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Permeable Reactive Barrier for Remediation of Acid Mine Drainage
By: Pimluck Kijjanapanich
I Introduction
O Objectives
S Scope of Study
L Literature Review
マスタ タイトルの書式設定M Methodology
マスタ タイトルの書式設定R1
Results and Discussion
C Conclusions
R2Recommendations
Contents
Acid Mine Drainage• the result of oxidation by air and water of metal
sulfides contained within mined rock as well as mine wastes.
• high acidity and high amounts of dissolved heavy metals such as Fe, Zn, Ni, Cu and Pb.
• extremely toxic to most organisms in both terrestrial and aquatic ecosystems.
HSOFeOHOFeS S 2227 2
42
222
OHFeHOFe 23
22 2141
HOHFeOHFe S 33 32
3
HSOFeOHFeFeS S 16215814 2
42
23
2
The oxidation of pyrite
Abandoned Gypsum mineSurat Thani Province
Abandoned Lignite coal mineLamphun Province
• The pH modification method - by using lime (CaO), limestone (CaCO3), sodium hydroxide (NaOH) or sodium carbonate (Na2CO3)
• Ion exchange
• Adsorption treatment
• Electrochemical treatment
• Membrane process
An interested approach to AMD treatment has been developed that imitate sulfate reduction phenomena occurred in the nature that carry out by sulfate reducing bacteria (SRB) and developed to use for AMD treatment.
The methods for treating AMD
Disadvantages of the conventional active treatment of AMD (Brown et al., 2002)
• Relatively high operation and equipment maintenance cost• The sludge is chemically complex, unstable, low density and gelatinous resulting
large volumes, making difficult and causes long-term problematic disposal
Biological Sulfate Reductionthe use of anaerobic sulfate reducing bacteria
(SRB), which can reduce sulfate to sulfide by oxidizing an organic carbon source.
OHCOSHHSOOCH 222242 22
HMSMSH S 22
2
Permeable Reactive Barrieran emplacement of reactive materials in the subsurface
designed to intercept a contaminant plume, provide a flow path through the reactive media and transform the contaminant(s) into environmentally acceptable forms to attain remediation concentration goals down-gradient of the barrier (Powell and Puls, 1997).
The two basic designs of PRBs
Funnel-and-gatePRB
Continuous PRB
•No need for expensive above-ground facilities for storage, treatment or transport, other than monitoring wells.
•After the installation the above-ground can be reused.
•There are no energy input and limited operational and maintenance costs.
•The in situ contaminant remediation is more effective than the simple migration control achieved by the impermeable barriers.
•Contaminants are not brought to the surface so that there is no potential cross media contamination.
•There no disposal requirements or disposal costs for treated wastes.
•Avoid the mixing of contaminated and uncontaminated water that occurs with pumping.
Advantages of Permeable Reactive Barrier(Powell and Puls, 1997; Puls et al., 1999)
To develop an appropriate PRB system for treating Acid mine drainage (AMD)
The specific objectives are:
• To select the appropriate organic material used as electron donors for treating AMD using PRB.
• To investigate the reaction rate through batch and continuous studies for evaluation of residence time in PRB
• To investigate the effect of pH and alkalinity on PRB performance.
• To investigate the performance of PRB in removing of heavy metal.
Objectives
Scope of Study• Five types of organic material were used including; 1) rice husk 4) septage2) coconut husk chip 5) composted pig manure3) bamboo chip• Sludge from Sanguan Wongse Industry wastewater treatment
was used as sulfate reducing bacteria (SRB) source.• Batch experiment is conducted in order to select reactive
materials and the appropriate residence time for treating AMD.
• Column experiment is conducted in order to investigate the effect of pH and alkalinity on PRB performance and heavy metal removal efficiency.
• The experiments is conducted in laboratory PRB model under anaerobic condition at ambient temperature.
• AMD from lignite coal mine will be used as a raw water.
Literature ReviewThe criteria for selection of electron donor• Reactivity• Stability• Availability and cost• Hydraulic performance• Environmental compatibility• Safety
Waybrant et al., 1995 the combination of more than one organic source is more successful than the use of solely one material.
Gibert et al., 2004 The lower the content of lignin in the organic substrates, the higher its degradability and capacity for developing bacterial activity and sheep manure was the most successful electron donor (sulfate removal level of > 99%)
Sulfate Reducing Bacteria (SRB)
• A group of anaerobic bacteria that can reduce sulfate to form sulfide.
• The genus Desulfovibrio is one of the most mentioned species in studies of SRB in natural water and wastewater.
• Gram negative, curved rods and usually having a single polar flagellum.
The specific environment requirement for SRB to enable sulfate reducing activity
(Gibert et al., 2002)
• Anaerobic environment (Eh around -200 mV)
• pH 5-8• The presence of electron donor
and appropriate sulfur species• A physical support
According to the study of Costa et al. (2007), no SRB activity was observed at pH 2. On the other hand, at pH 5 and 7 SRB growth was observed and this different pH (5 and 7) was not significantly to affect SRB growth.
METHODOLOGYLiterature Review
Selection of organic carbon sources
Laboratory Analysis
Data analysis and Discussion
Conclusion and Recommendation
Phase I: Batch Test
• Experiment set-up• Investigate appropriate
organic carbon sources and optimum residence time.
Phase II: Column Test
• PRB column design• Select the two of the best organic
carbon.• Investigate the effect of pH and
alkalinity and heavy metal removal efficiency.
Methodology: Batch Experiment
To investigate appropriate organic carbon sources and optimum residence time.
Five organic materials
Rice husk Coconut husk chip
Bamboo chip Municipal compost (septage)
Composted pig manure
BATCH EXPERIMENT
valves
gas releasing pipe
30 cm
7 cmOrganic Material 300 mL (20% by volume)
SRB source 100 mL (7% by volume)
AMD pH 6-7 1000 mL (66% by volume)
1.5 L
Reaction Bottle
BATCH EXPERIMENT
The criteria for making mixtureThe 3 types of single material were selected:
• the two of the single materials that have maximum sulfate reducing rate (composted pig manure, rice husk).
• the single material that has long lasting (coconut husk).
P R
C
Type of Organic Material
MixtureRice husk
Coconut husk chip
pig manure
Rice husk & Coconut husk (RC) 50:50 + + -Pig manure & Rice husk (PR) 50:50 + - +Pig manure & Coconut husk (PC) 50:50 - + +Pig manure, Rice husk & Coconut husk (PRC) 33:33:33 + + +
=> Mixed MaterialBATCH EXPERIMENT
RC PR PC PRC
Remark: + Have this type of organic material in the formula- No have this type of organic material in the formula
=> Batch
Parameters MethodsAlkalinity Titration Method
Oxidation-reduction potential (Eh) ORP meter
pH pH meterSulfate Turbidimetric Method
Volatile solid per total solid (VS/TS) Dried at 105 and 550 oC
ANALYTICAL METHODS
=> SamplingTwo of the reaction bottles were finished for analyzing at each sampling time.
Methodology: Continuous Experiment
To investigate the effect of pH and alkalinity and heavy metal removal efficiency.
Log phase
ktSOSO t 0
24
24 lnln
Estimation of the Reduction rate and Residence time
kk
S
S
HRT
t
100
10lnln
0
Slope = -k
Column Design
NaOH
30 mL/hr (0.155 cm/hr)
screen
gas releasing pipe
0.4 cm
Name A1 L1 A2 L2
Lime adding - + - +
Formula 1 1 2 2
ANALYTICAL METHODS
Parameters MethodsAlkalinity Titration Method
Dissolved Organic Carbon (DOC)
High-Temperature Combustion Method
Heavy Metal (Fe, Cu, Zn and Mn)
Inductively Coupled Plasma (ICP)
Oxidation-reduction potential (Eh) ORP meter
pH pH meterSulfate Turbidimetric Method
=> Continuous
Results: Batch Experiment part I
Characteristic of AMD from Banhong mine(Huttagosol and Kijjanapanich, 2008).
Parameters Value Standard* Standard**pH 4.20 - 5.0-9.0Acidity, mg/L CaCO3 91 - -
Total hardness, mg/L CaCO3 740 - -
Calcium, mg/L 260 - -Magnesium, mg/L 54 - -Sulfate, mg/L 623 - -Iron, mg/L 0.58 - -Manganese, mg/L 15.1 not excess 0.5 not excess 1.0Copper, mg/L 0.074 not excess 1.0 not excess 0.1Lead, mg/L 0.005 not excess 0.01 not excess 0.05Zinc, mg/L 1.80 not excess 5.0 not excess 1.0
* Groundwater Quality Standards of Thailand** Surface Water Quality Standards of Thailand
BATCH EXPERIMENT
BATCH EXPERIMENT
Type of organic materials Volatile solid/Total solid in 22 days (VS/TS)
rice husk Reduced from 0.788 to 0.763coconut husk chip Maintained at 0.957bamboo chip Maintained at 0.984municipal compost (septage) Reduced from 0.455 to 0.412composted pig manure Reduced from 0.625 to 0.594
Results: Batch Experiment IVolatile solid per Total solid (VS/TS)
Results: Batch Experiment I
=> pH
Alkalinity =>
Results: Batch Experiment I
=> Oxidation Reduction Potential (Eh)
Sulfate Removal =>
=> Color change in effluent Results: Batch Experiment I
Bamboo chip media Septage media Composted pig manure media
Coconut husk media Rice husk media Change of color in effluent of each organic material in 8 days
=> Color change in media Results: Batch Experiment I
composted pig manure media in 16 days
bamboo chip media in 16 days
Results: Batch Experiment part II
Results: Batch Experiment II
=> Alkalinity
Oxidation Reduction Potential (Eh) =>
Results: Batch Experiment II
=> Sulfate Reduction
84
9599
96
Sulfate Removal =>
Results: Continuous Experiment
Log phase
ktSOSO t 0
24
24 lnln
Using % Sulfate removal = 90%
From the calculation, HRT = 8.22-11.23 days
Safety factor = 1.5, HRT = 12.33-16.84 days
Reactor size = 15 L
kk
S
S
HRT
t
100
10lnln
0
Estimation of the Reduction rate and Residence time
Column Design
Name PRN PRL PRCN PRCL
Lime adding - + - +
=> Alkalinity
Results: Continuous Experiment
Oxidation Reduction Potential (Eh) =>
=> Sulfate Reduction
Results: Continuous Experiment
Sulfate Removal =>
=> Heavy metal RemovalResults: Continuous Experiment
Fe Cu
Zn Mn
Hydroxide Precipitation
=> Dissolved Organic Carbon (DOC)
Results: Continuous Experiment
Conclusion• Composted pig manure and rice husk had maximum sulfate
reducing rate and coconut husk had long lasting
• The suitable hydraulic retention time (HRT) was 16 days.
• The percentage of sulfate removal was up to 98%, which the residue sulfate concentration was 14.5 mg/L in PRL media.
• Effluent pH can be maintain in neutral range (6-8) and effluent alkalinity from composted pig manure was the highest.
• The concentrations of iron reduced from 23.34 mg/L to around 2 mg/L and copper & zinc concentrations could reach below groundwater quality standards of Thailand.
• The percentages of iron, copper, zinc, and manganese removal were 93 %, 99 %, 88%, and 96 % respectively in PRL reactor.
• The column reactors, which added lime into the media, had more efficiency than the reactor that no lime in the media.
Recommendation• Other type of organic materials should be tested. • The appropriate ratio of each type of organic material should be defined.• The lower pH of AMD should be tested on PRB system.• Other type of heavy metal and other concentrations of iron, copper, zinc, and manganese should be tested on PRB system.• Plug flow system reactor should be developed to solve the completely mixed problem.•AMD from different type of mine should be investigated on PRB system.• Performance of pilot should be further investigated.
THANK YOU