what are emerging contaminants and why are we concerned · • given to humans in large dose = what...
TRANSCRIPT
![Page 1: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/1.jpg)
www.eatonanalytical.com
What are EmergingContaminants and why are weConcerned
William Lipps CSO
Monrovia South Bend
![Page 2: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/2.jpg)
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)
![Page 3: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/3.jpg)
www.EurofinsUS.com/Env
Some History
![Page 4: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/4.jpg)
Water testing before the EPA
4
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
![Page 5: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/5.jpg)
Pre-EPA organics analysis involvedsolving mysteries – took weeks
5
Fish Kills
Taste and Odor
Credit to Larry H Keithfor this and photos on
next few slides
![Page 6: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/6.jpg)
Large volumes of samplescollected and extracted
6
![Page 7: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/7.jpg)
Data manually analyzed – no QA/QC
7
Ron Webb – capillary columnsPlotting and interpreting mass spectra by hand
![Page 8: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/8.jpg)
1975 report – 66 chemicals found inNew Orleans water supply
8
• Newly formed EPA got sued
• Consent Decree 1976 – requiredEPA to:
• Develop methods• Develop sampling procedures• 65 pollutants• 21 industrial categories• In 15 months
![Page 9: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/9.jpg)
Some overlooked aspects of theconsent decree
9
• “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?
![Page 10: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/10.jpg)
Priority Pollutants are born
10
• 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
![Page 11: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/11.jpg)
We got 129 Priority Pollutants withdefined methods
11
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
![Page 12: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/12.jpg)
These 129 pollutants are still with ustoday
12
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
![Page 13: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/13.jpg)
www.EurofinsUS.com/Env
Emerging Contaminants
![Page 14: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/14.jpg)
Other compounds that are not on alist are = Emerging Contaminants
14
• 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)
![Page 15: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/15.jpg)
Over years, talk of emergingcontaminants but not much action
15
• 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)
![Page 16: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/16.jpg)
So what is the difference between nowand then?
16
No consent decree
![Page 17: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/17.jpg)
www.EurofinsUS.com/Env
Pharmaceuticals and Personal CareProducts
![Page 18: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/18.jpg)
18
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)
![Page 19: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/19.jpg)
19
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
![Page 20: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/20.jpg)
20
Bacteria in the WWTP can developinto antibiotic resistant strains
https://www.sciencedirect.com/science/journal/00431354
Antibiotic resistant strains can be released
![Page 21: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/21.jpg)
21
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
![Page 22: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/22.jpg)
22
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
![Page 23: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/23.jpg)
www.EurofinsUS.com/Env
Perchlorate
![Page 24: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/24.jpg)
Perchlorate, another big boom
24
• Highly oxidized polyatomic anion• Naturally occurring – arid• Man-made• Soluble and mobile
![Page 25: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/25.jpg)
First measured in UCMR1
25
• 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
![Page 26: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/26.jpg)
Perchlorate regulations by States
26
• California proposed 1 ppb
• Now at 6 ppb with 4 ppb action level
• Most States 1 – 6 ppb
![Page 27: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/27.jpg)
Perchlorate difficult to remove bytraditional treatment
27
• Ion Exchange
• Reverse Osmosis
• Biological Reduction
• Biological Activated Carbon
• Granular Activated Carbon
![Page 28: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/28.jpg)
Analyze Perchlorate to verifyremoval from Drinking water
28
EPA method 314.0 Ion Chromatography (2-4 ppbMRL)
EPA Method 331 LCMSMS (0.5 – 2 ppb MRL)
![Page 29: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/29.jpg)
www.EurofinsUS.com/Env
Micro-Plastics
![Page 30: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/30.jpg)
Microplastics in water, and what itcould mean
30
• Plastics debris and microplastics occurworldwide• Beaches• Surface water• Wastewater• Drinking water• Food• Inside fish, birds, mammals
![Page 31: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/31.jpg)
Where do micro-plastics come from
31
• Primary• Health and beauty products• Toothpaste• Spills
• Secondary• Larger products become smaller
• Bottles• Bags• Carpet
• Size < 5 mm
![Page 32: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/32.jpg)
There is about 322 million tonsplastic manufactured per year
32
Polypropylene(PP)
Low DensityPolyethylene
(LDPE)
High DensityPolyethylene
(HDPE)Polyvinyl
Chloride (PVC)
PolyethyleneTerephthalate
(PET)
Polystyrene(PS)
Polyurethane(PUR)
Other
![Page 33: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/33.jpg)
How much plastic is released intothe environment?
33
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
![Page 34: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/34.jpg)
Once plastic is released it weathersto micro-plastic
34
• Wave activity• Abrasion• UV irradiation• Microbes
• Systematically break down into smaller particles• Higher surface area• Greater sorption capacity• Different shapes
![Page 35: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/35.jpg)
Microplastics in the POTW
35
• 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?)
![Page 36: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/36.jpg)
Microplastics in ambient water andsource water
36
• 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
![Page 37: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/37.jpg)
Most challenging aspect of micro-plastic analysis is sampling
37
• Sample preparation“breaks” particles
Sampling
Extraction
SelectiveDigestion
Isolation
Analysis
![Page 38: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/38.jpg)
How to sample varies per sampletype, so does processing
38
![Page 39: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/39.jpg)
Analysis of Micro-plastics, using anIR-Microscope
39
80010001200140016001800200024002800320036004000cm-1
AbsMeasurement samplePolystyrene (PS)
Count particles, determine ID, Size and shape
Can only estimate mass
![Page 40: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/40.jpg)
Analysis of Micro-plastics, usingPyrolysis GCMS
40
https://doi.org/10.1016/B978-0-08-100116-5.00017-X
Mass / Volumemeasurement
ID polymer
Don’t know:• # particles• Size• Shape
![Page 41: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/41.jpg)
www.EurofinsUS.com/Env
That other stuff
![Page 42: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/42.jpg)
The compounds that shall not benamed (aka – the other plastics)
42
Per and polyfluorinated AlkylSubstances - PFAS
![Page 43: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/43.jpg)
What are PFAS, really?
43
• Man-made• Surfactant or “fatty acid”• Carbon backbone – fluorine instead of
hydrogen• Very inert• Residual and persistent• Still in use – thousands of products
![Page 44: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/44.jpg)
Let’s compare PFAS tohydrocarbons - surfactants
44
Anionic detergent(Linear octyl sulfonate)
PerfluoroOctyl Sulfonate(PFOS)
![Page 45: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/45.jpg)
Let’s compare PFAS tohydrocarbons – fatty acids
45
Fatty Acid(Octanoic Acid)
PerfluoroOctanoic acid(PFOA)
![Page 46: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/46.jpg)
Definition of what PFAS really is
46
• 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)
![Page 47: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/47.jpg)
The magical carbon-fluorine bond
47
• C-F bond = one of strongest in organic chemistry• High thermal stability• Fluorine “shields” carbon from oxygen, etc.
• Think Teflon™
![Page 48: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/48.jpg)
The difference between per andpoly
48
• Perfluorinated – every carbon (except head)surrounded by a fluorine
• Polyfluorinated – one or more carbon notsurrounded by fluorine, or a break in the chain
![Page 49: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/49.jpg)
Naming conventions of PFAS
49
• 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)
![Page 50: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/50.jpg)
Treating PFAS out of your water,not your average kind of bear
50
• Surfactants and grease donot behave like pesticides,normal organics
• Grease traps, oil/waterseparators
• Bugs – BOD removal
Fatty Acid = food
![Page 51: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/51.jpg)
PFAS behaves like oil andsurfactants, but are inert
51
Micelles Float on surface
They are not “dissolved” in water, either coagulate, float, or stick to sides
![Page 52: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/52.jpg)
Bugs cannot eat PFAS
52
![Page 53: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/53.jpg)
The smaller chains are watersoluble
53
https://www.researchgate.net/figure/Structures-of-major-perfluoralkyl-substances-PFBA-perfluorobutanoic-acid-PFPeA_fig1_316313698
![Page 54: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/54.jpg)
Carbon will clean some, but not all
54
PFBA about same PFOS about 90% removal
![Page 55: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/55.jpg)
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.?
55
![Page 56: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/56.jpg)
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
![Page 57: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/57.jpg)
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
57
![Page 58: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/58.jpg)
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
![Page 59: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/59.jpg)
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
59
![Page 60: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/60.jpg)
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
![Page 61: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/61.jpg)
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
61
![Page 62: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/62.jpg)
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
62
![Page 63: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/63.jpg)
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)
63
![Page 64: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/64.jpg)
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)
64
![Page 65: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/65.jpg)
Potential existing PFAS methods
Ø Total Oxidizable Precursor
§ Measures before and after oxidation
§ Increase assumes pieces “broken off” larger chains
65
![Page 66: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/66.jpg)
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
66
![Page 67: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/67.jpg)
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
67
![Page 68: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/68.jpg)
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.
68
![Page 69: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/69.jpg)
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.
69
![Page 70: What are Emerging Contaminants and why are we Concerned · • Given to humans in large dose = what is effect on microorganisms (wastewater and ambient water) 19 Antibiotics affect](https://reader033.vdocuments.net/reader033/viewer/2022050715/5e0c6f98c3cd9f7b023e501c/html5/thumbnails/70.jpg)
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.