what are emerging contaminants and why are we concerned · • given to humans in large dose = what...

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What are EmergingContaminants and why are weConcerned

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)

www.EurofinsUS.com/Env

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 OxfordPaper Company Will at Rumford

on the Androscoggin River06/1973

Charles Steinhacker / EPA

Mills of the Brown PaperCompany in Berlin, on the

Androscoggin River06/1973

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 involvedsolving mysteries – took weeks

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Fish Kills

Taste and Odor

Credit to Larry H Keithfor this and photos on

next few slides

Large volumes of samplescollected 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 inNew Orleans water supply

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• Newly formed EPA got sued

• Consent Decree 1976 – requiredEPA to:

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

Some overlooked aspects of theconsent decree

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

• No minimum detection levels were specified.

• No standardized methods for collecting, preserving, oranalyzing for thousands of chemicals at low levels incomplex industrial waste waters were available.

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

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 withdefined 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 ustoday

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Different US EPA programs = same pollutants plusmore

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

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

• RCRA = Priority Pollutants, BTEX/GRO,explosives

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Emerging Contaminants

Other compounds that are not on alist 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 emergingcontaminants 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 nowand then?

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No consent decree

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Pharmaceuticals and Personal CareProducts

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Pharmaceutical and Personal CareProducts (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 onmicroorganisms (wastewater and ambient water)

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Antibiotics affect bacteria in WWTPand ambient

• 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 developinto 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

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Analyze PPCP to optimize treatmentprocess, ensure removal

We routinely monitor for PPCP using EPA method539,Standard Methods 6810,or our in-house LCMS high resolution massspectrometry capable of quantitative determinationof nearly 100 PPCPs, pesticides, and artificialsweeteners, and the non-targeted screening forthousands more

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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

• No federal MCL as of 2019

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 bytraditional treatment

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• Ion Exchange

• Reverse Osmosis

• Biological Reduction

• Biological Activated Carbon

• Granular Activated Carbon

Analyze Perchlorate to verifyremoval from Drinking water

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EPA method 314.0 Ion Chromatography (2-4 ppbMRL)

EPA Method 331 LCMSMS (0.5 – 2 ppb MRL)

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Micro-Plastics

Microplastics in water, and what itcould mean

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• Plastics debris and microplastics occurworldwide• 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 tonsplastic manufactured per year

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Polypropylene(PP)

Low DensityPolyethylene

(LDPE)

High DensityPolyethylene

(HDPE)Polyvinyl

Chloride (PVC)

PolyethyleneTerephthalate

(PET)

Polystyrene(PS)

Polyurethane(PUR)

Other

How much plastic is released intothe environment?

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Degradationà fragmentation into smaller particles

Do not dissolve

Are not biodegradable

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

Once plastic is released it weathersto 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 andsource 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

Most challenging aspect of micro-plastic analysis is sampling

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• Sample preparation“breaks” particles

Sampling

Extraction

SelectiveDigestion

Isolation

Analysis

How to sample varies per sampletype, so does processing

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Analysis of Micro-plastics, using anIR-Microscope

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80010001200140016001800200024002800320036004000cm-1

AbsMeasurement samplePolystyrene (PS)

Count particles, determine ID, Size and shape

Can only estimate mass

Analysis of Micro-plastics, usingPyrolysis GCMS

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

Mass / Volumemeasurement

ID polymer

Don’t know:• # particles• Size• Shape

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That other stuff

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

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Per and polyfluorinated AlkylSubstances - 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 tohydrocarbons - surfactants

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Anionic detergent(Linear octyl sulfonate)

PerfluoroOctyl Sulfonate(PFOS)

Let’s compare PFAS tohydrocarbons – 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 andpoly

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

• Polyfluorinated – one or more carbon notsurrounded 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 donot behave like pesticides,normal organics

• Grease traps, oil/waterseparators

• Bugs – BOD removal

Fatty Acid = food

PFAS behaves like oil andsurfactants, 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 watersoluble

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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/regulatorypredicament = which ones to test?

• 2 (PFOA & PFOS)?

• 6 UCMR3 compounds?

• 12 or all 14 EPA 537 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, UCMRlist, 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 C1256

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 includesall 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 2.058

Plus some extra for a total of 31

Compound Acronym MRL (n/L)

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)

Compound Acronym MRL (n/L)

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

6:2 Fluorotelomer sulfonic acid 6:2 FTS 2.0

8:2 Fluorotelomer sulfonic acid 8:2 FTS 2.0

10:2 Fluorotelomer sulfonic acid 10:2 FTS 2.060

In-house Test: 31 Extra (Cont’d)

Compound Acronym MRL (n/L)

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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In-house Test: 31 Extra (Cont’d)

Compound Acronym MRL (n/L)

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

Ø 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, butwe can look for unknowns

• Use EPA 537 for SDWA monitoring - Eaton

• Targeted list

• Use Eurofins Eaton High Resolution in house methodfor discovery of unknowns

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Cautions on existing PFASdata

• Only EPA 537 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 certified lab (Eurofins Eaton) for

drinking water analysis.

• Use our bottles/preservatives

• Use our “high resolution” methods for discovery ofunknowns.

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

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

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Conclusions• There will always be CECs

• CECs need standardized methods for sampling andanalysis

• With standardized methods you can set limits.

• With standardized methods and limits you candetermine 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 Lippswilliamlipps@eurofinsus.comEurofins Eaton Analytical, LLC

www.eurofinsus.com