Leachate Treatment for a Variety of Emerging Contaminants

Leachate Treatment for a Variety of Emerging Contaminants

NY ANNUAL SOLID WASTE & RECYCLING CONFERENCE MAY 21, 2019

Ivan A. Cooper, PE, BCEE Civil & Environmental Consultants, Inc. Charlotte NC

Agenda

► Emerging Contaminants – ▪ PPCP ▪ 1,4 Dioxane ▪ Microplastics ▪ Nano Particles ▪ PFAS

► Treatment Technologies ► Summary

2 | New York Federation Conference May 21 2019

Emerging Contaminants

►Emerging contaminants are chemicals that have been detected in global drinking water supplies at trace levels and for which the risk to human health is not yet known. They include pharmaceuticals, personal care products, pesticides, herbicides and endocrine disrupting compounds. EPA includes 1,4 dioxane and PFOA and PFOS, amongst others.


Concerns Regarding Emerging Contaminants

► Increased utilization of new and unique compounds in consumer products ▪ Are these compounds in leachate?

► Potential risk to human health and the environment is largely unknown. o affect growth, learning, and behavior of infants and older children o lower a woman’s chance of getting pregnant o interfere with the body’s natural hormones o increase cholesterol levels o affect the immune system o increase the risk of cancer

► Appropriate treatment methods? ► Detection and quantification can be challenging – ▪ can we sample/analyze reliably at ppt or lower levels?


Pharmaceuticals and Personal Care Products

► Product that is utilized: ▪ Consumers for either cosmetic or health related reasons ▪ Agribusinesses to protect the health or to improve the growth of livestock.

o Treatment o Control o Prevention o Growth

► Low levels and vast number of parent and daughter compounds or degradation products that could be present.


PPCP

► 600,000 chemicals ► Sources: ▪ Prescription drugs; shampoo, detergents, deodorant, cosmetics,

artificial sweeteners, triclosan ► Up to 40% of unused pharmaceutical disposed in landfills ► Some easily degraded ▪ Acetaminophen ▪ Ibuprofen

► Many recalcitrant ▪ Synthetic estrogen, many others ▪ Goes right through biological treatment

► Some state and local regulation starting – California, Washington, Oregon, Utah

► Ends up in water supplies


1,4 Dioxane

► Stabilizer for TCA, paint stripper, dyes, grease, varnish, wax, deodorant, cosmetics, food packaging

► Kidney and Liver Damage – nervous system impacts1 ► Worker exposure at high levels cause several deaths ► Health risks, likely carcinogen, irritant, breaks down in the body2 ► Highly miscible and highly mobile ► Drinking water guidelines MassDEP – 0.3 ug/L (USEPA – 0.35 ug/L) ► Great interest in New England ▪ Mass DEP implicates landfills, WW discharges, HW sites ▪ Eastham Landfill – MassDEP responded ▪ Acton, MA ▪ NH study – in 30 landfill leachate ▪ Dewey Loeffel Landfill near Troy, NY ▪ Lowry Landfill, Colorado

1. Toxicological Profile nih.gov 2. Atsdr.cdc.gov 8 | New York Federation Conference May 21 2019

Microplastics Health Aspects

► Plastic particles <5 mm in size in any one dimension, EPA 2017

► Leachate from plastics has previously been shown to cause acute toxicity in the freshwater species Daphnia magna. (Bejgam, 2015)

► Ingestion of MPs by aquatic organisms has been demonstrated, but the long-term effects of continuous exposures are less well understood. (Lambert, 2017)

► Bisphenol A (BPA) is commonly found in landfill leachate at levels exceeding acute toxicity benchmarks (Morin, Norway , 2015)


Nanoparticles

► NPs2 - Metals, carbon, clays, silica ▪ Ag (as an antibacterial agent), ▪ SiO2 (as a polishing and binding agent), ▪ TiO2 (in solar cells) and ▪ ZnO (as a UV-absorber in sun screen lotion)

► Used for drug delivery and pharmaceuticals, cosmetics, environmental remediation, nanotechnology, biomaterials, and energy production. ▪ As of October 2013, 1,628 consumer products contained NPs.1 ▪ Nanocomposites include materials that are reinforced with nano-fillers (nano-clay

and nano-silica) for weight reduction, carbon nanotubes (CNTs) for improved mechanical strength, drug delivery uses, and nano-silver utilized as an antimicrobial agent in plastic food packaging materials.

1. Nanotech Project, 2016

2. Reinhart et al., 2010 10| New York Federation Conference May 21 2019

Nanoparticles

► Concerns about the impacts on waste degradation and leachate treatment1 and aerobic (leachate treatment) processes associated with landfills in addition to the potential release of these NMs to the environment (Bolyard et al., 2013; Reinhart et al., 2010).

► Nanomaterials (NMs) could initiate adverse biological responses that can lead to toxicological outcomes. ▪ generates reactive oxygen species and oxidant injury. Toxicological potential of

engineered and ambient ultrafine NMs particles.3

▪ Airborne emissions to receptors - lungs to the brain, the liver, the spleen and possibly the fetus in pregnant women

1. Bolyard et al., 2013; Reinhart et al., 2010 2. Bolyard et al., 2013 3. Xia, Annu Rev Public Health. 2009


Where PFAS is Used? Product Uses/Sources

Fluoropolymer coatings Plastics/polymers Oil, stain, water repellent (, Stainmaster® carpets, Scotch Gard™ and Gore-Tex®) Surfactants used in firefighting foams Mist suppressants for metal plating operations Photomicrolithography process to produce semiconductors Photography and film products

Some grease-resistant paper Fast food containers/wrappers (27 fast food chains) Microwave popcorn bags Pizza boxes Candy wrappers Non-stick cookware such as Teflon™-coated pots/pans Used on carpets, upholstery, and other fabrics Water-resistant clothing - Hush Puppy Shoes (Wolverine Worldwide) Adhesives/Metal Plating Wastes Aviation hydraulic fluids Cleaning products Personal care products such as shampoo, dental floss, and cosmetics (nail polish, eye makeup) Paints, varnishes and sealants


Fluorinated Compounds

► Water soluble responsible for presence in leachate and potential release to the environment.

► Linked to many health impacts, linked to cancer ▪ Example – 50,000 people sued DuPont in Parkersburg WV for PFOA in drinking

water from plant making Teflon2

▪ Current estimates are 15 million people have contaminated drinking water in US ▪ Found in virtually every persons blood, US and worldwide

1.Huset et al., 2011 2. Environmental Working Group, 2018


PFAS Landfill Cycle


National Attention to PFAS

► In 2016, Vermont adopted a legal limit of 20 ppt for both PFOS and PFOA in groundwater, and an identical advisory level for tap water.

► In October 2017, Minnesota set advisory levels of 15 ppt for PFOS and 35 ppt for PFOA in tap water.

► In November 2017 , New Jersey accepted state scientists’ recommendation of legal limits of 14 ppt for PFOA and 13 ppt for another fluorinated chemical, PFNA, in tap water.

► In January 2018, Michigan adopted a legal limit of 70 ppt for PFOS and PFOA in groundwater used for tap water

► NC concerned with GenX (140 ppb) and PFBS ▪ DuPont, 3M phased out PFOA & PFOS, but considered GenX safer. ▪ Now EPA assessment – very small doses cause serious health risks

o Prenatal, immune system, liver, kidney, thyroid.


State Limits State Drinking Water Action Compound Level (ppt)

California Interim Response Levels Notification Levels

Sum of PFOA and PFOS PFOA PFOS

70 14 13

Connecticut Action Level Sum of PFOA, PFOS, PFNA, PFHxS, PFHpA 70

Massachusetts Office of Research & Standards Guideline

Sum of PFOA, PFOS, PFNA PFHxS, PFHpA 70

Minnesota Health Based Guidance for Water Surrogate of PFOS HBV

PFOA PFOS PFHxS

35 15 47

New Hampshire Rulemaking Initiated 12/31/18

PFOA PFOS Sum of PFOA and PFOS PFHxS PFNA

38 70 70 85 23

New Jersey Adopted Regulation Regulation in Development Guidance Value

PFNA PFOA PFOS

13 14 13

North Carolina Health Advisory GenX 140

Vermont Drinking Water Health Advisory Sum of PFOA, PFOS, PFNA, PFHxS, PFHpA 20

https://www.waterboards.ca.gov/drinking_water/certlic/drinkingwater/PFOA_PFOS.html

https://www.waterboards.ca.gov/drinking_water/certlic/drinkingwater/PFOA_PFOS.html

https://www.asdwa.org/wp-content/uploads/2018/01/CT-PFASActionLevel.pdf

https://www.mass.gov/files/documents/2018/06/11/orsg-pfas-20180608.pdf

https://www.mass.gov/files/documents/2018/06/11/orsg-pfas-20180608.pdf

http://www.health.state.mn.us/divs/eh/hazardous/topics/pfcshealth.html

https://www.des.nh.gov/media/pr/2019/2019-0102-pfas.htm

https://www.nj.gov/dep/rules/rules/njac7_10.pdf

https://ncdenr.s3.amazonaws.com/s3fs-public/GenX/NC DHHS Risk Assessment FAQ Final Clean 071417 PM.pdf

http://www.healthvermont.gov/environment/drinking-water/perfluoroalkyl-and-polyfluoroalkyl-substances-pfas-drinking-water

PFAS in Landfill Leachate

Lang et al, National Estimate PFAS Release to US Municipal Landfill Leachate, 2017


Site Example – Wolverine Dump Sites, Michigan ► Wolverine Worldwide dumped PFAS wastes in many Michigan landfills

► Wolverine World Wide tannery waste dumped into Northeast Gravel mine and landfill daily between 1970 and 1979. Keeler Brass also dumped electroplating wastes.

► A well near the Wolverine Gravel dump less than 10 miles away has almost 59,000 ppt PFAS, now a Superfund site

► Central Sanitary landfill, located in the Montcalm County village of Pierson, recently tested at concentrations above 70 parts-per-trillion.

► Kent County MI Landfill also has high concentrations PFAS

► Michigan very active in landfill identification and leachate for PFAS


Vermont Landfill Leachate (Vermont DEC, May 2018)

Vermont Guidelines, May 2018

Transborder implication – data and evaluations to the Gouvernement du Quebec Ministere de l’Environnement. 1,000 feet to Lake Memphremagog – water supply to Quebec.


Vermont PFAS in Closed Landfills (Vermont DEC, May 2018)


PFAS in NH Landfills

Criteria PFOA PFOS PFBA PFPEA PFHPAMin 0.5 0.44 0.55 1.0 0.89Max 2200 1560 493 260 410Mean 12.9 18.0 13.7 14.0 8.0

Median 9.0 17.1 21.7 18.5 10.8

Concentration in ng/LPFAS Concentrations in NH Landfill Leachate


PFAS in Landfill Leachate Nationwide - 20 Billion Gals/yr - 1900 Landfills *

►Main Typical PFAS*:

► Typical Concentrations: 0.1 to 10 ppb * ► PFOA perfluorooctanoic acid ► PFHxA perfluorohexanoic acid ► 5:3 FTCA fluorotelomer carboxylic acids

► Other PFAS:

► Typical Concentrations: 0.2 to 1.5 ppb ► PFOS ► PFBS ► PFHpA ► PFNA ► PFDA

* Ref. Lang, Johnsie PFAS in MSW Landfill Leachate 2016 Thesis UNC

Primary Source: Carpets and Clothing 26 | New York Federation Conference May 21 2019

Emerging Contaminants/PFAS Treatment Technologies

▪ Activated Carbon ▪ Ion Exchange ▪ Reverse Osmosis ▪ Deep Well Injection ▪ Innovative Technologies

o Thermolysis/combustion o Biological/Bioremediation o Advanced Remediation Catalysis (ARC) o Advanced Reduction Processes (ARP) o Non-Thermal Plasma Reduction o Advanced Oxidation – Persulfate; Nano-ZVI o Electro-Oxidation/Transmembrane Systems o Others?


Current PFAS Remediation Options for Water Supplies

Membrane Filtration Carbon Adsorption

Single-Use Resin Methanol/Brine Regenerable Resin

ECT2


Activated Carbon

► Granular Activated Carbon (GAC) Well Demonstrated ▪ Bituminous GAC – increasing full scale installations ▪ Competing Organics fill absorption sites ▪ Needs high quality leachate treatment before GAC

Influent Bulk solution + Contaminants

GAC

Effluent Treated Solution

General Comments: Typically operate downflow Typically Empty Bed Contact Time (EBCT) is in minutes Typical Superficial Velocities: 2-5 gpm/ft2

Isotherm testing initially done for feasibility Accelerated Column Test (ACT)/Rapid Small Scale Column Test (RSSCT) or pilot performed to validate system design Some usage rates/performance can be computer modeled in water GAC can be reactivated once it has been used


GAC Adsorption

► With GAC, adsorption occurs on the surface of the interior graphite platelets which are the solid part of the porous structure of the granules

► Adsorption is an equilibrium process and capacity is concentration dependent

► Exhausted GAC can often be sent to a reactivation furnace to destroy the adsorbates and produce a reusable product – air emissions?


GAC PFAS Adsorption


So absorption characteristics depend on type of PFAS!! – See vertical scale on both graphs.

IX - Ion Adsorption

► Many competing constituents ▪ Constituents Slows transport kinetics (speed that constituents adsorb) ▪ Limits adsorption capacity (how much PFAS can be adsorbed) ▪ Background organics ▪ Anions (chlorides, sulfates) ▪ May be restricted to batch treatment given limitations


General Process Flow Scheme Using Ion Exchange

Clarifier Suspended Solids &

TOC Reduction

S/Solids Filter

Ion Exchange Resin Lead & Lag Vessels

Leachate

Treated Water

Selective IX Capacity in leachate : Expect 10,000 to 20,000 BV


IX - Single-Use Selective Resin + Incineration

Short Contact Time ~3 mins Simple & Effective - Operator Preferred.

Cement Kiln Incineration 1400oC to 2000oC

PFAS –free water

Complete Destruction of PFAS

PFAS in water


Must Consider Negative Impact of Leachate Chemistry on GAC & IX

Ref. Raghab,Safaa, Treatment of Municipal Solid Waste Landfill HBRC Journal 2013 Vol 9 187-192


Some constituents interfere more than others!!

Removal Mechanisms for IX vs GAC

GAC removes by adsorption

using hydrophobic “Tail”

Sulfonic group

PFOS – Perfluoroalkyl Sulfonic Acid

Hydrophobic “Tail” Ionized “Head)

Selective IX Resins removes by both ion exchange and

adsorption using both “Head” & “Tail”

32 New York Federation Conference May 21 2019

Reverse Osmosis

► Should work effectively ► Membrane Based Separation Process. ► Separates Water from Organic and Inorganic Compounds. ► Effluent for reuse or disposal. ► What to do with Reject??? ► If recirculation is allowed, returns the contaminants to the landfill where they

were originally deposited. ► Solidification – Lime, others? ► Evaporation – Crystallization ▪ Heat needed ▪ Air Emissions


Reverse Osmosis

► Membrane Based Separation Process. ► Separates Water from Organic and Inorganic Compounds. ► If recirculation is allowed, returns the contaminants to the landfill where they

were originally deposited. ► Effluent for reuse or disposal.


Second Stage to reduce reject volume – or Evaporation

Reverse Osmosis Expected Removal (µg/l concentrations)

Compound Molecular Weight 2-Pass Rejection Acetone 58.1 96% Xylene 106.2 99% Chloroform 119.4 99.9% Tetrachloroethylene 165.8 99.9% 2,4-D 221.0 >99.9% 4,4’-DDT 354.5 >99.9% Chlordane 409.8 >99.9% PFOA 414.1 99.9%+ Expected PFOS 500.1 99.9%+ Expected

Source: Rochem, 2018


PFAS/PFOS

Compound (ng/l) Leachate RO 1

Permeate RO 2

Permeate Rejection Perfluorobutanesulfonic acid (PFBS) 280 <2 <1.9 >99.3%

Perfluorobutanoic acid (PFBA) 1100 5 <1.9 >99.8%

Perfluoroheptanoic acid (PFHpA) 480 <2 <1.9 >99.6% Perfluorohexanesulfonic acid (PFHxS) 690 <2 <1.9 >99.7%

Perfluorohexanoic acid (PFHxA) 2100 7.8 <1.9 >99.9% Perfluorooctanesulfonic acid (PFOS) 200 <2 <1.9 >99.1%

Perfluorooctanoic acid (PFOA) 820 2.5 <1.9 >99.8%

Perfluoropentanoic acid (PFPeA) 880 2.7 <1.9 >99.8%

Total 6550 18 0 >99.9%

Source, Rochem 2018 36 | New York Federation Conference May 21 2019

Accelerated Remediation Catalysis (ARC)

1. e- Donor/Acceptor 2. Low-Cost Catalyst 3. Shear Forces > Rxn

One cost example - CAPEX AOP: $1 MM ECT2: $1.2 MM ARC: $700 K (High Estimate


Accelerated Remediation Catalysis (ARC) for Landfill Leachate

► Contaminants Tested for Removal from Groundwater: ▪ 1,4-dioxane ▪ Perfluorocarbons ▪ Chlorinated ethenes ▪ Trihalomethanes ▪ Perchlorate ▪ Chlorobenzene ▪ Selenium ▪ Cr and As

► AFTER physical or biological treatment


Other Innovative Technologies

► Various studies of advanced oxidation / reduction: all on bench scale ▪ Ozone, perozone, heat-activated persulfate, cavitation oxidation, non-thermal

plasma, electrochemical oxidation, solvated electron reduction, zero valent iron (ZVI) reduction

► Advanced Reduction Processes (ARP) ▪ Catalytic generation of reductants using sulfite

► Electro-Oxidation – ▪ Reported 96 - 99% removal for Perfluorooctanoic acid (PFOA), Perfluorooctane

sulfonate (PFOS), Perfluorononanoic acid (PFNA) - RO before or after for polishing?

► Plasma – Limited sites - application in Australia ► Most Have Limited Bench-Scale Evaluations


Treatment Technologies – Pretreatment?

Contaminant Biological Treatment

Activated Carbon1

Ion Exchange1

Reverse Osmosis2 Electro Oxidation

AOP ARC

COD/Ammonia

Yes Possible Possible Possible – Reject Yes Possible Possible

I,4 Dioxane Possible OK OK OK – Reject OK OK OK DON and rDON

Possible OK Possible OK – Reject Possible Possible Possible

PPCP Possible OK OK OK – Reject OK OK OK

Nanoparticles /Microplastics

No No No Yes – Reject No No No

UV Absorbing No Possible No Yes <500 nm, Reject

Possible No Possible

PFAS No OK OK OK – Reject Possible Possible OK

1. Residuals from spent activated carbon or ion exchange requires replacement and disposal

2. RO reject flow requires management by concentration, evaporation, solidification, deep well injection, or other means. 48 | New York Federation Conference May 21 2019

Thank You !!!

► Ivan A. Cooper, PE, BCEE ► Civil and Environmental Consultants, Inc. ► [email protected] ► Direct: (980) 260-2110 ► Mobile: (980) 238-0373

49| New York Federation Conference May 21 2019

mailto:[email protected]

Documents

Leachate Treatment for a Variety of Emerging Contaminants