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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

Removal of Sulphate and Heavy Metals from Acid Mine

Drainage using Permeable Reactive Barrier Technique

Rissa Anungstri1,** , Himawan Tri Bayu Murti Petrus1,2 , Agus Prasetya1,2,*

1. Department of Chemical Engineering (Sustainable Mineral Processing Research Group),
Faculty of Engineering, Universitas Gadjah Mada, Jalan Grafika No. 2 Kampus UGM
Bulaksumur, D.I. Yogyakarta, 55281, Indonesia

2. Unconventional Geo-resources Research Group, Faculty of Engineering, Universitas Gadjah

Mada, Jalan Grafika No. 2 Kampus UGM Bulaksumur, D.I. Yogyakarta, 55281, Indonesia

Corresponding author: *aguspras@ugm.ac.id **rissa.anungstri@mail.ugm.ac.id or

rissa.anungstri@amman.co.id

Abstract. Containing sulphates and heavy metals, acid mine drainage (AMD) should be
managed strategically to mitigate and control the migration of the contaminants to the
downstream area. Conventional treatment techniques such as using lime to increase pH levels
and metal precipitation or using imported material are usually inefficient and unsustainable. The
AMD treatment investigated in this study uses the permeable reactive barrier (PRB) technique
to enhance bacterial sulphate reduction and metal sulphide precipitation. The AMD treated is
seepage water from industrial mining waste rock dump. This study aims to calculate the removal
efficiency percentage of reactive materials to reduce contaminants in a batch test. Reactive
materials used were organic waste generated locally i.e. domestic sewage sludge (SE), municipal
compost (CO), cocopeat (CP), and the inorganic waste material is fly ash (FA) from a coal-firing
power plant. A batch test was conducted in 56 days in an anaerobic chamber using nitrogen gas
to support an anaerobic environment during subsampling. Mine water used in this test has a low
pH level of 3.2, alkalinity (as CaCO3) < 1 mg/L, high sulphate 3280 mg/L, and contains Fe 46
mg/l, Al 54 mg/L, Cu 2.3 mg/L and Zn 3.4 mg/L. The test result at day 56 from using individual
reactive material shows increased pH levels to 6.9; 5.6; 3.7; and 11.6 for sewage (SE), compost
(CO), cocopeat (CP), and fly ash (FA), respectively. Alkalinity was increased to 1450 mg/L (SE),
323 mg/L (FA), 15 mg/L (CO), 1 mg/L for CP. The highest sulphate removal was measured in
85% from addition of FA. Sulphate removed from organic material reactor were 52% by (SE),
17% by (CO), 20% by (CP). %RE of dissolved metals (Al, Cd, Co, Mn, Ni, Fe, Cu, Zn), from
SE reactor was 80%, CO reactor 80%, CP reactor 52%, FA reactor 94%. Oxidation-Reduction
Potential (ORP) was measured to determine reducing conditions. ORP were measured at -551
mv, 255 mv, 156 mv, and -113 mv for SE, CO, CP and FA respectively. SE has the potential to
remove metals and favour reducing conditions for sulphide precipitation at medium pH levels.
Meanwhile, metal precipitation from addition of FA is mainly due to hydroxide precipitation at
high pH levels. FA was able to decrease the most sulphate due to ion adsorption.

Keyword: Acid Mine Drainage, Fly ash, Organic Waste, Permeable Reactive Barrier

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

1. Introduction
The oxidation of sulphide minerals from waste rock dump releasing acid mine drainage (AMD) has low
pH levels, high sulphate and heavy metal concentrations. Controlling AMD by source control combined
with migration control will be more effective in managing the environmental impacts to ambient surface
water or groundwater [1]. Permeable reactive barrier (PRB), consisting of reactive materials, is installed
in the path of groundwater migration to treat contaminated groundwater. PRB is an alternative option in
replacing the pump and treatment method. Lime treatment techniques are usually inefficient due to
armoring effect [2]. Biological based treatments will result in high sulphate recovery and heavy metal
reduction to treat AMD [3][4]. Using the PRB principle, anaerobic cells has been applied underground
to treat AMD [5]. It can be combined with other treatments, such as wetland and reactive drainage [5]
[4] [6]. PRB is should be specifically designed based on its contaminant quality, hydrological, geological
speciation, construction, and reactive material selection [6]. Experiments using various reactive
materials will be conducted using batch and column studies [7]. The selection of materials was carried
out to consider their availability, cost and environmental sustainability [9]. This research is a batch study
that focuses on the different reactivities of selected materials as a single source. The single batch study
is carried out prior to conducting mixture batch and the column test. Organic substrates were locally
obtained from a sewage treatment plant (SE), coco-net industry waste (CP), and mess hall compost
(CO). While fly ash (FA), selected as an inorganic material, was collected from a coal-firing power
plant. Target of removal efficiency (%RE) for sulphate in groundwater is 70% to achieve the standard
of sulphate concentration based on class I water stipulated in Indonesian Government regulation number
22/2021 [10] while for metals reduction, targeted %RE for Mn, Fe and Cu are 92%, 50%, 76%
respectively. Organic material acts as the electron donor and source for sulphate reducing bacteria (SRB)
to reduce sulphates and favor metal sulphide precipitation. The sulphates reduction mechanism
remediated by SRB activities according to the generalized reactions (1) and (2)[11] for inorganic and
organic substrate. Reduction of SO4 releases H2S, HCO3-(or fully become CO2), NH3+, and PO4- [12].
Cationic metal (Me) will be precipitated as sulphide (equation 3). Where, Inorganic substrate such as H2
and CO2,. Organic matter represents for (CH2O)x.(NH3)y.(H3PO4)z undergoing oxidation.

SRB

4 H2 + SO4 → H2S + 2 H2O + 2 OH-

2-
Inorganic substrate (1)
SRB
Organic Substrate (2)
Organic matter + SO4 → HS- + HCO3- + H2O
2-

Men+ + HS- à Me(S)n + H+ (3)

In equations (4) and (5), under acidic pH of AMD, CaO in fly ash will undergo dissolution and release
OH- and Ca2+ will react with SO4- to form gypsum [13]. Cationic metal (Me), like Fe2+,, Al3+ and Mn2+ ,
will be precipitated as hydroxide (equation 6) [2].
CaO + H2O à Ca 2+ + 2 OH- (4)
Ca 2+ + SO42- à 2H2O + Ca.SO4.2H2O (5)
Men+ + OH- à Me(OH)n (6)

2. Materials and Methods

2.1 Properties of Acid Mine Drainage
AMD was collected from a seepage waste rock dump and placed in a refrigerator in 4o C until needed.
AMD from the waste rock is chosen for its high sulphate and metal concentration that suits a short period
batch reaction test to simulate the reaction in an aquifer. The characteristics of AMD used in this study
as described in Table 1, AMD has low pH levels at 3.2; no alkalinity and high sulphate concentrations

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

at 3280 mg/L. Fe dominates metal content in AMD with 46 mg/L, Mn with 26 mg/L, Zn with 3.4 mg/L,
Cu with 2.52 mg/L and Al with 54 mg/L.

Table 1. Characteristic of Acid Mine Drainage from Waste Rock Dump

Parameter Unit Value
pH Unit pH 3.2
Electrical Conductivity (EC) us/cm 3637
Dissolved Oxygen (DO) mg/L 1.4
Oxidation Reduction Potential (ORP) mV 528
Alkalinity (as CaCO3) mg/L <1
Sulphate (SO4-) mg/L 3280
Aluminium (Al) mg/L 54
Arsenic (As) mg/L 0.002
Barium (Ba) mg/L 0.053
Boron (B) mg/L 0.011
Cadmium (Cd) mg/L 0.0138
Cobalt (Co) mg/L 0.649
Copper (Cu) mg/L 2.32
Chromium (Cr) mg/L 0.001
Iron (Fe) mg/L 46
Lead (Pb) mg/L 0.003
Lithium (Li) mg/L 0.01
Manganese (Mn) mg/L 26
Molybdenum (Mo) mg/L 0.0005
Nickel (Ni) mg/L 0.102
Selenium (Se) mg/L 0.01
Strontium (Sr) mg/L 0.467
Zinc (Zn) mg/L 3.4

2.2 Properties of Organic Substrate

Municipal sewage sludge (SE), mess hall compost (CO) and cocopeat (CP) were analyzed based on the
dry weight. They were measured for pH, moisture content, elemental metal, total organic carbon (TOC)
C, C/N, S, TOC, semi quantification of sulphate reducing bacteria (SRB) present in the substrate, and
leaching characteristic [7]. Solid materials were digested using EPA 6020 method followed by metal
analysis using inductively coupled plasma (ICP-MS) with APHA 3125 (2017) method, TOC analysis
using a TOC analyzer with APHA-5310-B (2017) method, and SRB was estimated using SRB-BART
Kits. Leaching tests of each organic substrate were carried out to determine the leachable component in
Mili-Q water for dissolved metal, alkalinity, sulphate and dissolved organic carbon (DOC) [7].

2.3 Chemical Properties of Fly Ash

The chemical composition of coal fly ash is highly heterogeneous and dependent on the origin of the
source coal and combustion system in a power plant. Fly ash was digested using the EPA method and
analyzed for elemental metal concentration using APHA 3125 (2017) method, while its oxide content
Al2O3, Fe2O3, Ca2O3, K2O, MgO were analyzed using ASTM D4326 method.

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

3. Batch Test
3.1 Experimental Set Up
The batch test was conducted in a capped 1000 ml glass bottle (Figure 1). Each material was wet weighed
200 g for SE, 100 g for CO, 50 g for CP, 100 g for FA and then poured and mixed well with AMD in
the bottle. If corrected to dry mass, the ratio between SE, CO, CP to AMD was 0.03. The mixture purged
with nitrogen gas for 40 minutes to remove dissolved oxygen from the solution. All bottles were kept in
the dark place until sampling and measurement. No inoculum bacteria were used in this experiment. In
addition, one bottle full of AMD was prepared for control.

Figure 1. Batch Test Reactor

3.2 Sampling and Analysis

Sampling and sample preparations were conducted in an anaerobic chamber using Aldrich Atmost bag.
Prior to working in the chamber, N2 gas was purged until dissolved oxygen (DO) concentration
measured inside the chamber was less than < 0.5 mg/L (Figure 2). Water samples were measured to
determine the temperature, pH level, electrical conductivity (EC), oxidation-reduction potential (ORP),
and dissolved oxygen (DO) using YSI multimeter professional plus on days 0, 1, 2, 7, 14, 21, 28 and 56
which was calibrated each day of sampling.

Figure 2. Sampling and Analysis Set Up

Sampling was taken on days 0, 7, 14, 28 and 56 for alkalinity, SO4+, and dissolved metals (Al, As, B,
Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Pb, Li, Mg, Mn, Hg, Mo, Ni, Na, Se, Si, Ag, Sr, and Zn). For H2S, TOC
and NH3 analysis, samples were taken on days 0 and 56. At the end of treatment, the residual sediment
was taken from each reactor and froze until analysis. The pH was determined based on APHA 4500-H+
(2017) method, APHA 2500 (21017) for EC, APHA 4500-O (2017) for DO, and APHA 2580 for ORP.
Unfiltered samples were analyzed for Alkalinity, SO4-, NH3, TOC and H2S. Alkalinity was measured
using APHA 2320-B (2017). H2S sample is preserved with NaOH and Zn Acetate and analyzed using
ion selectivity method, while NH3N and TOC samples are preserved with H2SO4 and analyzed with
APHA 4500 NH3 (2017) for NH3N. TOC, Cl- and SO4- were measured using spectrophotometry method.
Dissolved metal samples were filtered using a Nalgene filter set and Millipore filter of 0.45 µm and
acidified with HNO3 1:1. The metal analysis was conducted using ICP-MS APHA-3125-B (2017)
method, The sediment underwent an acid digestion using EPA Method 6020 and followed by elemental
analysis same with analytical methods for water analysis.

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

3.3 Removal Efficiency

Removal efficiency of batch treatment is calculated using equation (7).
!"#$%!&' (7)
% 𝑅E = !&'
∗ 100%
Where, % RE is the percentage of removal, Cout = final concentration of reaction (mg/L) and Cin= initial
AMD concentration (mg/L).

4. Result and Discussion

4.1 Organic Substrate
From Table 2, SE has the lowest C/N ratio of 5 among other organic materials, which has 18 and 97 for
CO and CP, respectively indicating excess nitrogen over carbon. Although, the ideal C/N ratio for
organic degradation by bacteria is 10 [4], Nevertheless, only observing the C/N ratio does not correctly
show the potential carbon degradation capacity [7]. Among other organics, SE has a relatively higher
total metal concentration of As, B, Co, Cr, Cu, Pb, Mn, Ni and Zn and will possibly be leached out
during treatment.
Table 2 Main Composition of Reactive Materials
Parameter Unit SE CO CP FA
pH - 7,2 7,6 5,5 12,3
Moisture % 83 74 45 <10
Carbon (C) % 22 31 44,49 <0,01
Nitrogen total (N) % 4,4 1,7 0,46 <0,01
C/N - 5 18 97
Total Organic Matter (TOM) % 16 57 29 <0.01
Phosphor (P) mg/kg 14200 506 2710 197
Sulfur (S) mg/kg 13600 380 4060 2200
Cation Exchange Capacity 0.01 meq/100g 6.03 10.2 18.2 0.68
Calcium (Ca) mg/kg 32900 5650 1510 43500
Magnesium (Mg) mg/kg 4090 2840 943 17000
Sodium (Na) mg/kg 1050a 603 772 1140a
Potassium (K) mg/kg 3060 15700a 18600 1040
Aluminum (Al) mg/kg 3920 2790 240 10200a
Arsenic (As) mg/kg 4 2 0,1 11a
Boron (B) mg/kg 80* 19 16 188a
Barium (Ba) mg/kg 57 22 2,6 150
Cadmium (Cd) mg/kg 0.75 0.14 0.07 0.11
Cobalt (Co) mg/kg 2.2 4.7 <0.5 16.8a
Chromium (Cr) mg/kg 12.1 4.2 0.5 18.8a
Copper (Cu) mg/kg 283 103 45.1 14.6
Iron (Fe) mg/kg 4940 9500 689 26100
Lead (Pb) mg/kg 13.0a 3.4 2.1 4.7
Manganese (Mn) mg/kg 290a 160 120 320a
Nickel (Ni) mg/kg 14.1 2.9 1.4 26.2a
Selenium (Se) mg/kg 6.4 <0.5 <0.5 0.8
Strontium (Sr) mg/kg 108a 36 10 170a
Zinc (Zn) mg/kg 592a 64 8 34
asignificant amount or highest value among other material

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

According to Table 3 leaching test characteristics to organic material using Mili-Q water indicates that
some metals, such as As, Cu, Ba, B, Fe, Pb, Mn, Sr, and Zn have the potential to leach out; Alkalinity
was generated from SE and CO but not from CP, and SE also generates sulphate. From the indicative
test for SRB presence in organic material, SE contained 325 cfu/ml SRB with moderate aggressivity
while low SRB presence in CO and CP material.
Table 3. Leachate Characteristic of Organic Material
Parameter Unit SE CO CP
pH pH unit 7.43 6.0 6.0
Alkalinity mg/L 48 51 4
Sulphate (SO4-) mg/L 14 <5 <5
Dissolved Organic Carbon (DOC) mg/L 4 24 33
As mg/L 0.0030 0.0030 < 0.0005
Ba mg/L 0.004 0.012 0.003
Cu mg/L 0.003 0.054 0.002
Sr mg/L 0.049 0.025 0.004
Zn mg/L 0.013 0.042 0.009
SRB population cfu/ml 325 20 -
Aggressivity moderate low -

4.2 Fly Ash Properties

Fly ash used in this test contains 22% CaO and a sum of SiO2, Al2O3 and Fe2O3 is 61.4%, which classifies
fly ash as a class C ASTM, that if exposed to water, will be hardened within 45 minutes [16]. With a pH
of 12.3, fly ash also has corrosive properties. Metallic contents such as Al, B, Ba, Ca, Cr, Fe, Mn, Mg,
Ni and Na are the highest compared to SE, CO and CP.

4.3 pH, DO, Conductivity and ORP

From Figure 3,Figure 4 all reactors except CP showed a sharp increase in pH levels, which occurred
from the first two weeks and then flattened or slightly increase from day 28th to 56th. The SE reactor
provides a pH increase of up to 6.9, while the CO reactor can increase the pH of AMD to 5.6. The
increase in pH in SE and CO reactors corresponds to equations (1) and (2) influenced by SRB activities
as electron acceptors. The pH value of treated water from the FA reactor rose from 3.2 to 11.6. The
increase in pH from the FA reactor is caused by CaO on the surface of FA, which is highly soluble in
releasing OH-, as stated in equation (4)

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

14
600 1600
12 1400

Alkalinitas (mg/L)
400

ORP (milivolt)
10 1200
200
pH

8 1000
0 800
6
600
4 -200
400
2 -400 200
0 -600 0

9 8000 5000
8
7 4000

SO4 - (mg/L)
EC (us/cm) 6000
DO (mg/L)

6
3000
5
4 4000
2000
3
2 2000 1000
1
0 0
0
0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56
0 7 14 21 28 35 42 49 56
Day Day Day

Figure 3. Value of pH, DO, ORP, EC, SO4-, and Alkalinity of Each Reactor during Batch Test.

The ORP on the SE reactor reached -200 mV on day 7th and reached -396 mV on day 56th. Eh value
between -150 to -200 mV is the primary metabolic condition for SRB in reducing sulphate [17] [8]. CO
and CP reactors can only lower the ORP but not until the reducing condition (ORP negative), although
CP did supports anaerobic condition [18]. This different reducing process and anaerobic condition
remediated by bacteria on SE reactor consistent with higher availability of SRB on SE material which
also more aggressive than in CO and CP material (Table 3).
Table 4. Physical Characteristic of Treated Water after 56 Days

Parameter Unit AMD Reactor Reactor Reactor Reactor

SE_D56 CO_D56 CP_D56 FA_56D
pH Unit pH 3.2 6.9 5.6 3,7 11.6
EC us/cm 3637 4763 5236 6029 2640
DO mg/L 1.4 0.7 0.6 0.6 0.5
ORP mV 528 -396 255 168 -156
Eh a mV 596 -328 329 242 -87
a. Eh = Eh (mv) = ORP measured + ( -0.716*T + 220) (Groundwater Geochemistry and Isotopes, Ian Clark, 2015)

The lowest dissolved oxygen concentration (DO) is found in the SE reactor. DO in other bottles are
slightly above 0.5 mg/L which indicates a decreasing anaerobic condition [19], but DO in AMD is still
in the range of the actual field condition. Major anion and cation concentrations (Ca+, Na+, Mg+, K+,
SO42-, HCO3-, OH-, Cl-) reflects to the total dissolves value. The Increase of EC in organic reactors are
due to some cation release from material. However, in the FA reactor, decreasing EC indicates ion
adsorption in precipitates [13].

4.4 Alkalinity, Sulphate, H2S, Ammonia and TOC

The SRB activities on reducing conditions strengthen by the data from SO4-, alkalinity and H2S
concentration. On the SE reactor, SO4- could be reduced from 3280 mg/L to 1580 mg/L, with %RE
reached 52%, the alkalinity increasing to 1450 mg/L, with the presence of 0.653 mg/L H2S on Day 56th,
high NH3N (73 mg/L) was also detected. Compared with %RE SO4- from CO and CP reactor that only

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

17% and 20% respectively, and producing low alkalinity (15 and 1mg/L) with H2S detected only <0.001
mg/L and ammonia <1 mg/L (Table 5).

Table 5. Final Concentration of Alkalinity, Sulphate, H2S, and NH3+ In Batch Test
Parameter Unit AMD Reactor Reactor Reactor Reactor
SE_D56 CO_D56 CP_D56 FA_56D
Alkalinity mg/L 1 1450 15 1 322
1580 2730 2610 489
Sulphate (SO4-) mg/L 3280
(52%) a (17%) (20%) a (85%) a
H2S mg/L <0.001 0.653 <0.001 <0.001 <0.001
Ammonia (NH3+) mg/L 0.35 73 0.63 0.30 0.53
TOC mg/L <1 162 25 43 2
a. In bracket is %RE value.

Contrary to the decrease of SO4- in the FA reactor to 489 mg/L or %RE was 85%, medium alkalinity
was generated up to 322 mg/L, indicates chemical precipitations at high pH and the deposition of
sulphate caused by ionic adsorption FeOH3 and AlOH3 [13]. Increasing alkalinity in the FA reactor was
mainly in the form of OH- according to equation (5) and SiO2 decay. TOC concentration reflects total
organic carbon content in water. SE produces highest TOC, 162 mg/L TOC at the end of treatment. The
CP reactor produced a higher TOC concentration than the CO reactor (43 over 25 mg/L), but the % RE
of SO4- for both CO and CP reactors were similar (20% and 17%). This fact was due to the high lignin
content in CP [20], which Carbon will be degraded more slowly than Carbon from CO [20]. The profile
of changes in significant ion concentrations within 56 days showed in Figure 4. There were indications
of cation exchange processes in which K, Na & Cl arose compared to the initial concentration of AMD
water. Elevated values from them were obtained from leached-off reactive material.

800 1400 700

700 1200 600
600 500
1000
Na+ (mg/L)
K+ (mg/L)

Cl- (mg/L)

500 400
800
400
600 300
300
400 200
200
100 100
200
0 0
0

700 350 100

90
600 300 80
500 250 70
SiO2 (mg/L)
Mg2+ (mg/L)
Ca 2+ (mg/L)

400 60
200
50
300 150 40
200 100 30
20
100 50 10
0 0 0
0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56
Day Day
Day

Figure 4. Concentraion changes of K+, Na+, Cl-, Ca2+, Mg2+ , SiO2 for Each Reactor during the
Batch Test

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IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

4.5 Dissolved Metal

4.5.1 Removal Efficiency
From Table 6, The main mechanism of dissolved metals removal on organic reactor occurred within 3
hours of AMD treatment, which reached an average %RE of 41%, 45%, 34% respectively. Over a
period of 56 days the efficiency reached 80%, 80%, 52% and 94%.
Table 6. Removal Efficiency Percentage in of Batch Test
AMD Reactor SE Reactor CO Reactor CP Reactor FA
Parameter (mg/L) %RE %RE %RE %RE
H-3 a D-56 b H-3 D-56 H-3 D-56 H-3 D-56
As 0.002 35% -650% 45% -55% 60% -85% -50% 88%
Al 54 62% 100% 70% 100% 52% 73% 78% 99%
Cd 0.0138 49% 100% 42% 86% 26% 11% 6% 98%
Co 0.649 29% 100% 36% 81% 22% 16% 9% 100%
Cu 2.32 64% 100% 83% 100% 79% 90% 48% 100%
Ni 0.102 33% 81% 47% 91% 26% 14% 6% 100%
Zn 3,4 39% 100% 34% 84% 22% 44% 17% 100%
Cr 0.001 50% 0% 50% 50% 0% 50% -800% -30000%
Fe 46.3 58% 100% 70% 100% 59% -3% 43% 100%
Pb 0.003 67% 83% -33% 83% -100% 83% -100% 83%
Li 0.01 10% 30% 10% -30% 0% -80% -80% -970%
Mn 26 28% 84% 20% 15% 16% -6% 6% 100%
Mo 0.0005 0% -100% 0% -500% -300% -300% -900% -27900%
Se 0.01 57% -9% 79% 89% 77% 85% -18% -1%
Sr 0.467 -91% -315% -59% -258% 3% -104% -93% -168%
B 0.053 -96% -96% -238% -521% -109% -334% -2334% 64%
Ba 0.011 -82% -91% -709% -573% -55% -618% -400% -91%
Elements Removed 14 11 14 11 13 9 8 11
Elements Increasing 3 6 3 6 4 8 9 6
% RE average 41% 80% 45% 80% 34% 52% 27% 94%
a. H-3 : 3 hours after mixing
b. D-56 : day 56 after mixing
c. %RE targeted for Mn, Fe and Cu are 92%, 50%, 76%.

From Figure 5, dissolved metals such as Al, Cu, Cd, Co, Fe, Mn, Ni, Zn show a decreased concentration
While the decrease of metals concentration in FA is related to the high pH level and hydroxide deposits
[2], the decline of metals in SE occurs at a moderate pH, with the primary control mechanism being the
deposition sulfide at ORP < -150 mv. Metal removal at moderate pH level depends on anaerobic
condition (ORP negative), organic carbon dan SRB [22]. Otherwise, the metal reduction mechanism in
the CO and CP reactor is indicated more by the ion adsorption process[19].

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

80 3,0 35
70 30
2,5
60

Cu (mg/L)
25

Mn (mg/L)
2,0
Al (mg/L)

50
20
40 1,5
15
30 1,0
20 10
0,5
10 5
0 0,0 0

0,8 6,0
0,14 0,7
5,0
0,12 0,6
0,1 0,5 4,0

Zn (mg/L)
Co (mg/L)
Ni (mg/L)

0,08 0,4 3,0

0,06 0,3
2,0
0,04 0,2
0,02 0,1 1,0

0 0 0,0
0 7 14 21 28 35 42 49 56
0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56
Day Day
Day

Figure 5. Concentration changes of of Al, Cu, Mn, Ni, Co, and Zn in Treated Water Concentration
For Each Reactor in the Batch Test

4.5.2 Leached Metals

Some elements were leached out from the reactive materials, which were indicated by higher
concentrations in AMD treated water and showed negative results on the %RE calculation (Table 6).
From Figure 6, At FA reactor, Ba, Se and Sr were leached out from fly ash at pH <11or less than 14 day
but then precipitated in the end, but Cr, Li & Mo continued to leach during treatment. At CO Reactor,
As, Li, Mo, Se, B, and Ba were elevated. At the SE reactor, As Mo, Se, Sr, B and Ba. At CP reactor, As,
Fe, Li, Mn, Mo, Se, Sr, B, Ba cannot be reduced during treatment.

0,0200 2,50 0,20

2,00
0,0150 0,15
Boron, mg/L

Ba (mg/L)
As (mg/L)

1,50
0,0100 0,10
1,00
0,0050 0,05
0,50

0,0000 0,00 0,00

0,35 0,12 0,16

0,30 0,10
0,12
0,25
Mo (mg/L)

0,08
Cr ( mg/L)

Li (mg/L)

0,20 0,08
0,06
0,15
0,04
0,10 0,04
0,02
0,05
0
0,00 0,00

0,020 6,0 60
5,0 50
0,015
4,0
Se (mg/L)

40
Sr (mg/)

Fe (mg/L)

0,010 3,0 30
2,0 20
0,005
1,0 10

0,000 0,0 0
0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56 0 7 14 21 28 35 42 49 56
Day Day
Day

Figure 6. Concentration changes of As, B, Ba, Cr, Li, Mo, Se, Sr and Fe in in the Bacth Test

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

From 17 dissolved metals measured (Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Pb, Li, Mn, Ni, Se, Sr, and
Zn), the SE reactor managed to reduce the concentration of 11 elements. While the CO decreased 11,
the CP reactor lowered 9 elements, and the FA reactor reduced 11 elements.

4.6 Sediment Quality

On the 56th day, the batch tests were ended. The floating and sedimental in CP reactor deposits stayed
light brown as the original material. The SE reactor has greyish water and black and foul-smelling
sediment, indicating intense bacteria and hydrogen sulphide gas activities. Sediments in FA have a thin
white gypsum layer above a grey hardened cement-like material due to the pozzolanic nature of FA. CO
deposits were unchanged black, and odorless. In a glass bottle containing only AMD, there is a thin
orange layer inside the glass bottle that indicates the deposition of Fe.

Carbon Nitrogen Sulphur

40 35000
35 30000
% Carbon and Nitrogen

mg/kg Sulphur
30 25000
25
20000
20
15 15000
10 10000
5 5000
0 0
SE

SE_D56

FA_D5
CO

CP

FA
CO_D5

CP_D5
6

6
6

Figure 7. Concentration of Carbon, Nitrogen and Sulphur after Treatment AMD with Sewage Sludge (SE),
Compost (CO), Cocopeat (CP) and Flyash (FA).

From Figure 7 the sewage sludge lost 65% of C during the reaction and 62% of N and resulted in 124%
S from SE material precipitated in sediment during treatment. At CO reactor, 23% C was used, 11% of
N, and added 3768% of S in sediment. For CP reactor, 34% C was used, 93% of N, and -130% S. While
in FA, S added to sediment was calculated as 391%. SE could be categorized as fast reactive material,
CO is a medium reactive material, and CP is low reactive material.

5. Conclusion
The sulphate and metal removal capability at moderate pH levels remediated by SRB is only favored in
SE reactor while CO and CP did not support anaerobic reducing condition due to the low availability of
SRB that exist in the original material. The metal removal mechanisms in the FA reactor occurred at
high pH while sulphate removal is due to ion adsorption on hydroxide precipitates. From the four studied
materials, every one of them can lower AMD's primary contaminants, namely Sulphate, Al, Cd, Co, Cu,
Pb, Ni, and Zn. Although, some elements will be leached out from each of them. Sulphate reduction is
expected to be 98% by FA, 52% by SE, 17% by CO, and 20% by CP. If compared to targeted 70%
removal sulphate in groundwater, only FA and SE reactor met the target. The average %RE from
dissolved metals (Al, Cd, Co, Mn, Ni, Fe, Cu, Zn), from SE reactor was 80%, 80% from CO reactor,
52% from CP reactor, and 94% from FA reactor. If compared to %RE target for main contaminant Fe,
Mn and Cu, only FA reactor has successfully achieved the target of metals removal. Some adjustments
need to be considered to achieve the target %RE in the following study. They are including additional
of SRB source, the composition of the mixtures based on organic carbon release characteristics (fast,
medium and slow) to sustain longer carbon sources to SRB in the barrier, amount of fly ash added to

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SIBE-2022 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 1065 (2022) 012059 doi:10.1088/1755-1315/1065/1/012059

system, and also combined treatment possibility. The right amount of fly ash needs to be determined to
be just enough to increase pH for metal sulphide precipitation and favor the optimum life of SRB,
without producing more leached metals into the environment.

Acknowledgments
The Authors acknowledges the full support and funding from PT Amman Mineral Nusa Tenggara in
treatability test before implementation of passive treatment using PRB principle on-site and special
assistances and support from colleagues and Laboratory technical staffs.

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