Use of Ultrafiltration for Mercury Removal
CMS Land Company
Little Traverse Bay Environmental Project (LTBEP)
(Bay Harbor Development, Petoskey, MI)
2011 MWEA Annual Conference
Shanty Creek Resort, Bellaire MI
June 28, 2011
Prepared by:
Environmental Consulting & Technology, Inc.
Peter F. Hill, P.E.
Jeremy S. Lewandowski
Mark D. Mikesell, Ph.D.
William E. Stone
Environmental Consulting & Technology, Inc.
2200 Commonwealth Blvd., Ste. 300
Ann Arbor, MI 48105 Traverse City, MI 49684
Ph: (734) 769-3004
Ph: (231) 946-8200
Fax (734) 769-3164
Fax: (231) 946-8208
SUMMARY OF LITTLE TRAVERSE BAY
ENVIRONMENTAL PROJECT (LTBEP)
GOALS & RESULTS
• Characterize Cement Kiln Dust (CKD) Leachate for Hg, TSS & other parameters.
• Determine effectiveness of Ultrafiltration (UF) Technology to Treat CKD Leachate.
• Characterize Effluent from UF to Determine Compatibility with WQS.
• Demonstrate CKD Leachate can be Treated & Discharged to Little Traverse Bay (LTB).
• Assist CMS Land Co. (CMSL) in obtaining Permits/Authorizations to discharge Leachate.
• UF achieved 97% Hg Removal (1.8 ng/L achieved).
• MDEQ considers UF as Best Available Technology (BAT) for this site.
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BAY HARBOR – SITE LOCATION
Little Traverse Bay (Lake Michigan)
• CMSL Bay Harbor Site located 5 miles
west of Petoskey
• Located on south shore of Little Traverse
Bay, Lake Michigan.
Photo Source: Google Earth.
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Emmet
County
HISTORICAL USE OF SITE
CEMENT-MANUFACTURING TIMELINE:
•
1917 - Petoskey Portland Cement Co.
formed.
•
1954 – Penn-Dixie Cement Co. purchased
land.
•
1980 – Cement-Making Operations end Penn-Dixie files for bankruptcy.
Photo Source:
http://www.flickriver.com/photos/odalaigh/
1532444089/
Source: Tip of the Mitt Watershed Council,
www.watershedcouncil.org.
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CEMENT MAKING PROCESS & CKD
•
Leftover material from grinding /heating limestone + other raw materials is CKD.
•
Leachate formed when water contacts CKD…caustic & contains heavy metals
(mercury, arsenic, & lead).
•
Estimated 2.5 Million CY of CKD waste left behind.
Source: Tip of the Mitt Watershed Council, www.watershedcouncil.org.
Photo Source: Friends of the Jordan, Concerning the Bay Harbor Cercla Site,
Presentation by Edward E. Timm, Ph.D., P.E.
5
BAY HARBOR – RE-DEVELOPMENT OF SITE
• 1993 – Bay Harbor Resort Properties Ltd.
& CMSL team to develop site.
6
Photo Source: Friends of the Jordan, Concerning the Bay
Harbor Cercla Site, Presentation by Edward E. Timm,
Ph.D., P.E.
ISSUES WITH SITE
• Oct. 1988 – Caustic groundwater found leaching
into LTB.
• 1989 – East & West CKD areas show detectable
concentrations of arsenic, chromium, copper,
lead, nickel, selenium and zinc.
Source: Tip of the Mitt Watershed Council, www.watershedcouncil.org.
Photo Source: Friends of the Jordan,
Concerning the Bay Harbor Cercla Site,
Presentation by Edward E. Timm, Ph.D., P.E.
7
ISSUES WITH SITE (CONT’D)
• 1994 – CKD piles contoured, covered with topsoil & turned
into golf course.
• 1997 – Leachate still reaching LTB @ Seep 2…
Seepage collection line installed.
• Collected Leachate transported to Petoskey’s WWTP.
• 2003 – CMSL constructed Pre-Treatment Facility to ↓ pH of
Leachate & built discharge to Petoskey’s sanitary sewer.
Source: Tip of the Mitt Watershed Council, www.watershedcouncil.org.
Photo Source: Friends of the Jordan, Concerning the Bay Harbor
Cercla Site, Presentation by Edward E. Timm, Ph.D., P.E.
8
ISSUES WITH SITE (CONT’D)
• Petoskey WWTP complications…
Leachate drained directly to LTB for several months.
• Sept. 2004 – HIGH pH readings in LTB lead to Public Health Advisory from
NW Michigan Health Dept. & restricted access for > 1 mile of BH shoreline.
• CMSL accepts environmental liability due to prior agreements.
• Feb. 2005 – Admin. Order of Consent issued by EPA…
CMSL to take immediate remedial action & ultimately
“remove, isolate or contain” the CKD.
Source: Tip of the Mitt Watershed Council, www.watershedcouncil.org.
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REMEDIATION EFFORTS: COLLECT & TREAT
BAY HARBOR DEVELOPMENT
PRE-TREATMENT
FACILITY
Photo Source: Google Earth.
Short-Term Response: Collect & Pre-Treat
1. System of collection drains/trenches:
2. Pump to Pre-Treatment
• Seep 1
Facility (↓ pH)
• Seep 2W (Seep 2 + West CKD)
• Edge Drain
• Total Leachate Collection System (TLC)
Ongoing Efforts:
• Plan for extensive testing of hydrology/geology.
• Up-gradient groundwater interceptor wells.
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COLLECTION DRAIN LOCATIONS
– Lake Michigan
– (Little Traverse Bay)
Map Source: Barr Environmental
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LEACHATE INTERCEPT SYSTEM
Photo Source: Friends of the Jordan, Concerning the Bay Harbor Cercla Site,
Presentation by Edward E. Timm, Ph.D., P.E.
12
BAY HARBOR DEVELOPMENT
PRE-TREATMENT FACILITY
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BAY HARBOR DEVELOPMENT
PRE-TREATMENT FACILITY (CONT’D)
• Automated Acid
Injection System
• Loading/
Transport
System
• Frac Tanks to Store Pre-Treated Leachate)
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BAY HARBOR DEVELOPMENT
PRE-TREATMENT FACILITY (CONT’D)
• pH-neutralize ~ 150,000 gpd w/ concentrated H2SO4.
• Storage in Frac Tanks.
• Treated leachate transported to deep well injection facility
near Gaylord, MI.
• Leachate previously transported to GT Co. Septage Treatment
System (discharges to TC WWTP).
• Period when leachate transported to Petoskey’s WWTP.
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BAY HARBOR – LEACHATE
• Dark brown in color
• Brown color, TOC &
COD due to dissolved
organic acids…fulvic,
humic, tannic, etc.
• CKD originally placed in
cedar swamp.
• Caustic (pH >12)
• TDS = 2,700 to 21,000 mg/L
• TSS = Non-Detect to 17 mg/L
• Mercury = 15 to 544 ng/L
• Copper = 19 to 84 µg/L
• Vanadium = 42 to 130 µg/L
• High COD & TOC
• Low BOD
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• pH, TDS & metals due to
groundwater flow
through CKD piles.
BAY HARBOR – LEACHATE (CONT’D)
• COSTLY $$ !!
• Trucks run 24/7/365 disposal to deep well injection.
• Public opposition to both deep well injection &
constant trucking.
• CMSL begins to explore other options!!
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PREVIOUS/ON-GOING STUDIES
• CMSL has done extensive research on Hg treatment & disposal tech., including:
• On-site deep well injection;
• Discharge into municipal sanitary sewer (City of Petoskey);
• Creation of interceptor trenches, collection and hauling of waste to off-site deep
well (Current Operation);
• On-site collection and treatment with point source discharge to Little Traverse
Bay;
• Adsorption Technology
• Ultrafiltration Technology
• Ultrafiltration is seen as the most promising Best Available Technology (BAT).
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PREVIOUS STUDIES
U.S. EPA
• Aug. 2007 - Treatment Technologies for Hg in Soil, Waste and Water, U.S. EPA
Office of Superfund Remediation and Technology Innovation, Washington D.C.
PARSONS GROUP
• 2005 - Pilot scale study conducted over a 6-week period (Nov. to Dec.).
• Demonstrated that Pretreatment (pH adjustment ) + UF could reduce Hg from 700
ng/L to 200 ng/L.
• Hg reduced further to 20-30 ng/L when Coag./Precip. added.
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ON-GOING STUDIES
CAPTUR TECHNOLOGY
• On-going evaluation of proprietary system using coag./floc. and
adsorption technology to remove Hg.
• Promising effluent Hg concentrations < 1.3 ng/L (WQS).
• If technology is effective & efficient @ full-scale,
Captur technology will likely be used at Bay Harbor.
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SUMMARY OF UF TECHNOLOGY
• Low pressure (5 psig to 150 psig) process .
• Uses semi-permeable tubular membrane.
• Removes high MW components/suspended solids from
aqueous solutions.
• Low MW components pass through UF membranes.
• Membranes are physical barrier that permits passage of
materials up to a certain size/shape/character.
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SUMMARY OF ECT PILOT STUDY
• Nov. 2009 - ECT begins UF pilot treatment study.
• Changes in volume/quality of Leachate since Parsons study.
• New waste stream – TLC.
• Used technology & operating conditions determined as optimal by Parsons study:
• pH-adjustment using 98% H2SO4
• Coag.-Floc. w/ Aluminum sulfate (alum)
• Cationic polymer floc. aid (metal precipitant)
• UF
• Provided additional data for National Pollutant Discharge Elimination System
(NPDES) Permit Application.
• Koch Membrane Systems (KMS) provided UF Pilot System & Operational/Technical
assistance.
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INFLUENT COLLECTION
• 4 Influent Streams
• Edge Drain
• TLC
• Seep 1
• Seep 2W (Seep 2 + WCKD)
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“COMBINED” INFLUENT
Influent
Daily Avg. Flow
Rate (GPM)
Percent (%) of Total
Daily Flow
Flow1
(GPM)
Flow1
(GPH)
Flow1
(mL/MIN)
Batch2
(gal)
pH (Standard
Units; S.U.)
Hg (ng/L)
Seep 1
38.29
39.0%
2.7
163.9
10,339.0
117.0
12.5
50
Seep 2W (Seep 2 +
WCKD)
51.00
52.0%
3.6
218.3
13,771.7
156.0
12.0
20
Edge Drain
8.09
8.2%
0.6
34.6
2,184.7
24.6
12.5
80
TLC
0.75
0.8%
0.1
3.2
202.5
2.4
13.2
500
Total
98.13
100%
7.0
420.0
26,497.9
300
-
-
• Batches combined based on daily avg. flow of each stream.
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INFLUENT METERING/MIXING
• 55-GAL.
head tanks
25
pH-ADJUSTMENT
• ↓ From >12 to 7.5 - 8.5
• 98% H2SO4
• 300-GAL. tank
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COAGULATION/FLOCCULATION
MP
Addition
Alum
Addition
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ULTRAFILTRATION
28
ULTRAFILTRATION (CONT’D)
Process
Tank
(50 GAL.)
Feed/Supply
Tank (280 GAL.)
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STORAGE OF EFFLUENT/CONCENTRATE
• 2 x 1,500-GAL. polytanks
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PILOT TREATMENT – FLOOR PLAN
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SUMMARY OF UF TECHNOLOGY
• Koch Membrane Systems (KMS) provided UF Pilot System
& Operational/Technical Assistance.
Photo Source: Koch Membrane Systems
32
SUMMARY OF UF TECHNOLOGY (CONT’D)
Photo Source: Koch Membrane Systems
Photo Source: Koch
Membrane Systems
33
Photo Source: Koch
Membrane Systems
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UF PERMEATE/CONCENTRATE
LEACHATE/
FEED WATER
(INFLUENT)
PERMEATE
(EFFLUENT)
UF
CONCENTRATE
• `
• Combined Influent
• Water, salts, ↓MW
constituents
• To Discharge
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• Solutes ↑ than UF
membrane pore size
• Suspended solids
• Circled back to feed tank
• Needs disposal
UF FLOW – SIMPLE BATCH PROCESS
Figure Source: Koch Membrane Systems
36
UF FLOW – MODIFIED BATCH PROCESS
Figure Source: Koch Membrane Systems
37
UF FLOW – ONE-STAGE CONTINUOUS PROCESS
Figure Source: Koch Membrane Systems
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SUMMARY OF PILOT RUNS
Runs 1 -3:
• Used Combined Influent (based on daily avg. flow of each
seep).
• Purpose: Demonstrated effectiveness to MDEQ, EPA &
Stakeholders.
39
SUMMARY OF PILOT RUNS (CONT’D)
Runs 4 - 14:
• Determined optimum mix of seeps.
• Collect WQ & System Operation Data to support full-scale commercial treatment system
design.
• Used individual seeps, various combinations, various additives, various concentration
factors, longer run-times, etc.
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SUMMARY OF PILOT RUNS (CONT’D)
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SUMMARY ANALYTICAL DATA
• Analysis included:
•
•
•
•
•
•
•
•
COD
TDS*
TSS*
TOC
Alkalinity
Hardness
Anions (incl. Chloride* & Sulfate*)
Various individual stream component concentrations…
• Heavy metals: Cu* , Hg*, Pb, Ni, Mo*, Se* & V*
• Sulfate
• salts
Note: Asterisk (*) indicates “Constituent of Concern”
• Acute & Chronic Toxicity Data
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ANALYTICAL RESULTS
• 97% Hg Removed
(Influent 42 to 78 ng/L)
(Effluent 1.8 to 8.1 ng/L)
• 97% TSS Removed
(Influent 13 to 107 mg/L)
(Effluent <3.3 to 8.5 mg/L)
• 90% Cu Removed
(Influent 13 to 49 µg/L)
(Effluent <5.0 to 14 µg/L)
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ANALYTICAL RESULTS
• 32% Molybdenum Removed
(Influent 76 to 100 µg/L)
(Effluent 53 to 140 µg/L)
• 30% Selenium Removed
(Influent 16 to 23 µg/L)
(Effluent 14 to 27 µg/L)
• 28% TDS Removed
(Influent 4,700 to 7,200 mg/L)
(Effluent 4,000 to 8,300 mg/L)
• 24% Sulfate Removed
(Influent 1,700 to 2,900 mg/L)
(Effluent 1,700 to 3,900 mg/L)
• 23% Chloride Removed
(Influent 330 to 1,100 mg/L)
(Effluent 310 to 1,200 mg/L)
• Use of both Alum & Metal Precipitant provided best metals removal
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RESULTS – MERCURY REMOVAL
• 97% Hg Removed
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RESULTS – TSS REMOVAL
• 97% TSS Removed
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RESULTS – COPPER REMOVAL
• 90% Copper Removed
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TCLP RESULTS
TOXICITY CHARACTERISTIC LEACHING PROCEDURE:
• Effluent Does NOT exceed regulatory limits for hazardous waste.
Constituent
Abbreviation
TCLP Metals
Limit (mg/L)
Run 1 UF Concentrate 10X
TCLP Results (mg/L)
Run 2 UF Concentrate
30X TCLP Results (mg/L)
Run 3 UF Concentrate 20X
TCLP Results (mg/L)
Arsenic
As
5.0
<0.10
<0.10
<0.10
Barium
Ba
100.0
<0.35
0.38
<0.35
Cadmium
Cd
1.0
<0.010
<0.020
<0.010
Chromium
Cr
5.0
<0.050
<0.050
<0.050
Lead
Pb
5.0
<0.050
<0.050
<0.050
Mercury
Hg
0.2
0.00025
0.00043
0.00025
Selenium
Se
1.0
<0.10
<0.10
<0.10
Silver
Ag
5.0
<0.010
<0.010
<0.010
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FULL-SCALE TREATMENT SYSTEM
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CONCLUSION
• UF System Effective in Removing Hg:
• 97% Hg Removal
• 1.8 ng/L [Hg] achieved
• MDEQ Considers UF To Be Best-Available-Technology In This Case
• NPDES Permit Issued for Discharge to LTB
• With Hg Limits
• With WET Limits
• New Treatment Building currently under construction.
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Little Traverse Bay Environmental Project (LTBEP)
(Bay Harbor Development, Petoskey, MI)
QUESTIONS/COMMENTS?
Prepared by:
Environmental Consulting & Technology, Inc.
Peter F. Hill, P.E.
Jeremy S. Lewandowski
Mark D. Mikesell, Ph.D.
William E. Stone
Environmental Consulting & Technology, Inc.
2200 Commonwealth Blvd., Ste. 300
Ann Arbor, MI 48105 Traverse City, MI 49684
Ph: (734) 769-3004
Ph: (231) 946-8200
Fax (734) 769-3164
Fax: (231) 946-8208