Technical Advisory Group
Transcript of Technical Advisory Group
Technical Advisory Group Meeting “Sustainable Management of Pollutants Underneath Landfills”
“Onsite Treatment of Leachate Using Energized Processes” By D.E. Meeroff (Florida Atlantic University)
Funded by the Hinkley Center for Solid and Hazardous Waste Management (HCSHWM)
DATE: Friday, November 2, 2012
TIME: 1:00 pm
WHERE: Florida Atlantic University Boca Raton Campus
Computer Center Building
CM Building (22), Room 130 (Studio 1)
777 Glades Road, Boca Raton, Florida 33431
Attendance:
Dan Meeroff (FAU), Tim Vinson (Hinkley Center), Demaris Lugo (Broward County),
Sam Levin, Paul Wierzbicki (DEP Southeast District), Dan Schauer (Geosyntec
Consultants), David Bromstad (Orange County), Vanessa Cruz (Orange County),
Ricardo Moore (Orange County), Arnaldo Mercado (Orange County), Cleevens
Geurrier (FAU), Fred Bloetscher (FAU), Ahmed Albasri (FAU), Frank Youngman
(FAU)
1. Opening address by Dr. Meeroff followed by introduction of the group members
and participants both through GoToMeeting and live (1:08 pm)
2. Introduction to Landfill Technology Research by Dr. Meeroff
Dr. Meeroff presented the agenda of the meeting, the objectives of the research, and
provided an overview of current and past research projects funded by the Hinkley
Center for Solid and Hazardous Waste Management. He also presented the newly
published journal article “Application of photochemical technologies for treatment of
landfill leachate” by Daniel E. Meeroff, Frederick Bloetscher, D.V. Reddy, Francois
Gasnier, Swapnil Jain, André McBarnette, and Hatsuko Hamaguchi published in the
Journal of Hazardous Materials. Dr. Meeroff showed the TAG members the project
website (http://labees.civil.fau.edu/leachate.html), and presented a preview of the
newest joint project on leachate clogging at the Solid Waste Authority of Palm Beach
County with University of Florida and the Hinkley Center.
3. Laboratory Studies of Groundwater Circulation Well Technology by Ahmed
Albasri
Ahmed began discussing the background on the research. He explained how the
treatment process is intended to work. Then he went over the methodology of the
aquarium experiments. He reported 3‐log removal of iron in the early stages of the
process, but iron speciation still remains an issue. The need to run the experiments
for longer than one week was brought up. Dan Schauer of Geosyntec Consultants
asked if the “shadow effect” was evaluated. Tim Vinson asked about the zone of
influence, radius of wells and effects of varying pump flowrates. Dan Schauer
offered to provide some reference material for help in developing a design equation
to estimate the zone of influence of the groundwater circulation model. He offered
to provide data on how long GCW or similar technologies are operated in the field.
An idea to load the aquaria until a steady state concentration is found in the well,
and then turn on the GCW was put forward. David Bromfield asked if the system
needs to be constantly “on.” The answer to that question should be answered after
the experiments are concluded. However, it could be possible that the system may
need only to be online seasonally as a preventative measure. Fred Bloetscher asked
about the contribution of iron bacteria or if encouraging the growth in the
subsurface can help. He asked if the biological profile of the samples had been
analyzed, and mentioned that Micrim Labs can do this test. He also offered to share
MODFLOW or Groundwater Vistas to create a localized model of the well. Tim
Vinson mentioned that Gang Chen from FSU has done some work on iron bacteria.
He also asked if we had any measurements to determine the extent of circulation,
and Ahmed mentioned that he had a video of a dye test. Ahmed had questions for
the TAG:
Is there any information on GCW or sparging well design equations? Dan
Schauer offered that he has information on soil types, porosity, etc. requirements
that he would share.
Any information on iron speciation? Tim Vinson mentioned that Tim Townsend
from UF can provide a resource, and Dan Schauer offered to send the team a
contact from his geochemistry division.
Where else is iron an issue? Tim Vinson mentioned Polk County and North
Florida. Paul Wierzbicki mentioned that all of the landfills in the Southeast
District are also having this issue. Demaris Lugo mentioned that Tim Townsend
has some data. Dan Schauer offered to provide a short list.
Information on costs? Dan Schauer offered to provide some rough cost estimates.
Dr. Meeroff mentioned that preliminary costs are premature at this time until we
can define the zone of influence and the process efficiency.
4. Pilot Studies of Photocatalytic Oxidation of Leachate by Frank Youngman
Frank began discussing the background on the research. He explained how the
treatment process works. Then he went over the methodology of the pilot scale
experiments. He reported on the progress of catalyst optimization, process
removal efficiency and kinetics of COD, ammonia, and color, and he described
upcoming catalyst recovery experiments. Fred Bloetscher asked about the impact
of pH on the ammonia removal. Demaris Lugo asked about chlorides and arsenic.
It was concluded that the process would not be effective for chloride removal.
Tim Vinson asked how the number of variables can be teased out of the kinetics
testing, in particular the variability in the leachate sampled. It would be better if
the same leachate could be used for all of the optimization tests. He also inquired
about control experiments, such as the effect of aeration and dark controls. Frank
mentioned that those experiments were conducted by a previous student,
Richard Reichenbach. Paul Wierzbicki asked if Frank relied on any leachate
quality data and then mentioned that the legislature has removed the lab testing
requirements for landfills unless they are under assessment monitoring to meet
the requirements of hazardous waste (this was enacted in the last legislative
session). Demaris Lugo mentioned that she provided a CD with leachate data for
the Hinkley Center and Dan Meeroff has a copy for Frank to review. She also
asked about how the process will be tested in the field, and Dr. Meeroff provided
some thoughts about a batch tank, which is already existing at the Monarch Hill
site.
5. Adjourn (3pm), thank you for participating!
For more information, contact Dr. Daniel E. Meeroff at:
777 Glades Road, Building 36, Room 222, Boca Raton, FL 33431‐0991
Tel.(561) 297‐3099 FAX.(561) 297‐0493 http://labees.civil.fau.edu
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
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
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Agenda
1. Introductions/Opening Remarks
2. Overview of Projects
3. Circulation Well Experiments
4. Photocatalytic Oxidation Studies
Dr. Meeroff
Dr. Meeroff
Ahmed
Frank
5. User Input/Open Forum Everyone
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Introductions
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Overview of Projects• “Sustainable Management of
Pollutants Underneath Landfills”
• “On-Site Treatment of Leachate Using Energized Processes”
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
http://labees.civil.fau.edu/leachate
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Previous Work• “Options for Managing Municipal Landfill Leachate”
• Englehardt and Meeroff (2005)• “Investigation of Energized Options for Leachate
Management Year One”• Meeroff and Tsai (2006)
• “Investigation of Energized Options for Leachate Management Year Two”• Meeroff and Tsai (2008)
• “Interactive Decision Support Tool for Leachate Management”• Meeroff and Teegavarapu (2010)
• “Energized Processes for Onsite Treatment of Leachate”• Meeroff (2011)
• “Management of Subsurface Reductive Dissolution Underneath Landfills”• Meeroff and Albasri (2012)
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Journal Article
• We are very proud to announce the publication of a journal article from this research
• Journal of Hazardous Materials
• Published February 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Exciting New Joint Project
• “Critical Examination of Leachate Collection System Clogging at SWA Disposal Facilities”
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Technical Advisory Group Meeting
1. “Reducing The Iron Pollution In Landfill Soils By Using Aeration Wells”
Ahmed Albasri, MSCE CandidateDepartment of Civil, Environmental & Geomatics Engineering
Laboratories for Engineered Environmental Solutions
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
The Problem• Iron is being detected in monitoring wells
downstream of Florida landfills• State Enforceable Secondary Drinking Water Standard
(62-550 FAC) and Groundwater Cleanup Target Level (62-777 FAC) set at 300 µg/L (0.3 mg/L)
• Evaluation monitoring required by 62-701.510(7)(a) if levels are detected significantly above background
• Requires installation of compliance monitoring wells• Requires additional sampling• Stipulates corrective measures (62-780 FAC)
• Pump & treat with filtration, biological treatment, chemical treatment
26
Fe55.845
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Sources• Landfill
leachate• Iron liberated
due to the presence of the landfill
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Iron from Leachate?
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Iron Mobilization in Leachate Plumes• Landfill leachate plume chemistry:
• High oxygen demand• High levels of strongly reduced organic matter • pH 6.5-8 (typical Florida landfill leachate)
• Groundwater chemistry:• Soils high in subsurface iron oxides• Low DO, reducing conditions
• Food source + environmental condtions favor iron-and sulfate-reducing bacteria (Shewanella and Desulfovibrio)• Microbially-mediated liberation of ferrous iron
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Landfill Leachate• If the source of the elevated iron is landfill leachate,
then we would expect to see:• Other conservative tracers (TDS, chlorides, etc.)• Other leachate contaminants (VOCs, As, etc.)• Dilution effects compared to the measured leachate
water quality
• Caveats:• Variability caused by field sampling methods• Reliability of redox-sensitive parameters • Well construction materials (non-steel)• Variations in landfill construction methods
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
North Florida Results
Monitoring Well 7S
Monitoring Well 2S
• Townsend 2008
• Timmons et al. 2008
• Wang and Stone 2008
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Case Study
• Iron presence was detected in 22 observation wells on 29 April 2008 in North Central Landfill (NCLF) higher than PDWS (Florida Primary Drinking Water Standard) which is 300 µg /L
• High Iron presence exceed the CTL (Clean-up Target Level) which is 3000 µg /L were observed in 15 monitoring wells including compliance wells
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
NE
SESW
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Possible Corrective Measures• Options:
• Either Pump and treat with packed column, sedimentation, membrane filtration system (Sim et al. 2001)
• Excess iron bacteria disinfection
• Lack of iron bacteria microaeration, pH-adjustment, chelation with organic acids, nutrient addition
• Ferrous iron ion exchange or oxidation + filtration or adsorptive filtration or oxidation trenches
• Ferrous + Arsenic advanced oxidation recirculation wells
• Hydrology restore non-reducing conditions
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Treatment Method• Soil aeration is one of the successful decontamination processes
used to treat volatiles • Groundwater circulation well (GCW) systems attempt to create a 3-
dimensional circulation pattern in an aquifer by drawing ground water into the well
• The main goal of this system is to oxidize the Iron in the soil from Fe(ll) form to Fe(lll) form, which is insoluble to stop Iron migration with ground water
• The advantage is that treatment of the contaminated groundwater takes place below grade and does not require that it be pumped out the ground
• Another advantage over conventional pump-and-treat is that GCWs induce a groundwater circulation zones that “sweeps” the aquifer• Pump-and-treat systems cause drawdown around the well, leaving
contaminated zones that are not treated
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Air
SandFilter
Another Option
• In situ remediation process
• Metals and radionuclides
• Volatiles
• Biodegradables
• Simple to operate
• Rapid
• InexpensiveReactionZone
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Groundwater circulation well (GCW)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Objectives
1. To develop a list of viable engineering alternatives for controlling the release of iron in-situ
2. To conduct lab experiments for iron (and possible co-contaminant) removal in-situ using groundwater recirculation well technology
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Samples Collection• Boca soil samples were collected
• 4 samples were collected from Polk County Landfill
• The first 2 samples where collected from SE & NE of the site on 05/11/2011
• The second set of 2 were collected from SE & SW on 11/10/2011
• The samples collected after removing the top 15 cm from the soil surface
• The soil has a homogeneous profile
• The samples were kept at room temperature until testing
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Aquarium Experiments• GCW model consists of the following parts:
• Transparent glass aquarium of (11.5 × 5.5 × 7.75) inch dimensions
• A prototype of sparging well (vinyl tube ½” outside DIA)
• Two well screens with 4 slits/cm and 1 inch long separated by 1 inch
• Vinyl tube within a tube to create the negative pressure head of the air bubbles which induces circulation
• Gravel filter around the well with #20 Sieve for a diameter of 1.5 inch around the well
• Aquarium Air pump (elite 799) with 1 cubic ft / min flowrate and with pressure of 1.0 PSI
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Test with Boca Soils• For conservative demands the test has started with soil from Boca
Raton to prove the ability of contaminant removal
• Boca soil is sandy as it lies in the Eastern Sandy flatland area according to physiographic region.
• The geographical distribution of the soil in Florida reflects that Boca soil is sposdsol type which has an expected iron content of 300 mg/kg
• Iron reference of 100 mg/L was added to the water and soil in the aquarium
• Two aquarium tests were running simultaneously to obtain replicate results
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Results of Boca Soil Tests• Iron concentration found in Boca Raton was close to
the theoretical data (~300 mg/kg) for all samples• Iron removal readings through the 72 - 264 hr
running time show arbitrary numbers as it cannot be decided whether the Iron is in Fe(II) or Fe(III) form as they both can be occur in spectrometric test
• Independent lab results were also inconclusive due to the limitations of the phenanthroline colorimetric method
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
0
100
200
300
400
500
1 2 3 4
fFe
mg
/Kg
Boca Raton test Results compare with chen.1999
Fe soil test withoutrover
Fe with Rover
Spodosols(0.033*10^4)
0
0.5
1
1.5
2
0 1 2 3 4 6 24 48 54 72
Fe(
C/C
0)
Time (hours)
Iron reading in Boca Soil
Sample1
Sample2
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Test for Polk County Soils
• 3 samples for each one of the 2 samples collected in May 11-2011 for Iron digestion Hot Block experiment are in process
• 2 Aquariums of the SE and NW landfill soil which was collected in May 11-2011 are built already
• The 2 which were collected in November are in the drying process
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Tests with Polk County Soils
• 4 Aquariums for the soils Collected from Lakeland landfill.
• Same Construction were adopted for Boca tests.
• SE & NE soil samples were sandy profile which enable setting them quickly in their 2 aquariums.
• SE & SW were need further process as they were clay constructed soil.
• Soils had been dried for 24 hour with 100 degree Celsius
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Tests with Polk County Soils
• 4 samples were homogenized with a hammer and added to 2 aquaria
• 94 mg/L Iron has been created FeCl2 with HCl
• 4 Aquaria were saturated with iron for 1 day
• 4 Aquaria tests were started on 10/31/2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Testing Results
• Spectrophotometer test conducted and samples collected 1, 2, 4, 6, 8 & 12 hours
• The results show fast decreasing after 1 hour of running the experiment in 4 aquaria
• Iron reading were 0.11 - 0.08 mg/L for the 4 test experiments after 1 hour running and keep decreasing through time
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
0 1 12FE 94.3 0.1195 0.0909
0
50
100
Iro
n
Fe for NE 05/11/11
0 1 12FE 94.3 0.08969 0.05764
0
50
100
Iro
n
Fe for SE 05/11/11
0 1 12FE 94.3 0.08 0.0933
0
50
100
Iro
n
Fe for SW 11/9/11
0 1 12FE 94.3 0.08 0.04
0
50
100
Iro
n
Fe for SE 11/9/11
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Step to be Achieved
• Keep collecting samples to see the iron development
• Determine the reaction time needed for adequate Iron removal using GCW
• Develop design criteria for GCW for iron removal
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
I Have Questions for YOU
• Do you have any knowledge of design equations that govern groundwater circulation well (GCW) systems or sparging wells?
• Do you have any suggestions for an appropriate test method to speciate the forms of iron, Fe(II) and Fe(III), in groundwater and soils?
• Where else is iron reductive dissolution a problem?
• What are the costs associated with remediation of iron dissolution?
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Technical Advisory Group Meeting
2. “Onsite Treatment of Leachate Using Energized Processes”
Frank Youngman, BS/MS StudentDepartment of Civil, Environmental & Geomatics Engineering
Laboratories for Engineered Environmental Solutions
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Problems with Leachate
Turbidity
Elevated TDS, COD,
NH3
High COD/BOD
ratio
pH toxicity
Heavy metalsPb, As, Cd, Hg
Quantity and quality highly
variable
OdorPathogens
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
What will we do with leachate in the future?
Hauling
POTWs Deep Injection Wells
Pretreatment
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
One Solution
• Pre-treatment on-site
• Advanced oxidation using ultraviolet light activation (Energized processes)
• FAU has investigated photochemical iron mediated aeration (PIMA) and TiO2 photocatalysis
• And TiO2 photocatalysis seems to be promising
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Titanium dioxide
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Hydrogen
Peroxide
Photon (UV)Hydroxyl Radical
Contaminant
Copyright © Trojan Technologies Inc. All Rights Reserved
Water
How Do Energized Processes Work?
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
h+
e‐Mn+
(aq)
M0(s)
[ Photoreduction ]
+
hν[ Photooxidation ]
Oxygen
Water
TitaniumDioxide
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Titanium Dioxide MechanismTiO2TiO2
O2 UV O.
2
H+
O.
2 HO.
2
H2O OHO.
2 HO.
2 O2 H2O2
HO.
2 H2O2TiO2 H+
TiO2
H2O2TiO2 TiO2
.OHOH
49 Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Procedures
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Wiles RdP
owerlin
e Road
Leachate Sample
•Location
•Monarch Hill, formerly known as CDSL
•Pompano Beach, FL
•Sample Point
•Waste Management•South East Step-Up Station
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Leachate/ TiO2
CE 584 Falling Film Reactor
• Reservoir (10L)
• Temperature Sensor
• Pump (360 L/h)
• Flow Regulator
• Sampling Port
• 3 Way Valve
• Weir Compartment
• UV Power Source (120W)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Mechanical Improvements• Catalyst
build-up in pump
• Installed a 3-way valve to allow flushing of the pump
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Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Temperature Control• VWR Recirculating Cooler
1150S
• 13 L Capacity
• Temp: -30°C to 150°C
• Filled with Dynalene HC-50 (hydrocoolant)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Temperature Curves
0
5
10
15
20
25
30
35
40
45
50
0 50 100 150 200 250
Temperature (C)
Time (minutes)
Temp. with Recirculating Cooler
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Parameters• COD/ Alkalinity Testing
• Leachate Sample Volume (8L)
• Degussa P25 TiO2 Catalyst• 4, 16, 25, 30, 40 g/L
• Constant Aeration
• Recirculating Cooler (-9.9°C)
• 4 - Hour Test Segments
• Flow Rate: 300 L/hr
• UV intensity:• 0.0110 - 0.365 mW/cm2
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Sample Testing
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Experimental Protocol
59 Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
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11
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Experiment #1
• Leachate collected 9/23/2011
• 4 grams TiO2 per liter leachate
• CODo = 6250mg/L
• Ammoniao = 1710 mg/L as NH3-N
• Alkalinityo = 4630 mg/L as CaCO3
• Coloro = 1125 Platinum Cobalt Units (PCU)
• pH = 8.35
• 44 hour total run
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
What is the limiting parameter?• Clearly COD
is the limiting parameter
• COD is primary concern for determining reaction kinetics
0
0.2
0.4
0.6
0.8
1
1.2
0 5 10 15 20 25 30 35 40 45 50
C/Co
Time (hours)
C/Co comparing degradation of COD, Ammonia, and Alkalinity
COD Ammonia Alkalinity Linear (COD) Expon. (Ammonia) Expon. (Alkalinity)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – Zero Order• Initial Values
• 4.0 g/L TiO2
• CODo = 6250 mg/L
• Zero order kinetics
k = - 56 mg/L-hour
• Estimated time for 100% COD removal would be 112 hours and 97 hours to get to 800 mg/L
y = ‐56.005x + 6261.3R² = 0.9825
0
1000
2000
3000
4000
5000
6000
7000
0 5 10 15 20 25 30 35 40 45 50
COD (mg/L)
Time (hours)
Experiment #1 (4g/L) COD Concentration
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – First Order• Initial Values
• 4.0 g/L TiO2
• CODo = 6250 mg/L
• First order kinetics
k = - 0.0112 hour-1
• Displays a slightly higher correlation coefficient than zero order• Estimated time to
reach 800 mg/L = 180 hours
y = ‐0.0112x + 8.7589R² = 0.9832
8.2
8.3
8.4
8.5
8.6
8.7
8.8
0 5 10 15 20 25 30 35 40 45 50
lnCOD
Time (hours)
Experiment #1 (4g/L) ln(COD Concentration)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – Second Order• Initial Values
• 4.0 g/L TiO2
• CODo = 6250 mg/L
• Second order kinetics
k = 0.000002 L/mg-hour
• Displays a lower correlation coefficient than first and zero order
y = 2E‐06x + 0.0002R² = 0.9779
0
0.00005
0.0001
0.00015
0.0002
0.00025
0.0003
0 5 10 15 20 25 30 35 40 45 50
1/COD
Time (hours)
Experiment #1 (4g/L) 1/(COD Concentration)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Experiment #2
• Leachate collected 3/9/2012
• 16 grams TiO2 per liter leachate
• CODo = 5270mg/L
• Ammoniao = 1310 mg/L as NH3-N
• Alkalinityo = 3560 mg/L as CaCO3
• Coloro = 825 Platinum Cobalt Units (PCU)
• pH = 7.52
• 40 hour total run
12
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – Zero Order• Initial Values
• 16 g/L TiO2
• CODo = 5270 mg/L
• Zero order kinetics
k = - 52 mg/L-hour
• Estimated time for 100% COD removal would be 98 hours and 83 hours to get to 800 mg/L
y = ‐52.229x + 5140R² = 0.9776
0
1000
2000
3000
4000
5000
6000
0 5 10 15 20 25 30 35 40 45
COD (mg/L)
Time (hours)
Experiment #2 (16g/L) COD Concentration
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – First Order• Initial Values
• 16 g/L TiO2
• CODo = 5270 mg/L
• First order kinetics
k = - 0.0129 hour-1
• Displays a higher correlation coefficient than zero order• Estimated time to
reach 800 mg/L = 150 hr
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – Second Order• Initial Values
• 16 g/L TiO2
• CODo = 5270 mg/L
• Second order kinetics
k = 0.000003 L/mg-hour
• Displays a lower correlation coefficient than first order, but higher than zero order
• First order takes precedence
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Experiment #3
• Leachate collected 3/9/2012
• 25 grams TiO2 per liter leachate
• CODo = 5360mg/L
• Ammoniao = 1380 mg/L as NH3-N
• Alkalinityo = 3560 mg/L as CaCO3
• Coloro = 790 Platinum Cobalt Units (PCU)
• pH = 7.54
• 40 hour total run
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Reaction Kinetics – First Order• Initial Values
• 25 g/L TiO2
• CODo = 5360 mg/L
• First order kinetics
k = - 0.0158 hour-1
• Estimated time to reach 800 mg/L = 120 hr
y = ‐0.0158x + 8.5351R² = 0.9749
7.8
7.9
8
8.1
8.2
8.3
8.4
8.5
8.6
8.7
0 5 10 15 20 25 30 35 40 45
ln(COD)
Time (hours)
Experiment #3 (25g/L) ln(COD Concentration)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Experiments #4 & 5• Leachate collected 7/18/2012
• 40 g/L TiO2 (Exp. 4) and 30 g/L TiO2 (Exp. 5)
• CODo = 6560mg/L
• Ammoniao = 1635 mg/L as NH3-N
• Alkalinityo = 4125 mg/L as CaCO3
• Coloro = 756 Platinum Cobalt Units (PCU)
• pH = 7.66
• 24 hour total run
13
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
y = ‐0.0011x + 1R² = 0.9411
y = ‐0.0015x + 1R² = 0.963
y = ‐0.0022x + 1R² = 0.9235
y = ‐0.0021x + 1R² = 0.9193
y = ‐0.0018x + 1R² = 0.9509
0.94
0.95
0.96
0.97
0.98
0.99
1
1.01
0 5 10 15 20 25 30
COD lnC/lnCo
Time (hours)
COD lnC/lnCo
4 g/L 16 g/L 25 g/L 40 g/L 30 g/L
Linear (4 g/L) Linear (16 g/L) Linear (25 g/L) Linear (40 g/L) Linear (30 g/L)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Rate constant comparisonTiO2 Dosage (g/L) Rate constant (hr‐1)
4 ‐0.0102
16 ‐0.0127
25 ‐0.0167
30 ‐0.0146
40 ‐0.0160
• 25 g/L exhibits the largest rate constant
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Catalyst Optimization for COD• Seems to
follow logarithmic pattern
• Next step is to try 10 g/L TiO2
to see if it falls on the curve
0
5
10
15
20
25
30
35
40
0 5 10 15 20 25 30 35 40 45 50
% COD Rem
oval at 24 hours
TiO2 dosage (g/L)
Catalyst Optimization Curve
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Ammonia• 4 g/L shows
highest degradation
• k = -0.073/hr• Time to reach
25 mg/L = 58 hr
y = ‐0.0103x + 1R² = 0.9838
y = ‐0.0039x + 1R² = 0.9585
y = ‐0.004x + 1R² = 0.8967
y = ‐0.0035x + 1R² = 0.943
y = ‐0.0037x + 1R² = 0.9803
0.75
0.8
0.85
0.9
0.95
1
1.05
0 5 10 15 20 25 30
lnC/lnCo
Time (hours)
Ammonia (lnC/lnCo)
4 g/L 16g/L 25 g/L 40 g/L 30 g/L
Linear (4 g/L) Linear (16g/L) Linear (25 g/L) Linear (40 g/L) Linear (30 g/L)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Alkalinity• 4 g/L shows
highest degradation
• k = -0.078/hr
y = ‐0.0087x + 1R² = 0.9713
y = ‐0.0041x + 1R² = 0.844
y = ‐0.0028x + 1R² = 0.8301
y = ‐0.007x + 1R² = 0.9113
y = ‐0.0074x + 1R² = 0.9416
0.75
0.8
0.85
0.9
0.95
1
1.05
0 5 10 15 20 25 30
lnC/lnC0
Time (hours)
Alkalinity (lnC/lnC0)
4 g/L 16 g/L 25 g/L 40 g/L 30 g/L
Linear (4 g/L) Linear (16 g/L) Linear (25 g/L) Linear (40 g/L) Linear (30 g/L)
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Conclusions
• At optimal TiO2 dosage to date, it would take approximately 120 hours to achieve 800 mg/L COD target for sewer disposal• Ammonia: 58 hours to achieve 25 mg/L target
• Alkalinity: 29 hours for 90% removal
• Color: 105 hours for 90% removal
14
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Next Steps• Optimize Catalyst
• Attempt next experiment at 10 g TiO2/L to determine if the COD removal follows the logarithmic pattern of optimization
• Catalyst Recovery• 3 bag sizes (5, 10 and 20 micron)
will be tested for recovery efficiency after approximately 10 hours of treatment
• Cost Analysis• Understand Alkalinity
Dependence
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Open Forum
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
I Have Questions for YOU
• Are there more contaminants of great concern? • Treatment targets?
• How much does your leachate management cost?• Will this process be cost competitive?
• How much leachate is produced at your landfills?
• Do you want us to test your leachate?
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Huddle.net
Acknowledgements
• TAG Members
• Daniel Meeroff, PhD, EI
• Andre McBarnette
• Richard Reichenbach
• Jeff Roccapriore
• Florida Atlantic University
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
Sponsors
15
Presentation to the HCSHWM Technical Advisory GroupBoca Raton, FL, November 2, 2012
85
website: http://labees.civil.fau.edu