Technical Advisory Group Meeting Florida Atlantic University Funded - - PDF document

Technical Advisory Group Meeting Florida Atlantic University

Funded by the Hinkley Center for Solid and Hazardous Waste Management (HCSHWM)

DATE: Friday, January 30, 2015 TIME: 12:00 noon to 1:50 pm WHERE: CM Building (22), Room 130 (Studio 1) 777 Glades Road, Boca Raton, FL 33431 MEETING AGENDA

12:00 – 12:10 pm

Opening Address and Introduction of Participants

• D. Meeroff

12:10 – 12:40 pm

Leachate Collection System Clogging

• J. Dacey
• A. Harris
• D. Purdy

12:40 –1:10 pm

Safe Discharge of Landfill Leachate to the Environment J. Lakner

1:10 –1:40 pm

Groundwater Circulation Well Experiments

• A. Albasri

1:40 –1:50 pm

Open Forum Participants

1:50 pm

Adjourn, Thank You

• D. Meeroff

Attendance: Denys Purdy, Justin Dacey, Alyssa Harris , Tim Vinson, Ahmed Albasri, Joseph Lakner, Dan Meeroff, Megan Matson, Bishow Nath Shaha, Lisandre Meyer, Jeff Roccapriore, Craig Ash, Richard Meyers, Ravi Kadambala, Ron Schultz, Owrang Kashef

• 1. Opening address by D. Meeroff followed by introduction of the group members and participants (12:05

pm)

• 2. J. Dacey gave a presentation on the Flowmark antiscaling system. Essentially, the device doubled the

particulate calcium compared to upstream levels. Then he described the dilution system for scaling control and showed data to support the hypothesis that the compost industrial supply well’s groundwater improved the calcium carbonate precipitation potential of leachate as measured by the Langelier Saturation Index and the Ryznar Index. Then he described the upcoming flowmark side‐by‐ side experiment. The first question was about the impact of the dilution and leachate flows vs. rainfall.

• Dr. Meeroff responded that this work is currently ongoing. Dr. Kadambala asked for details how the

Flowmark system works, what pipe size, what other strategies did you test, what are the flows? J. Roccapriore asked about the pipe lengths, and revealed that Monarch Hill has experienced some calcium carbonate scaling in its leachate collection system, which has essentially no gravity lines because it is pumped to a force main directly from the hill.

• 3. A. Harris gave a presentation on her leachate aeration tests, crystal formation, and vibration table
• experiments. Then she showed her black sludge formation data. The stationary samples had much finer

particles compared to the rotated and aerated samples that had larger agglomerated flocs. She showed micrographs of two different organisms growing in the sludge and then mentioned new experiments which contrast the effect of HDPE v. PP to see if there are surface charge interactions with the pipe material itself that promote rock formation. In addition, she plans to heat the leachate to see the effect of

• temperature. Next she presented her results of the rubber‐like substance (“blob”). She tested loss on

ignition (86%, which revealed a dominant organic content), bleach reaction (which revealed microorganisms growing on the surface), acid reaction (which revealed calcium carbonate effervescence), X‐ray diffraction (which revealed chloride salts of ammonium, sodium, and potassium), and X‐ray fluorescence (which revealed calcite). Next she presented her work on testing the cationic polymer Clarifloc used by the wastewater treatment plant that delivers biosolids to the landfill. It was hypothesized that the polymer may play a role in the blob formation. She tested the polymer with lime and crushed drywall, and was planning to test with leachate, ash, and biosolids too. J. Roccapriore mentioned that Waste Management does not experience any intensive clogging and operates an 8‐inch forcemain flowing full with very few gravity lines in the system. They have never encountered any rubber‐like substance. Also they do not have a true ash monofill but do use ash for daily cover. He mentioned that Broward County operates an ash monofill and recommended to ask them if they experience anything like this. R. Meyers replied that he would be more than happy to supply leachate and ash samples for the experiments. C. Ash mentioned that Waste Management operates an ash monofill in Miami‐Dade but to his knowledge they do not experience any similar problems. Dr. Bloetscher asked about the pH acting in the opposite way as he would expect after aeration. Dr. Meeroff said that the observation was verified several times and is the basis of University of Florida doctoral candidate, Kevin Kohn’s dissertation on carbon dioxide stripping for scaling control.

• 4. J. Lakner presented his work on advanced oxidation of leachate from partially closed landfill leachates

for beneficial reuse of this water as a resource. He presented water volumes and water quality data. Then he explained how the processes work, and then he presented pilot testing results. First he verified the reaction mechanism, performed a UV scan to determine the maximum absorbance, then he ran tests to determine the effect of catalyst aids, but none of the metals tested performed better than UV/TiO2, and only zinc did not inhibit the reaction. Then he showed results using different lamps and reactor

• configurations. Comparing the lamp power of the two types of lamps in different wavelength regimes,

they were found to have similar output. The flow through reactor configuration has about 20x more power density and reaction detention time compared to the falling film reactor but light penetration is an issue. Next he presented preliminary results from the critical orifice advanced oxidation unit. With diluted leachate, the unit increased alkalinity, decreased pH, removed 70% of COD in just 20 minutes, but increased TDS. It was recommended to test the unit as a pretreatment or polishing step to photocatalytic oxidation. J. Roccapriore asked if the fixed volume tested in 8 hours could be scaled up to help offset the surcharge to a wastewater treatment plant. Safe discharge for onsite use is the goal of this project to be able to use for irrigation for dust control is an option at Monarch Hill. Previous work done by F. Youngman determined 44 hours treatment required for Monarch Hill leachate to meet the COD

• limit. At 24 hours detention, the process is cost effective, so the goal is to reduce the time required for
• treatment. C. Ash commented that this is a big concern for 50,000‐100,000 gallons per day of leachate

generated at these large facilities. More disposal options are needed. Dr. Bloetscher mentioned the

• rifice process increased the pH and alkalinity after superoxide formation in the microbubbles. This

needs to be investigated and experiments are being prepared. T. Vinson asked for clarification on the purpose of the absorbance tests, and J. Lakner described that the flow through experiments do not create a thin film, so UV light penetration is important because of the 2‐inch thick bulk solution. So this is why those absorbance tests tried to quantify the light penetration or shadow effect of titanium dioxide dose. Dr. Kadambala mentioned previous research conducted at UF on R/O pretreatment strategies for leachate recirculation. T. Vinson mentioned that Tim Townsend could provide these

• results. C. Ash mentioned that the Medley Landfill uses a biological pretreatment process primarily for

ammonia removal and arsenic, but the facility is now going to deepwell injection.

• 5. A. Albasri presented his fourth phase of work on iron removal from the subsurface using groundwater

circulation well technology. He is now using a 32‐gallon model with 3 monitoring wells to measure the

radius of influence. He loaded the system for several months to create a spiked 10‐50 mg/L iron groundwater/soil. On 01/19/2015, he turned on the GCW system and as of 01/22/2015, no removal of iron has been found yet. Three days’ worth of results is not enough to show any trend. Albasri is worried about ferric iron plugging the system. Dr. Bloetscher pointed out that bleach will control iron bacteria plugging. T. Vinson recommended that in the real world, you would just drill more wells and then he mentioned some work from UF regarding interceptor trenches with media. Dr. Bloetscher mentioned that wells will clog with iron bacteria and sloughing will create clogging in the subsurface and recommended to periodically use some sort of filtration (sand separator), which is what is used in municipal supply wells.

• 6. Dr. Meeroff thanked all of the participants, and the meeting was adjourned at 1:50 pm.

1

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Technical Advisory Group Meeting

• 1. “Sustainable Management of Pollutants Underneath

Landfills”

• 2. “Onsite Treatment of Leachate Using Energized

Processes” Daniel E. Meeroff, Ph.D.

Department of Civil, Environmental & Geomatics Engineering

Laboratories for Engineered Environmental Solutions

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Agenda

• 1. Introductions/Opening Remarks
• 2. Evaluation of Leachate Clogging
• 3. Photocatalytic Oxidation Studies
• 4. Circulation Well Experiments
• Dr. Meeroff

Dacey/Harris Lakner Albasri

• 5. User Input/Open Forum

Everyone Technical Advisory Group Meeting FAU ▪ January 30, 2015

http://labees.civil.fau.edu/leachate

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Current Projects

• "Critical Examination of Leachate Collection

Systems Clogging at SWA Disposal Facilities"

• "Safe Discharge of Landfill Leachate to the

Environment"

• "Sustainable Management of Pollutants Underneath

Landfills"

• "Assessing Options for On-site Leachate and

Groundwater Management Strategies at Florida Landfills“

• "Investigation of Effective Odor Control Strategies"

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Introductions

Technical Advisory Group Meeting FAU ▪ January 30, 2015

“Critical Examination of Leachate Collection System Clogging”

2

Technical Advisory Group Meeting FAU ▪ January 30, 2015 FAU Boca Raton, FL ▪ January 30, 2015

Florida Atlantic University College of Engineering & Computer Science

“Effects of Flowmark Water Treatment System and Dilution Water in Leachate Collection System”

Justin Dacey

Department of Civil, Environmental & Geomatics Engineering

Laboratories for Engineered Environmental Solutions

Agenda

• FlowMark Water Treatment System
• FlowMark Device Overview
• Placement in Leachate Collection System
• FlowMark Device Results
• Soluble Calcium v. Total Calcium
• Leachate Dilution Using Industrial Well Water
• Dilution Water System Overview
• Water Quality After Dilution
• Langlier Index
• Ryznar Index
• Next Steps

FlowMark Water Treatment System

FlowMark (Electronic Pulsed Power)

Leachatewatertreatment.com

FlowMark Device Overview

• Electrically Generated Catalytic Effect
• Claims to Help Precipitate Microscopic Seed

Crystals of CaCO3

• Intended to Prevent Mineral Scale

Accumulation

• Installed in Leachate Collection System at

Manhole 11 in April 2014

FlowMark and Sampling Locations

1 Cell 13

11 9 8 5 A 13

Cell 11 Cell 9 Cell 8 Cell 5

Cell 1 Cell 2 Cell 3 Cell 4 Cell 6 Cell 7 Cell 10 Cell 12 Cell 14

FlowMark in Manhole 11 Leachate Flow

3

FlowMark In Action at Manhole 11

Particulate Calcium (>45μm) with FlowMark

Parameter Units Upstream (Manhole 11) Downstream (Manhole 5)

pH 7.20 7.43 Alkalinity mg/L as CaCO3 3850 3660 Ca (Total) mg/L as CaCO3 5800 2200 Ca (Dissolved) mg/L as CaCO3 4700 1400

19.0% 36.4% Percent Particulate:

FlowMark Device Results

• Appears to Aid Particulate Formation
• Further Testing Required
• Short Circuiting Observed around FlowMark

in Manhole

• Untreated Leachate Introduced to Flow from

Landfill Cells Downstream

Leachate Dilution with Industrial Supply Well Water

Dilution Water System Overview

• Water Sourced from Composting Industrial

Supply Wells On-Site

• Intended to Reduce Scale Formation

Potential by Dilution of Leachate

• Decrease Langlier Saturation Index (LSI)
• Increase Ryznar Index (RI)
• Installed into Leachate Collection System at

Manhole 11 in May 2014

Dilution Water Location

Cell 13

11 9 8 5 13

Cell 11 Cell 9 Cell 8 Cell 5

Cell 1 Cell 2 Cell 3 Cell 4 Cell 6 Cell 7 Cell 10 Cell 12 Cell 14

Compost Well Dilution Water Leachate Flow

4

Dilution Water in Manhole 11 Water Quality After Dilution

• Water Quality
• Alk.: 330 - 400 mg/L as CaCO3
• Calcium: 360 – 450 mg/L
• pH: 6.5 – 7.3
• TDS: 590 – 2200 mg/L
• Temperature: 25 – 29 °C
• LSI: -0.2 - +0.5
• RI: 6.2 – 7.0
• Water Quality
• Alk.: 330 - 9700 mg/L as CaCO3
• Calcium: 1,000 – 26,000 mg/L
• pH: 6.1 – 7.8
• TDS: 7,100 – 69,000 mg/L
• Temperature: 25 – 36 °C
• LSI: +1.0 - +2.7
• RI: 2.2 – 6.5

Composting Industrial Supply Wells Leachate Composite: Manholes 5, 8, 9, 11, and 13

Saturation Indices, Before Dilution

RI = 2pHsat– pHobs

Heavy Scale

RI < 5.5

Some Scale

5.5<RI<6.2

Non- Scale

Forming

6.2<RI<6.8

Corrosive 6.8<RI<8. 5

Very

Corrosive RI>8.5

Langelier Saturation Index (LSI) Ryznar Index (RI)

LSI = pHobs – pHsat

Under- saturated

LSI < –0.4

Neutral

–0.4 < LSI < +0.4

Super- saturated

LSI > +0.5

Leachate LSI Target = +0.4 RI Target = 6.0

Compost Wells Compost Wells

Saturation Indices, After Dilution

RI = 2pHsat– pHobs

Heavy Scale

RI < 5.5

Some Scale

5.5<RI<6.2

Non- Scale

Forming

6.2<RI<6.8

Corrosive 6.8<RI<8. 5

Very

Corrosive RI>8.5

Langelier Saturation Index (LSI) Ryznar Index (RI)

LSI = pHobs – pHsat

Under- saturated

LSI < –0.4

Neutral

–0.4 < LSI < +0.4

Super- saturated

LSI > +0.5

Leachate LSI Target = +0.4 RI Target = 6.0

Compost Wells Compost Wells

Dilution Water Results

• Leachate LSI and RI Improved
• LSI Range Extends into Neutral
• RI Range Extends into Non-Scale Forming
• CISW Water Different Than Expected
• Higher LSI
• Lower RI

Operational Control

• Need to be able to adjust the dilution water based on

appropriate conditions (realtime monitoring)

• pH, Temperature, TDS, Alkalinity, Calcium, Flowrate
• Issues
• pH, TDS probes will not work
• Alkalinity/Calcium require titrations
• Temperature and flowrate are highly variable and not

correlated

5

Questions

• Seed crystals form and flow until they settle out

somewhere downstream

• What are the water quality impacts downstream vs.

upstream?

• Are we cleaning existing clogs?
• What are the power requirements for a full scale

system?

• What are the properties of this loose sludge material?
• Where will it collect? What if the material collects in

the deepwell?

• What is the frequency of pumping out this material?

Next Steps

• Set up FlowMark On/Off Direct Comparison
• Currently Being Designed
• Eliminate Short-Circuiting Around Unit
• Eliminate Leachate from Other Cells Interfering with

Comparison

• Evaluate Dilution Calculations with New Water

Quality Data

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aeration Experiment

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aeration Tests

pH v. time Turbidity v. time

6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 50 100 pH Elapsed Time (minutes)

Aerated Control

20 40 60 80 100 50 100 Turbidity (NTU) Elapsed Time (minutes)

Aerated Control

Technical Advisory Group Meeting FAU ▪ January 30, 2015

6

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Sample: Cell 8 Lat 3 March 6 2014 ”A” Cell 8 Lat 3 March 6 2014 ”B” Cell 8 Lat 3 March 6 2014 “C” Cell 8 Lat 3 March 6 2014 ”D” Amount of Leachate 100ml 100ml 100ml 100ml Aerated? Aerated (1hr 20 min, ~+1pH) Aerated(1hr 20 min, ~+1pH) Non-Aerated Non-Aerated Period of rotation 10.55s/5=2.11s Set 450 Stationary 10.68s/5=2.14s Set 450 Stationary Initial Weight 95.96g 97.96g 99.16g 99.60g Final Weight (5 days) 5.31g 5.73g 5.79g 4.42g Initial pH: 7.40 7.45 7.41 7.44 pH After Aeration 8.54 8.60 N/A N/A Initial 82.8 84.9 85.6 85.9

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Leachate After 2 days

Aerated and Rotated Non-Aerated and Rotated

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Leachate after 2 days

Aerated and Stationary Non- Aerated and Stationary

Technical Advisory Group Meeting FAU ▪ January 30, 2015

After 5 Days

Aerated and Rotated Non-Aerated Rotated

7

Technical Advisory Group Meeting FAU ▪ January 30, 2015

After 5 Days Stationary

Aerated Non-Aerated

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Summary

• The stationary samples did not appear to form

separate substances

• Stationary samples created fine particles
• The rotation seems to create larger particles

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aerated and Rotated Sample Dark Substance

Technical Advisory Group Meeting FAU ▪ January 30, 2015

400x Dark Substance

Technical Advisory Group Meeting FAU ▪ January 30, 2015

4000x Dark Substance

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Next Steps

• Currently running the experiment with HDPE

containers

• Results in progress
• Plan to use an immersion heater to increase the

temperature of the leachate

• Waiting for results from UF to see the composition of

solids formed

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Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

“Blob” from December 2014

• Collected from SWA

Leachate collection system

• Dark brown semi-

solid material

• Rubber-like
• Tests:
• Loss on Ignition
• Reaction to Bleach
• Reaction to Acid
• UF tested XRF and

XRD

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Loss on Ignition

Loss on Ignition: 86%

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Bleach and Acid Reaction Tests: A B C D

Bleach 10% Bleach 1M HCl 1M HNO3

Technical Advisory Group Meeting FAU ▪ January 30, 2015

(A) Bleach

Initial Final

Technical Advisory Group Meeting FAU ▪ January 30, 2015

(B) 10% Bleach

Initial Final

9

Technical Advisory Group Meeting FAU ▪ January 30, 2015

After soaking in bleach for several days

Technical Advisory Group Meeting FAU ▪ January 30, 2015

(C) 1M HCl

Initial Final

Technical Advisory Group Meeting FAU ▪ January 30, 2015

(D) 1M HNO3

Final Initial

Technical Advisory Group Meeting FAU ▪ January 30, 2015

XRF Data (UF)

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Possible Explanations

• Possibility of the blobs due to disposal
• f biosolids at the landfill
• Polymers could leach out of the

biosolids after they had been placed in the landfill

• Then move with the leachate into the

LCS and then reform as a semi-solid at a downstream point in the LCS

10

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Coagulation Polymer: Clarifloc

• Cationic water-soluble polymer in emulsion

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Clarifloc with CaO (Lime)

0.5 gram of CaO ~1 gram of CaO

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Clarifloc with CaSO4 (Dry wall)

~0.5g (CaSO4) ~1g (CaSO4)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Next Steps

• Results in progress
• Observe the samples over time
• Differences in consistency
• Separation (Does the polymer hold)?
• Visual observations
• What happens if we mix leachate with these samples?
• Measure the pH

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Hinkley Center for Solid and Hazardous Waste Management January 30, 2014

Florida Atlantic University College of Engineering & Computer Science

“Safe Discharge of Landfill Leachate to the Environment”

Joseph Lakner

Laboratories for Engineered Environmental Solutions

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Problem Statement

• In South Florida, several landfills combine leachate

for disposal

• Active leachate
• Mature leachate
• Partially closed landfill leachate
• The partially closed landfill leachate can account for

10-25% of the overall leachate flow

• 20,000 – 200,000 gpd

11

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Problem Statement

• Current disposal methods for Solid Waste Authority
• f Palm Beach is deep well injection.
• Is there a better way to cost effectively manage

these liquids?

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Beneficial Use of Closed Leachates

Surface Water Discharge

• The most

complex discharge requirements

Industrial Reuse

• Irrigation,

cooling water

• Hardness

scaling

Dilution Water

• To reduce

leachate clogging

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Dyer Park Landfill

Technical Advisory Group Meeting FAU ▪ January 30, 2015

SWA Leachate Quantity

1,000,000 2,000,000 3,000,000 4,000,000 5,000,000 6,000,000 1989 1991 1993 1995 1997 1999 2001 2003 2005 2007 2009 2011 2013 Leachate Generation (gallons per month) Year

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Typical Leachate Constituents

Parameter Mean Values from of Dyer Park ( Statom, 2004) Primary Drinking Water Standards Secondary Drinking Water Standards F.A.C. 62-550 F.A.C 62- 777 Antimony µg/L BDL 6 NR NR NR Arsenic µg/L BDL 10 NR NR NR Barium µg/L BDL 2000 NR NR NR Beryllium µg/L BDL 4 NR NR NR Cadmium µg/L BDL 5 NR NR NR Copper µg/L BDL NR 1 NR NR Lead µg/L BDL 15 NR NR NR Mercury µg/L BDL 2 NR NR NR Selenium µg/L BDL 50 NR NR NR Silver µg/L BDL NR 0.1 NR NR Thallium µg/L BDL 2 NR NR NR Zinc µg/L BDL NR 5 NR NR

Parameter Mean Values from of Dyer Park ( Statom, 2004) Primary Drinking Water Standards Secondary Drinking Water Standards F.A.C. 62-550 F.A.C 62- 777 BOD mg/L 47 NR NR 20 NR Total Kjeldahl Nitrogen (as N) mg/L 504.48 NR NR 10 NR Ammonia (as N) mg/L 473.01 NR NR 5 2.8 Total dissolved solids mg/L 3,442 NR 500 NR 500 Chloride mg/L 836.67 NR 250 NR NR Iron µg/L 4750.2 NR 0.3 NR 1000 Manganese µg/L 190.76 NR 0.05 NR NR COD mg/l 835 NR NR NR NR TOC mg/L 150 NR NR NR NR Nitrate (as N) mg/L 5.27 NR NR NR NR Phosphorus mg/L 3.18 NR NR NR NR Alkalinity mg/L 2,453 NR NR NR NR Bicarbonate mg/L 2,660 NR NR NR NR Calcium mg/L 176 NR NR NR NR TIC mg/L 54 NR NR NR NR Specific conductance (mhos/cm) 7,642 NR NR NR NR pH 7.07 NR 6.5-8.5 NR NR Magnesium mg/L 53.75 NR NR NR NR Fluoride mg/L 0.37 4000 2 NR NR Sulfate mg/L 20.09 NR 250 NR NR Chromium µg/L 20.45 100 NR NR NR Nickel µg/L 49.53 NR NR NR NR Boron µg/L 3193.33 NR NR NR NR Cobalt µg/L 16 NR NR NR NR Vanadium µg/L 10.56 NR NR NR NR

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Values Tested for during 2014

Parameter Mean Values from of Dyer Park ( Statom, 2004) Mean Values of Dyer Park (Meeroff) Values of Dyer Park (Lakner) Standards Ammonia (as Nh3) mg/L 473.01 365 ± 140 312 2.8 Total dissolved solids mg/L 3,442 2650 ± 190 2786 500 COD mg/l 835 650 ± 150 375 NR Alkalinity mg/L 2,453 1950 ± 260 1550 NR Calcium mg/L 176 450 ± 70 430 NR pH 7.07 7.23 ± 0.36 7.35 6.5-8.5

12

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Photocatalytic Oxidation

• Ultraviolet Radiation +

Semiconductor

• Simple, one stage

process

• Ultraviolet Light
• Titanium Dioxide

Technical Advisory Group Meeting FAU ▪ January 30, 2015

How Does Photocatalysis Work?

h+ e‐

Mn+

(aq)

M0

(s)

[ Photoreduction ]

• f metals

+

hν

[ Photooxidation ]

• f organics

Oxygen Water

Titanium Dioxide

Proton Hydroxyl radical Water and carbon dioxide

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Phase One 2014 Research

• TiO2 wavelength optimization
• Crystal Violet Test of TiO2 Oxidation process

reaction mechanism verification

• Optimization of COD Removal with Catalysis Aids
• Alternative Advanced Oxidation Process

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Phase One 2014 Research

• Falling Film Reactor 5 g/L TiO2
• 150-W
• 450-W
• Flow Through Reactor 5 g/L TiO2
• 150-W
• 450-W
• Flow Through Reactor with Aeration and 10 g/L TiO2
• 150-W
• 450-W
• 150-W Flow Through Reactor with Aeration and 0.2 g/L

TiO2

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Crystal Violet Test

• Test the hydroxide

ion generation of TiO2

• 1x 10 -4 Molar

Concentration

• 5 g/L TiO2

Technical Advisory Group Meeting FAU ▪ January 30, 2015

TiO2 Dosing Test

• Full spectrum scan from 400

nm to 200 nm

• Absorbance test conducted at

330 nm.

13

Technical Advisory Group Meeting FAU ▪ January 30, 2015

TiO2 Dosing Test

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Improving COD Removal with Catalyst

• Stock solution of 5 g/L TiO2
• Increase high potential bias of

solution

• Reduce recombination of

electrons into TiO2

• Zinc, Aluminum, Steel Wool

and Combinations of these catalysts

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Improving COD Removal with Catalyst

h+ e‐

Mn+

(aq)

M0

(s)

[ Photoreduction ]

• f metals

+

hν

[ Photooxidation ]

• f organics

Oxygen Water

Titanium Dioxide

Proton Hydroxyl radical Water and carbon dioxide

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Improving COD Removal with Catalyst

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Lamp Spectrum

Technical Advisory Group Meeting FAU ▪ January 30, 2015

(150-W) Lamp

Titanium Dioxide Absorption Spectrum

14

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Falling Film Reactor 450-W

Titanium Dioxide Absorption Spectrum Medium Pressure Mercury- vapor Spectrum

• 0.1

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 200 300 400 Absorbance Wavelength (nm)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Light Intensity Measurement

• 150-W UV A&B: 0.5 mW/cm2
• 150-W UV C: 7.21 mW/cm2
• 450-W UV A&B: 56.0 mW/cm2
• 450-W UV C: 0.06 mW/cm2

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Falling Film Reactor

Light Arch Length (cm) Circumference (cm) Area (cm2) Measured UV (mW/cm2) Total Power (W) Test Size (L) Falling time (Seconds) Exposure time (Seconds) Recirculated Rate (L/hr.) Number of Pass per liter per hour Exposure Time per hour (Seconds) Energy per Hour per liter (W/L) Length of test (hours) Total Watt Hours/ Liter (Whr/L) 450W UV A&B 27.94 15.70 438.66 56.00 24.56 9.30 0.41 0.14 320.00 34.41 4.75 0.03 8.00 0.26 450W UV C 27.94 15.70 438.66 0.06 0.03 9.30 0.41 0.14 320.00 34.41 4.75 0.00 8.00 0.00 150W UV A&B 79.30 15.70 1245.0 1 0.50 0.62 10.00 0.41 0.39 320.00 32.00 12.54 0.00 8.00 0.02 150W UV C 79.30 15.70 1245.0 1 7.21 8.98 10.00 0.41 0.39 320.00 32.00 12.54 0.03 8.00 0.25

Lamp Power Calculations

Time of Fall in Reactor Equation t= (2d/a).5

• Distance of fall: 83 cm
• Acceleration rate: 9.81m/s2

Time of Fall in Reactor 0.41 second per pass Technical Advisory Group Meeting FAU ▪ January 30, 2015 Flow Through Reactor

Light Arch Length (cm) Circumference (cm) Area (cm2) Measured UV (mW/cm2) Total Power (W) test size (L) Retention Time ( hr.) Percent Exposure per Retentions Time Times recirculated per hour per liter (1/hr.) Exposure per Liter (1/L) Watts per Liter (W/L) Test (hr.) Total Watt Hours/ Liter (Whr/L) 450W UV A&B 27.94 15.70 438.66 56.00 24.56 8.60 0.03 0.34 24.42 0.27 6.63 8.00 53.08 450W UV C 27.94 15.70 438.66 0.06 0.03 8.60 0.03 0.34 24.42 0.27 0.01 8.00 0.06 150W UV A&B 79.30 15.70 1245.0 1 0.50 0.62 9.10 0.03 0.96 23.08 0.72 0.45 8.00 3.61 150W UV C 79.30 15.70 1245.0 1 7.21 8.98 9.10 0.03 0.96 23.08 0.72 6.50 8.00 52.02

Lamp Power Calculations

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Falling Film Reactor

• Reservoir (10L)
• Temperature Sensor
• Pump (360 L/h)
• Flow Regulator
• Sampling Port
• 3 Way Valve
• Weir Compartment
• UV Power Source (150W)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor

• Reservoir (10L)
• Temperature Sensor
• Pump (360 L/h)
• Flow Regulator
• Sampling Port
• 3 Way Valve
• Weir Compartment

15

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Experimental Protocol

• Collection of Samples

87

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Experimental Protocol

• Operation of Pilot Reactor
• Leachate is measured using

2000 ml graduated cylinder

• TiO2 is measured in 1000 ml

beaker

• Slurry is made from TiO2 and

leachate then added to reservoir

88

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Cooling Solution

• Existing Problem
• 50 ft. Stainless Steel 5/16

coil

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Experimental Protocol

• Experiments were run reactor for 8 hours
• Samples were be collected at 2 hour intervals
• Sample collection procedure is as follows:
• Do not turn off reactor, take samples from

discharge pipe

• Take a sample (60 ml) and then placed in tubes to

be centrifuged

90

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Experimental Protocol

• Test centrifuged sample for COD, ammonia,

alkalinity and pH

• UV sensor was used to measure the light intensity

in the reactor

• Monitor off gas to determine where ammonia and

COD end up

• Monitor temperature of Leachate

91

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Experimental Protocol

• COD test using Hach DR4000U with a dilution of 1:5
• Ammonia test using Hanna Hi 937005 with a dilution
• f 1:10
• Alkalinity test using Hach digital titrator SM2320B

using 1.6 H2SO4 and a dilution of 1:10

• pH test using Hach Meter
• DO test using Hach Meter

92

16

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Falling Film Reactor

• 10 Liter of Leachate
• Added 5 g/L of TiO2
• Mixed for 10 minutes without

UV light activated.

• Sampled every 2 hours
• Flow of 320 L/hr.

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparing Falling Film Reactor 150-W vs. 450-W Temperature

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparing Falling Film Reactor 150-W vs. 450-W pH

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparing Falling Film Reactor 150-W vs. 450-W Ammonia

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparing Falling Film Reactor 150-W vs. 450-W Alkalinity

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparing Falling Film Reactor 150-W vs. 450-W COD

17

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Falling Film Reactor

• Starting Concentrations
• COD 375 mg/\L
• NH3 313 mg/L
• pH 7.35
• Alkalinity 1550 mg/L
• Final Concentrations 8 hours

150-W

• COD 300 mg/\L
• NH3 232 mg/L
• pH 8.2
• Alkalinity 1020 mg/L
• Final Concentrations 8 hours

450-W

• COD 255 mg/\L
• NH3 243 mg/L
• pH 8.95
• Alkalinity 1050 mg/L

Final Removal % 150-W 450-W COD 20 32 Ammonia 26 22 Alkalinity 34 32 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor

• 10 Liter Leachate
• TiO2 Concentration of 5 g/L
• Sampled every hour
• Reactor flushed every hour
• Flow of 210 L/hr.

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor 150-W vs. 450-W Temperature

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor 150-W vs. 450-W pH

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor 150-W vs. 450-W Ammonia

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor 150-W vs. 450-W Alkalinity

18

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor 150-W vs. 450-W COD

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor

• Starting Concentrations
• COD 300 mg/\L
• NH3 232 mg/L
• pH 8.2
• Alkalinity 1020 mg/L
• Final Concentrations 8

hours 150-W

• COD 225 mg/\L
• NH3 293 mg/L
• pH 8.7
• Alkalinity 900 mg/L

Final Removal % 150-W 450-W COD 25 8 Ammonia 17 45 Alkalinity 12 24

• Final Concentrations 8

hours 450-W

• COD 255 mg/\L
• NH3 243 mg/L
• pH 9.85
• Alkalinity 1050 mg/L

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration

• 10 Liter Leachate
• TiO2 Concentration of 10 g/L
• Sampled every hour
• Reactor flushed every hour
• Flow of 210 L/hr.

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W vs. 450-W Temperature

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W vs. 450-W pH

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W vs. 450-W Ammonia

19

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W vs. 450-W Alkalinity

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W vs. 450-W COD

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration

• Starting Concentrations
• COD 263 mg/\L
• NH3 193 mg/L
• pH 8.7
• Alkalinity 900 mg/L
• Final Concentrations 8

hours 150-W

• COD 243 mg/\L
• NH3 119 mg/L
• pH 9.0
• Alkalinity 620 mg/L

Final Removal % 150-W 450-W COD 7 31 Ammonia 38 25 Alkalinity 31

• Final Concentrations 8

hours 450-W

• COD 189 mg/L
• NH3 75 mg/L
• pH 8.76
• Alkalinity 700 mg/L

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration and 0.2 g/L TiO2 (150-W)

• 10 Liter Leachate
• TiO2 Concentration of 0.2

g/L

• Sampled every hour
• Reactor flushed every hour
• Flow of 210 L/hr.
• Anti-Foam 20 ml

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W and 0.2 g/L TiO2 Temperature

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W and 0.2 g/L TiO2 pH

20

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W and 0.2 g/L TiO2 Ammonia

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W and 0.2 g/L TiO2 Alkalinity

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration 150- W and 0.2 g/L TiO2 COD

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Flow Through Reactor with Aeration and 0.2 g/L TiO2 (150-W)

• Starting Concentrations
• COD 394 mg/\L
• NH3 193 mg/L
• pH 7.17
• Alkalinity 1310 mg/L
• Final Concentrations 8 hours
• COD 388 mg/\L
• NH3 173.5 mg/L
• pH 8.95
• Alkalinity 920 mg/L

Final Removal % 150-W COD

• 32

Ammonia 11 Alkalinity 31 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparison of COD % Removal

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparison of Alkalinity % Removal

21

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparison of Ammonia % Removal

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Comparison of Temperature

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation Process

Pump

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation Process

• 10 gallon of leachate
• Diluted to 17 %
• Test ran for 20 minutes

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation pH

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation Alkalinity

22

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation COD

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation TDS

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Critical Orifice Advanced Oxidation

• Starting Concentrations
• COD 281 mg/\L
• TDS 437 mg/L
• pH 7.99
• Alkalinity 230 mg/L
• Final Concentrations 20 Minutes
• COD 83 mg/\L
• TDS 677 mg/L
• pH 7.75
• Alkalinity 360 mg/L

Final Removal % COO COD 70 TDS

• 55

Alkalinity

• 56

Technical Advisory Group Meeting FAU ▪ January 30, 2015

TiO2 Recovery

• Centrifuge for experiment

samples

• 1 μm filter not effective
• Some removed with 0.45 μm

filter

• Settling and decanting

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Research for 2015

• Filter after reactor using 1 μm

felt filter

• Combination of Lights
• Zinc Powder
• Ozone Light
• Lime Soften
• Critical Orifice Device
• High Electrical Potential Bias

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Acknowledgements

23

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Any Volunteers?

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Hinkley Center for Solid and Hazardous Waste Management January 30, 2014

Florida Atlantic University College of Engineering & Computer Science

“Sustainable Management of Pollutants Underneath Landfills”

Ahmed Albasri

Laboratories for Engineered Environmental Solutions

Technical Advisory Group Meeting FAU ▪ January 30, 2015

4th phase of experimenting

• 2014-2015

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aquarium (testing cell) building

• Aquarium has been set by coating the discharge

pipe by thin layer of gravel.

• 1 inch of soil had been set in the bottom of the

aquarium to enable full circling

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aquarium (testing cell) building

• Setting the GCW and the 3 monitoring wells
• Each one of the 3 wells is 1 inch from the GCW
• The GCW and the 3 wells are 1 inch above the

bottom of the aquarium

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Aquarium (testing cell) building

• The aquarium filled with soil while setting the 3 well

cases with the GCW

• The 4 wells were set and coated with thin gravel

layer

• The cases were removed to make the soil with direct

contact with gravel coating

24

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Preparing Iron reference

• Preparing 5 patches of 12,000 mg/L of Iron reference

(IR) by dissolving 85.44 gm of FeCL2.4 H2O in 50 ml

• f HCL and filling the rest of D.I. water
• First Patch was (11434 mg/L)
• Second Patch was (8977 mg/L)
• Third Patch was (11500 mg/L)
• Forth patch was (11680 mg/L)
• Fifth patch was (11400 mg/L)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Preparing Iron reference

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Testing cell setting

• Aquarium has been set

with feeding system which include 2 water aquariums to stabilize the recharge to 50 ml/min.

• Iron reference were

pumped with 200 mg/L average.

• Readings took from the

discharge point to measure the saturation level

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015

Sampling

• A sample from the GCW were collected to evaluate

iron rise inside the well.

• Each 30 minutes time period a sample was collected.
• Portable spectrophotometer HACH DR 1900 were

used for testing the samples

• The following scatters show

the concentrations from the samples were collected .

25

Technical Advisory Group Meeting FAU ▪ January 30, 2015

y = 0.5425x - 22729 R² = 0.9426 10 20 30 40 50 60 70 8/29/2014 9/18/2014 10/8/2014 10/28/201411/17/2014 12/7/2014 12/27/2014 1/16/2015 2/5/2015 AVE CONCET. DATE

Average Daily Const.

Series1 Linear (Series1) y = 0.0505x - 2109.1 R² = 0.0252 5 10 15 20 25 30 35 40 45 50 8/29/2014 9/18/2014 10/8/2014 10/28/2014 11/17/2014 12/7/2014 12/27/2014 1/16/2015 Axis Title Axis Title

• Const. Inside Well

Series1 Linear (Series1)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Conclusion

• The slope of the average daily concentration shows

constant increase for the Iron for sample collected from the outlet which is desired as it reflect the increase of iron in the flow and soil in same time.

• R² value were 0.94 ≈ 1 for the average daily

concentration

• The slope of the well sample which were collected

from the core of GCW were very 0.05 reflect that well were ready to test as there is not to much deviation (except 2 points were out of the regular variance)

Technical Advisory Group Meeting FAU ▪ January 30, 2015

What has been noticed ?

• Iron reading were increased through the daily recharge

process then get stable for couple of samples.

• The samples reading which was collected at the end were

mostly shows the lower point.

• The reason for the last point might be the reflection of

water detention ( which spiked with iron ) inside the Aquarium.

• Aquarium start to have red color which reflect that some
• f the spiked iron start to convert to Fe3 form because of

air expose which led to start the experiment when Fe2 value were passed 50 mg/L limit.

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Dialy Data trend

12/10/2014 point mg/L time P0 48.2 5:30 P1 50.4 6:00 P2 49.6 6:30 P3 49.2 7:00 P4 47.8 7:30 P5 42 8:00 P inside 5 47.86667

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Air injection (Pumping)

• Air pumping started at

1/19/2015

• The air pump supply 1

cubic feel / min

• Samples collected each

30 minutes.

• The sampling process

were include the outlet and GCW in addition to the 3 monitoring wells installed around it.

Technical Advisory Group Meeting FAU ▪ January 30, 2015

Till now !

• 4 days of running air stripping and the process still
• n going.
• The data of samples don’t give any slope to make us

able to figure out the trend followed.

• Expected adjustment might be taken for the Air flow
• r the spiked iron reducing

26

Technical Advisory Group Meeting FAU ▪ January 30, 2015 Technical Advisory Group Meeting FAU ▪ January 30, 2015