• Use our “high resolution” methods for discovery of unknowns.

• Make sure lab is “qualified” to modify methods.

• Eaton routinely collaborates with EPA, ASTM, and Standard Methods to make new methods.

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Conclusions• There will always be CECs

• CECs need standardized methods for sampling and analysis

• With standardized methods you can set limits.

• With standardized methods and limits you can determine BAT for removal.

• Eaton can help you test for CECs.

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Eurofins Eaton Analytical• has analyzed over 10,000 samples from approximately 1800 public water

system customers during the 2013-2015 UCMR3 monitoring period • since then continues to analyze even more comprehensive PFAS lists for

hundreds of clients across the nation. • the only laboratory in California that has been uploading state monitoring

data below the UCMR3 limits (MRL = 2 – 2.5 ng/L) • the first laboratory to seek California accreditation for PFAS analysis in

drinking water. • With lower limits, we are able to provide you trusted and accurate data

to demonstrate compliance with the new notification levels.

Any Questions?

William [email protected] Eaton Analytical, LLC

www.eurofinsus.com

Documents

What are Emerging Contaminants and why are we Concerned · individual compounds. • No minimum detection levels were specified. • No standardized methods for collecting, preserving,