Journal of Environmental Chemical Engineering 8 (2020) 104056

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Journal of Environmental Chemical Engineering

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Membrane selection for the Gold mining pressure-oxidation process (POX) T

effluent reclamation using integrated UF-NF-RO processes
Ramatisa L. Ramos*, Luiza B. Grossi, Bárbara C. Ricci, Míriam C.S. Amaral
Department of Sanitary and Environmental Engineering, Federal University of Minas Gerais, P.O. Box 1294, ZIP 30.270-901, Belo Horizonte, MG, Brazil

A R T I C LE I N FO A B S T R A C T

Editor: Despo Kassinos The UF-NF-RO integrated route has emerged as a reclamation alternative for mine effluent from the pressure-
Keywords: oxidation processing (POX), producing concentrate metals stream, recover acid and water for reuse. Despite the
Pressure oxidation effluent route potentiality, it is still necessary to seek for more chemically stable membranes to increase the process
Industrial wastewater treatment sustainability, particularly because the membranes are exposed to aggressive conditions (acid effluent) and a
Reuse water high rejection is desired. Thus, in this study, commercial NF membranes (NF90, NF270, MPF34, DK, and
Nanofiltration Duracid) and RO membranes (BW30, LP, TFC-HR, XN45, and SG) were evaluated in terms of key performance
Reverse osmosis parameters, such as permeate flux, metals rejection, acid recovery, fouling potential, maximum permeate re-
Commercial membranes
covery (RR), and chemical stability. The DK and SG, as NF and RO membranes respectively, showed the highest
potential for POX effluent treatment application. In the NF process, an average concentration factor of 2 was
observed for metals concentration retentate at 50 % permeate RR. For metals, particularly for cobalt, nickel, and
copper, this concentration was favorable to subsequent recovery processes. The RO generated a retentate with
sulfuric acid 2.5 times more concentrated and low impurity content (0.00058 g L−1) and 40 % RR was chosen for
the process considering the permeate quality, which can be used as reuse water. Besides that, the amount of lime
demanded for neutralization in the proposed route is approximately 41 % lower compared to regular process.
The results showed that for the designing system the membrane selection is a critical part, mainly due the
effluent characteristics.

1. Introduction hydrometallurgical oxidation under elevated pressure and temperature,

Gold plays an important role in human society due to its dis-
tinguished physical properties such as difficult corrosion, low re-
sistance, easy malleability, and high reflectance, being a valuable metal
in all governments and banks [1]. However, despite the benefits of it,
gold extraction and processing cause severe environmental impacts,
that has been intensifying due to the scarcity of high-grade gold de-
posits and the demand to process low-grade gold.
When the exploitation of gold is made from refractory ore minerals,
a pre-oxidation step is required before the cyanidation leaching, since
gold is mainly locked up in sulfidic host minerals and therefore cannot
be directed leached. In this case, the gold ore slurry goes through a
in the presence of acid. Consequently, an effluent (POX-effluent) rich in
sulfuric acid and metals such as nickel, copper, and cobalt is generated
[2]. Normally, the treatment employed for this stream consists of a
neutralization process with lime that precipitates metals, causing their
immobilization. Although the simplicity of the method, its greatest
disadvantages are the possibility of the stripped metal to be transferred
to the environment and the large production of solid waste [3].
In the context of water scarcity, the treatment of mining effluent for
reuse and recovery of byproducts, water, metals, and acid has become a
viable environmentally and economically option, since it would not
only reduce environmental impact, but also add value to the effluent.
To the POX-effluent, an efficient alternative of treatment aiming

Abbreviations: A, Membrane area; AP, Acid purity; As, Arsenic; Cf, Solute content in the feed; Cp, Solute content in the permeate; DA, Daltons; FDChem.irrev,
Chemically irreversible flux decline; FDChem.rev, Chemically reversible flux decline; FDCP, Concentration polarization flux decline; FDFouling, Fouling flux decline;
FDTotal, Total flux decline; J, Permeate flux; Jalf, Water permeate flux after physical cleaning; Jalq, Water permeate flux after chemical cleaning; Jef, Permeate flux
with the final effluent; Jw, Permeate flux with water; Lp, Membrane permeance; MWCO, Molecular weight cut off; NF, Nanofiltration; POX, Pressure-oxidation
processing; PVDF, Polyvinylidene difluoride; R, Solutes rejection; RO, Reverse osmosis; RR, Recovery; UF, Ultrafiltration; Vf, Initial feed volume; Vp, Accumulated
permeate volume; ΔP, Transmembrane pressure; ΔT, Collection time; ΔV, Permeate volume collected; Δπ, Difference in osmotic pressure; μ, Water viscosity; σ,
Reflection coefficient
⁎
Corresponding author.
E-mail address: lramos.eng@gmail.com (R.L. Ramos).

https://doi.org/10.1016/j.jece.2020.104056
Received 11 March 2020; Received in revised form 13 May 2020; Accepted 14 May 2020
Available online 28 May 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
R.L. Ramos, et al.
cleaner principles would be to divide its constituents into three dif-
ferent streams: (a) one rich in metals to further recovery; (b) a pure acid
stream for reclamation, and (c) water with quality for industrial reuse.
As an option to address this issue, Nanofiltration (NF) – Reverse
Osmosis (RO) integrated processes are promising technologies for
treating this effluent. The combination of these processes is becoming
especially interesting due to the development of membranes more
chemically resistant to extreme pH conditions [4] and the ability to
treat water to an excellent quality for reuse. NF membrane can retain
multivalent ions and dissolved molecules with molecular weights of
200–1000 Daltons (DA) [5]. In contrast, RO membrane is permeable to
water but significantly impermeable to salts and can be used to separate
ionic species, dissolved metals, and organic molecules of low molar
mass [6]. Several studies have already been performed in order to
evaluate the use of NF and RO to treat different acidic streams con-
taminated with solutes, both as NF / RO single-step [7–9], or as an
integrated NF-RO route [10,11].
Our previous studies involving the treatment of the POX-effluent by
integrating NF-RO process showed that the NF (MPF-34) attained high
sulfuric acid permeation (82 %) and substantial acid purification (77
%), whereas RO (TFC-HR) increased the acid content by 99 % in rela-
tion to the feed solution. The final RO permeate presented low con-
ductivity and reduced contents of total solids and contaminants, thus
revealing a promising potential in industrial reuse. In addition, the acid
recovery did not lead to the loss of metals of high commercial value,
which were present in the raw effluent since their retention in the NF
concentrate was above 95 % [12,13]. The effects of continuous ex-
posure to the POX effluent on NF (MPF-34) and RO (TFC-HR) mem-
branes were also assessed. Results highlighted the importance to search
for more chemically stable membranes to increase the sustainability of
the membrane performance, especially for NF [14].
Thus, as a mean to broaden previous studies that were focused in
the UF-NF-RO route potential for POX effluent treatment and showed
that economic viability is significantly dependent on the membrane’s
performance, this research aimed to compare five NF and five RO
commercial membranes in the POX effluent treatment in terms of their
selectivity and productivity. The membrane chemical stability re-
garding this effluent were also investigated. Although each supplier
reports some membrane characteristics, their performance can only be
proven through experimental tests, giving space to think about new
materials and characteristics for new membranes production. Besides, it
was also intended to elucidate environmental and economic gains of the
integration of UF-NF-RO to treat the POX effluent, allowing water,
metals, and acid recovery under an optimized water recovery, as well as
affirming the viability of the proposed treatment route with membranes
already available on the market.
2. Materials and methods
2.1. Effluent characterization
The POX effluent was collected on a gold mining company located
in the state of Minas Gerais (Brazil), which produces 63 m3 of POX ef-
fluent per hour. Table 1 represents the main characteristics of the ef-
fluent collected bimonthly for one year.
2.2. Commercial NF and RO membranes
Five commercial NF membranes (NF90, NF270, MPF34, DK, and
Duracid) and five RO membranes (BW30, LP, TFC-HR, XN45, and SG)
were evaluated in this study. Technical specifications of each mem-
brane are presented in Table 2.
2.3. Experimental setup
Before NF and RO experiments, the raw POX effluent was initially
2
Journal of Environmental Chemical Engineering 8 (2020) 104056
Table 1
POX physicochemical characteristics.
Parameter Value Parameter Value
−1
pH 1.2 ± 0.4 Nickel (mg L ) 111 ± 28
Conductivity (mS cm−1) 19 ± 13 Cobalt (mg L−1) 25 ± 8
Arsenic (mg L−1) 15 ± 5 Copper (mg L−1) 98 ± 24
Sulphate (mg L−1) 24 ± 4 Aluminium (mg L−1) 348 ± 152
Calcium (mg L−1) 325 ± 89 Zinc (mg L−1) 64 ± 12
Potassium (mg L−1) 7±1 Iron (mg L−1) 323 ± 175
Sodium (mg L−1) 19 ± 6 Manganese (mg L−1) 242 ± 98
Chloride (mg L−1) 42 ± 2 Suspended solids (mg L−1) 72 ± 22
ultrafiltrate in order to mitigate NF and RO membrane fouling due to
the presence of suspended solids. The ultrafiltration (UF) was per-
formed using a commercial submerged PVDF-based polymer membrane
(ZeeWeed) with a filtration area of 0.047 m2 and mean pore diameter of
0.04 μm. UF was carried out at a pressure of 0.7 bar at batch mode until
a recovery of 80 %.
Both nanofiltration and reverse osmosis experiments were carried
out in a lab-scale cell. The POX effluent was placed in the feed tank and
transferred to the membrane cells using a rotary vane pump (Procon)
connected to a motor velocity controller (Motron CVE 8701 F). The feed
tank temperature was controlled using a Chiller (Gelaqua®1/3 HP) and
maintained at 25 ± 2 °C. Feed flow rate and transmembrane pressure
were set by varying the rotary vane pump speed and the needle valve in
the main retentate stream. Transmembrane pressure was monitored by
one manometer located at the inlet of the membrane module. Feed flow
rate was measured by a flow meter placed at the retentate outlet. The
stainless-steel membrane module had a diameter (2R) of 9 cm, pro-
viding a filtration area of 75 cm2. The radial inlet radius of the cell (r1)
was 64 mm and the internal channel height (2 h) was 1 mm. The tested
membranes were properly cut before being placed in the cell and a feed
spacer, supplied by Dow Filmtec Membranes, of 711 μm (28 mil) was
positioned over the membrane to promote flow distribution.
2.4. Experimental procedure
In order to define the most suitable NF and RO membranes to the
established goals, all ten membranes evaluated in this study were
submitted to the same experimental procedure, being differentiated
only by the feed provided for each group (NF and RO membranes). With
this regard, 4 L of UF-pretreated POX effluent was used as NF feed,
while sulfuric acid synthetic solution with a pH equal to 1.3, simulating
NF permeate, was used as RO feed.
Prior to each experiment, membranes were compacted by per-
meating deionized water at 10 bar until a stable water flux was reached.
Thereafter, filtration experiments were carried out during 4 h in batch
mode whereby the retentate was circulated back into the feed tank.
Feed flow rate, transmembrane pressure and temperature were set at
2.4 L min−1, 10 bar, and 25 ± 2 °C, respectively. By the end of each
experiment, the membrane was rinsed with deionized water with flow
rate of 1.2 L min−1 and cleaned by recirculating and draining a series of
solutions: citric acid solution (pH 2.5) for 30 min, water for 5 min,
NaOH solution (0.4 %) for 30 min, and finally water for 5 min.
The permeate flow rate was determined by measuring the volume of
permeate collected at regular time intervals. Feed and permeate solu-
tions were periodically collected and analyzed for conductivity, pH,
acidity, and metals concentration. Membranes were evaluated in terms
of their metal rejection, sulfuric acid retention, permeance, and flux
decline, according to what was expected in each stage of the treatment.
For the definition of maximum NF and RO water recovery, 6 L of UF
permeate and 6 L of NF permeate was transferred to NF and RO feed
tank respectively. The NF and RO were operated at feed flow rate,
transmembrane pressure and temperature were set at 2.4 L min−1,
10 bar, and 25 ± 2 °C, respectively. The permeate was collected over
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Molecular weight cut off; test conditions specified by the respective manufacturers: 12000 mg L−1 MgSO4, 25 °C, 15 % recovery at 4.8 bar; 250,000 mg L−1 NaCl; 32000 mg L−1 MgSO4, 25 °C, 15 % recovery at 7.6 bar;
2000 mg L−1 NaCl, 25 °C, 15 % recovery at 15.5 bar; 5500 mg L−1 NaCl, 25 °C, 15 % recovery at 10 bar; 6Feed solution containing 2000 mg L−1 NaCl, 25 °C, 15 % recovery at 15.5 bar; references: b [15]; c [16]; d [17]; e [18].
time while concentrate was returned to the feed tank. The water re-

500 mg L−1 h−1

covery was set as the maximum value for the permeate fraction in

72.9 ± 3.9b
17.3 ± 3.0b
which both membrane integrity and permeate quality were not harmed.

∼ 100 DA
Polyamide
composite
The effects of continuous and long-term exposure to the effluent on

98.5 %4
2 - 10

50 °C
GE the NF and RO membranes characteristics were evaluated by immersing
SG

one pristine membrane fragments in NF and RO effluent retentate (from

a 40 % permeate recovery) respectively. Periodically, fragments were

500 mg L−1 h−1

Poly piperazine-

removed from the solution and rinsed with deionized water.

Subsequently, filtration tests were carried out in order to measure the
∼ 100 DA
98.5 %3

hydraulic membrane permeance. After collecting a membrane fragment

Trisep

amide

2 - 11
XN45

45 °C
and proceeding with filtration tests, the immersion solutions were re-

19e
3e
placed, and the fragments were re-immersed.
< 0.1 mg L−1

2.5. Analytical methods

∼ 100 DA
Polyamide
composite

99.55 %6
TFC-HR

4 - 11

45 °C
Koch

The POX effluent and permeates obtained in the NF and RO stages

–
–

were physicochemical analyzed according to the following parameters:

pH (pHmeter Qualxtron QX 1500), conductivity (Hanna conductivity
< 0.1 mg L−1

meter HI 9835), suspended solids (2540D), acidity (2310B), ion con-

∼ 100 DA
Polyamide
composite

centration (ion chromatograph Dionex ICS-1000 equipped with AS-22

99.2 %5

and ICS 12-A columns), and metal concentration (Inductively Coupled

2 - 11
DOW
RO commercial membranes

45 °C
LP

Plasma Optical Emission Spectrometer (ICP-OES) Varian, 720-ES). The

–
–

analysis were performed in accordance with the Standard Methods for

the Examination of Water and Wastewater [19].
< 0.1 mg L−1

68.3 ± 12.5b
25.9 ± 4.7b
∼ 100 DA
Polyamide

2.6. Calculations
composite

99.5 %4
2 - 11
BW30

DOW

45 °C

The permeate flux at the permeation temperature [J(T)] was cal-

culated according to Eq. (1). It was considered for the calculation the
500 mg L−1 h−1

permeate volume collected (ΔV), the collection time (Δt), and effective
150 – 300 DA

62.2 ± 4.2d

membrane area (A).

composite
Polymer
Duracid

ΔV
< 10
98 %3

J (T ) =
70 °C

(1)
38d

AΔt
GE

J(T) was normalized to 25 °C [J(25 °C)] using a correction factor

Polymer composite

1000 mg L−1 h-1

calculated by the ratio of the water viscosity at the permeation tem-

150 – 300 DA

perature [μ(T)] and at 25 °C [μ(25 °C) ], as shown in Eq. (2).

40.6 ± 5.2b
16.4 ± 3.1b

μ (T )
98 %3

J (25°C ) = *J (T )
50 °C
3-9

μ (25 °C ) (2)
DK

GE

Through an adjustment of the methodology presented by Capar

et al. [20] the total flux decline (FDTotal) was calculated based on Eq.
26.9 ± 0.4c

(3). The flux decline caused by fouling (FDFouling), which is the sum of
composite
Polymer

200 DA

chemically reversible (FDChem.rev) and irreversible (FDChem.irrev) fouling,

MPF34

35 %2
0 - 14

70 °C
Koch

was estimated by Eq. (4), that is a result of the Eq. (5) and Eq. (6) sum.
No

The flux decline due to concentration polarization (FDCP) was also es-
timated from the permeate flux (Eq. (7)), since accumulation of solute
Polyamide with

< 0.1 mg L−1

on the membrane surface causes an increase in the osmotic pressure.

200 – 400 DA

32.6 ± 1.3b
9.0 ± 4.2b
> 97 %1

( Jw− Jef)
overcoat

FDTotal =
NF270

(3)
2 - 11

Jw
DOW

45 °C
NF commercial membranes

( Jw− Jalf)
NF and RO membranes technical specifications.

FDFouling =
Jw (4)
Polyamide with

< 0.1 mg L−1

( Jalq− Jalf)
44.7 ± 1.9b
72.4 ± 5.8b

FDChem . rev =
∼ 200 DA
> 97 %1

Jw (5)
overcoat

2 - 11
NF90

DOW

45 °C

( Jw− Jalq)
FDChem . irrev =
Jw (6)

( Jalf− Jef)
FDCP =
pH range (continuous

Maximum operating

Jw (7)
Chlorine tolerance

Contact angle (°)

temperature
Saline rejection

In Eq. (3)–(5), Jw is the permeate flux with water, Jef is the permeate
Characteristics

operation)
Manufacturer

flux with the final effluent (after two hours of permeation), Jalf is the
Roughness
Material

MWCOa

permeate flux with water after physical cleaning, and Jalq is the water
Table 2

permeate flux after chemical cleaning.

a

The observed rejection of solutes was calculated using Eq. (8), in

4

3
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Table 3
Performance of NF membranes for rejection of sulfuric acid, metals, and conductivity. (grey scale: observed rejection).

which Cf and Cp represent the solute content in the feed and permeate osmotic pressure average calculated for every recovery.
streams, respectively. The retentate osmotic pressure (πr,α) for a recovery α was measured
Cf − Cp considering the retentate concentration of dissolved species (ΣCr,α )
R (%) = × 100 determined by mass balance as shown in Eq. (14).
Cf (8)
100*ΣCf − α *ΣCpαavg
The water recovery (RR) was defined considering the accumulated ΣCr , α =
100 − α (14)
permeate volume (Vp) and initial feed volume (Vf) as shown by Eq. (9).
where ΣCf is the sum of the main dissolved species molar concentra-
Vp
RR = × 100 tions in the feed, and ΣCpαavg is the average sum of the main dissolved
Vf (9) species molar concentrations in the permeate.
Fouling resistance as a function of the NF and RO experiments re- Thus, with the retentate concentration of dissolved species (ΣCr,α ) as
covery was determined using a thermodynamic irreversible a function of the recovery given by Eq. (14), the retentate osmotic
Spiegler–Kedem model [21], which has been widely used to describe pressure was estimated according to the Van’t Hoff Eq. (15).
transport through RO/NF/UF membranes [22]. According to the model, πr , α = RT ΣCr , α (15)
the permeate flux may be described as a function of net transmembrane
pressure gradient (ΔP−σΔπα) as shown in Eq. (10). The sulfuric acid permeation was calculated according to Eq. (16).
CpH 2SO 4
(ΔP − σ Δπα ) acid permeation (%) = . 100%
Jα = CfH 2SO 4
μ (Rtα ) (10) (16)

In Eq. (8), Jα is the permeate flux for a recovery α, ΔP is the applied
transmembrane pressure, σ is the reflection coefficient estimated by the
averaged membrane rejection [23], and Δπα is the difference in os-
motic pressure of the solution at retentate (πr,α) and permeate streams
(πp,α) , Δπiα = πr,α − πp,α , for a recovery α, Rt is the total filtration re-
sistance for a recovery α, comprising intrinsic membrane resistance
(Rm) and fouling resistance (Rf), and μ is the water dynamic viscosity.
Eq. (10) can then be rewritten putting in evidence the total filtration
resistance, as shown in Eq. (11).
(ΔP − σ Δπα )
Rtα =
μ (Jα ) (11)
where Rt can be defined as:
Rtα = Rm + Rfα (12)
Permeate osmotic pressure (πp,α) was estimated by the Equation of
Van’t Hoff, described in Eq. (13).
πp, α = RT ΣCpα (13)
where R is the universal gas constant, T is the permeation temperature,
and ΣCpα is the sum of molal concentrations multiplied by the number
of ions generated from the molecular species dissolved in the permeate
for a recovery α. Since permeate quality was evaluated every 10 % of
recovery, the permeate osmotic pressure was estimated as equal the
where CpH2SO4 and CfH2SO4 are the concentrations of sulfuric acid in the
permeate and feed, respectively.
Furthermore, the acid purity (AP) was calculated according to Eq.
(17).
ΣC
AP =
CH2 SO4 (17)
where ΣC is the sum of the selected impurities concentration in a stream
(feed, permeate or retentate) and CH2SO4 is the concentration of sulfuric
acid in that stream.
3. Results and discussion
3.1. Evaluation of NF and RO commercial membranes
Five NF membranes were assessed regarding their metal rejection,
sulfuric acid retention, and permeance when treating the POX effluent.
As it can be seen from Table 3, all evaluated NF membranes presented
an elevated metal rejection (between 91–99 %). The low to moderate
arsenic (As) rejection can be associated to the As speciation at the
evaluated pH [24,25]. At pH 1.3, which corresponds to the NF feed, As
(III) and As (V) are in the neutral forms of H3AsO4 and H2AsO3, re-
spectively. For neutral species, the main retention mechanism is size
exclusion [13,26]. Therefore, a bigger ratio between the molecular

4
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

weight of these species and the molecular weight cut off (MWCO) for
the membrane will lead to a larger expected rejection [26]. The mo-
lecular weights of H3AsO4 and H2AsO3 species are respectively 141.94 g
mol−1 and 125.94 g mol−1, which are small when compared to the
MWCO for the evaluated membranes, between 150 - 400 g mol−1 for
these membranes (Table 2). Accordingly, a small rejection for the
neutral As species is expected, as observed in the present study.
The highest As rejection was observed for the NF90 membrane.
Although the MWCO for NF90 is approximately 200 g mol−1, the ex-
treme pH may affect the membrane pore size due to the dissociation of
membrane functional groups, which alters the size exclusion me-
chanism of removal for nanofiltration membranes [27]. Childress and
Elimelech [27] found that a pore size of a polyamide membrane similar
to NF90, which has both carboxyl and amine functional groups, can be
significantly reduced at both high and low pH. At high pH, the carboxyl
groups would be deprotonated (= COO-), and at low pH (this research
case), the amino groups would be protonated (=NH3+). In both cir-
cumstances, the electrostatic repulsion between the charged groups
would cause a reduction in pore size. Other studies have shown similar
As rejection behavior by the NF90 membrane [28,29]. Regarding the
acid permeation, the NF90 membrane presented a high rejection of
sulfuric acid (85 %), which is also typical for a RO membrane. These
results suggest that this membrane is unsuitable for the purpose of
purifying sulfuric acid in the nanofiltration step (through metals re-
tention) for later concentration in the RO operation.
Despite having a molecular weight cut off smaller than NF270, the
effect of sulfate speciation and membrane surface charge was promi-
nent in MPF34, resulting in the lowest sulfuric acid rejection (25 %)
observed. At lower pH’s, sulfate is mainly found at HSO4− form, and its
transport through the membrane is favored by the positive charge of the
active layer that is found under these pH circumstances [30,31]. Thus,
in order to ensure electroneutrality on the permeate side, HSO4-
transport must be coupled to cations. Given the mobility of H+, this
specie is more prone to permeate the membrane, thus diminishing acid
rejection. Results found are in accordance with that observed in pre-
vious studies [12,14]. In addition, although MPF-34 membrane was
selected for its stability over a wide range of pH (0–14), previous stu-
dies also indicated a decrease in the selectivity of the MPF34 membrane
during a long-term exposure, as well as to an acid solution, resulting in
acid production with lower purity as permeate and lower metal con-
centration in the retentate [14]. Increased flux observed for MPF34
after physical cleaning (Table 4) reinforces the low chemical stability
for the MPF34 membrane in relation to the effluent. Ricci et al. [14]
mentioned that this may be related to degradation of the nanofiltration
membrane selective layer and/or an increase of the pore size, if the
pores presence is considered. The MPF34 membrane was used in these
tests to allow comparison with previous studies where this membrane
was used in the integrated NF-RO system applied for the POX effluent
[12–14].
Concerning flux, Table 4 shows that NF270 and DK membrane
presented the highest permeate flux (27 and 25 L m−2. h-1 respectively),
which are in accordance with the structure of these membranes
[32,33]. The membrane flux decline is mainly associated to fouling
(chemically reversible and chemically irreversible fouling) and con-
centration polarization phenomenon. For DK, flux decline was caused
mainly by concentration polarization, while for the NF90 membrane,
fouling played the biggest role. The lower membrane fouling observed
for the DK and NF270 membranes could be attributed to the greater
pore diameter associated to a lesser surface roughness and lower hy-
drophobicity (Table 2) which could subsequently lead to lower fouling
potential when compared to other membranes. A high surface rough-
ness can increase the membrane fouling potential, since foulant parti-
cles may accumulate in the valleys on the membrane surface due to
higher local flux over valley regions [34]. Still, when compared to DK,
NF270 presented a slightly highest membrane fouling, that can be as-
sociated to the higher initial effluent permeate flux (40 L m−2 h−1) in
comparison to that (28 L m−2 h−1) for the DK membrane. The higher
permeate flux introduced more foulant to the membrane surface, and
subsequently encouraged fouling on the NF270 membrane. In addition,
the NF90 membrane presented a low cleaning efficiency (73 %) for
permeance recovery, which may be associated to the high membrane
fouling that occurred during effluent permeation. Chemical cleaning
requires further optimization for NF90 membrane application.
Confronting all these results, the DK membrane presented the
highest potential for implementation in POX effluent treatment, since it
demonstrated a combination of the desired characteristics: high rejec-
tion of metals of economic interest (Co, Cu and Ni), low sulfuric acid
retention, low fouling potential, and high permeance.
In order to reinforce DK membrane suitability to POX effluent
treatment, its permeance (Lp) was measured during 180 days of con-
tinuous exposure to the NF retentate (pH of 1.53 and conductivity of
18.64 mS), and the results are shown in Table 5. DK permeance reduced
30 % after 180 days, probably due to fouling at the membrane surface.
Nevertheless, a tendency of increased permeance (a strong indicative
that the membrane had significant losses at the surface) was not ob-
served, which points out to a chemical stability bigger than the one
observed by Ricci et al. [14] for MPF 34. These results imply that DK
may be suitable for the treatment of POX effluent, as long as periodic
cleaning in order to avoid fouling is performed.
As a next step, five different commercial RO membranes were
evaluated regarding their ability to reject sulfuric acid, high permeance
and high chemical stability for the treatment of POX-NF permeate. All
tests were carried out using a synthetic solution similar to those ob-
tained after NF filtration using DK membrane (Table 3). In Table 6, the
highest initial permeate flux for the acid solution was observed for the
XN45 membrane (40 L m−2 h-1); however, the permeate flux increased
throughout the test, reaching a flux of 45 L m−2 h-1 at the end of 2 h,
which suggests a low chemical stability for the membrane when oper-
ating at such low pH. The low rejection of sulfuric acid reinforces its
low stability, thus showing its unsuitability to this application.
By comparing BW30 and SG membranes performance, it can be
noticed that despite presenting similar permeate flux, the acid

Table 4
NF membrane permeance performance and fouling potential.
Membrane Jwa Jeob Jef c
Jalf d
Jalqe RR (%) Type of flux decline Resistance x 1013 (m−1) Cleaning Efficiency (%)

−2 -1 −2 -1 −2 -1 −2 -1 −2 -1 f g h i
(L m h ) (L m h ) (L m h ) (L m h ) (L m h ) FDTotal FDFouling FDCP Rf Rfr Rfir Physical Chemical

1
DK 55 28 25 48.7 55 12 0.55 0.11 0.43 7.02 6.08 0.95 89 100
Duracid 24.2 14 13.6 22.8 24 10 0.44 0.06 0.38 9.34 8.34 1.03 94 99
MPF34 29.7 15.1 13.9 38.7 49 11 0.53 n.e.j n.e. 11.2 n.e. n.e. 130 165
NF90 54.6 14.5 9.9 17.6 40 9 0.82 0.68 0.14 31.3 15.8 15.6 32 73
NF2701 108 40 27 92 110 11 0.75 0.15 0.6 9.39 8.74 0.65 85 102

a
Jw is the water permeate flux for new membrane; bJeo is the initial effluent permeate flux; cJef is the final effluent permeate flux; dJalf is the water permeate flux water
after physical cleaning; eJalq is the water permeate flux after chemical cleaning; fconcentration polarization; gfouling resistance; hreversible fouling resistance;
i
irreversible fouling resistance; j n.e., not measured, because the membrane did not show chemical stability in relation to the effluent; lfiltration time reduced to 3 h.

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R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Table 5 Table 7
DK permeance performance during long-term exposure to NF retentate. SG permeance performance during long-term exposure to RO retentate.
Day Lp (L m−2 h-1 bar-1) Lpfa / Lpib Day Lp (L m−2 h-1 bar-1) Lpfa / Lpib

0 6.59
50 6.41
66 5.44
108 5.05
180 4.60
a
final permeance in the day tested; binitial permeance in the day 0.
concentration in BW30 permeate was 3 times bigger than those ob-
served for SG. According to Tang et al. [35], BW30 membranes are
coated with a hydrophilic neutral coating layer rich in −COH groups,
while SG membranes are found to have a likely aliphatic coated/
modifier. This structural diversity lead to a difference both in the sur-
face roughness and the contact angle (Table 2), in which the first re-
sulted in a fouling resistance more than 10 times bigger for BW30
membrane, when compared to SG (Table 6). Conversely, the more hy-
drophobic surface found for SG membrane might favor the adsorption
of co-ions, therefore changing the membrane surface polarity, as ob-
served by Childress and Eimelech [36]. This change in polarity can be
associated to the increase in the rejection of HSO4− and, consequently,
H+, thus decreasing its concentration on the permeate side.
For all membranes, the resistance due to membrane fouling corre-
sponds mainly to irreversible scaling, which requires chemical cleaning
for its removal. Thereby, due to their high rejection of sulfuric acid and
permeate flux and low fouling potential – that might be related to the
low surface roughness (Table 2), SG membranes have shown to be
suitable for the discussed application.
The chemical stability of SG membrane in acid conditions was also
assessed. The SG membrane permeance (Lp) was measured during 212
days of continuous exposure to the RO retentate (sulfuric acid con-
centration around 11 g L−1), and the results are shown in Table 7. SG
permeance reduced 13 % after 212 days, probably due to fouling at the
membrane surface. Nevertheless, a tendency of increased permeance (a
strong indicative that the membrane had significant losses at the sur-
face) was not observed, which points out to a chemical stability bigger
than the one observed by Ricci et al. [14] for TFC-HR membrane. At the
end of eight weeks, the TFC-HR membrane permeance increased 33 %.
These results point that SG may be suitable for the treatment of
permeate from nanofiltration of POX effluent and that periodic cleaning
must be performed in order to mitigate fouling. NF and RO water re-
covery
Since NF and RO membranes are much more permeable to water
than to solutes, by increasing the recovery, the salt concentration in the
retentate is also enlarged, therefore increasing both fouling potential
and osmotic pressure. Thus, for a fixed operating pressure, an increase
in the recovery leads to a reduction in the permeate flux. On the other
hand, at higher recovery, a larger amount of permeate is generated
from a given volume of effluent [37]. Therefore, it is necessary to
– 0 2.3 –
0.97 30 2.4 1.04
0.83 62 2.2 0.96
0.77 212 2.0 0.87
0.70
final permeance in the day tested; binitial permeance in the day 0.
a
determine the most suitable RR to optimize both permeate flux and
productivity.
For the DK nanofiltration membrane (Fig. 1), it was observed that
the decay of the permeate flux occurred linearly (R² = 0.98), with a
reduction of approximately 0.6 L m−2 h-1 for each increase of 1 % in the
RR. This was due to the accumulation of solutes at the membrane
surface, causing increased fouling and osmotic pressure (which leads to
a decline in the permeate flux if constant pressure is maintained).
On the other hand, it was also noticed that the permeate quality
(conductivity and metal concentrations) remained approximately con-
stant up to a RR of 50 % (Table 8), above which there is a distinct
increase in all constituent’s concentration in the permeate. This result is
consistent with those found by Bi et al. [38], who observed that the
concentration polarization on a NF membrane increases from approxi-
mately 1–1.45 when the recovery increases from 20 % to 70 %, which
leads to reduced removal efficiency.
In that way, the 50 % RR was chosen as being most suitable for the
process considering that the flux decay rate in relation to RR is ap-
proximately constant, but after a certain point there is a significant
reduction in the permeate quality and that operation at higher RR fa-
vors the development of fouling. No significant change in pH was ob-
served by increasing the RR. An average concentration factor of 2 was
seen for the concentration of metals in the retentate at a RR of 50 %. For
metals, particularly of cobalt, nickel, and copper, this concentration
was favorable to subsequent recovery processes.
For the SG reverse osmosis membrane, the decline in permeate flux
followed the decay profile of applied effective pressure, being asso-
ciated with increasing osmotic pressure of the concentrate as can be
seen in Fig. 2. The resistance caused by membrane fouling remained
relatively constant until reaching a recovery of 30 %, from which an
increase in fouling resistance was observed to reach 4 × 1014 m−1.
Table 9 presents the SG permeate and retentate quality data. A 92 %
increase in the acid concentration in the retentate was observed in re-
lation to the feed as was expected, due the high rejection of acid by the
RO membranes. In that way, the 40 % RR was chosen as being adequate
for the process considering that the flux decay can be controlled by
improving the operation and hydrodynamic conditions and that
permeate quality and acid concentration was not compromised up to
this RR.

Table 6
RO membrane permeance performance, fouling potential and H2SO4 rejection.
Membrane/ Jwa Jeob Jefc Jalfd Jalqe Type of flux decline Resistance x 1013 (m−1) H2SO4 permeate H2SO4 retentate
Sample (g L−1) (g L−1)
(L m−2 (L m−2 h-1) (L m−2 h-1) (L m−2 h-1) (L m−2 h-1) FDTotal FDFouling FDCPf Rf g Rfrh Rfiri
h-1)

TFC-HR 19.6 12.6 11.5 15.55 19.6 0.41 0.21 0.21 2.64 0.69 1.96 0.03 10.25
SG 22.8 21.4 14.5 18.2 22.6 0.36 0.20 0.16 2.09 043 1.67 0.03 11.11
BW30 24 14.9 13.9 23 24 0.42 0.04 0.38 21.89 8.66 13.23 0.90 10.24
LP 26 18.7 16 21 27 0.38 0.19 0.19 19.01 – – 0.24 10.9
XN45 46 40 45 47 55 0.02 n.e. n.e. 7.99 n.e. n.e. 3.15 7.99

a
Jw is the water permeate flux for new membrane; bJeo is the initial effluent permeate flux; cJef is the final effluent permeate flux; dJalf is the water permeate flux after
physical cleaning; eJalq is the water permeate flux after chemical cleaning; fconcentration polarization; gfouling resistance; hreversible fouling resistance; iirreversible
fouling resistance; n.e., not measured, because the membrane did not show chemical stability in relation to the effluent.

6
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Fig. 1. NF permeate flux, applied effective pressure, permeate and retentate electric conductivity as functions of DK membrane RR.

Table 8
DK nanofiltration membrane rejection of sulfuric acid and metals at different RR (grey scale: observed rejection).

3.2. Integration of UF-NF-RO processes
Table 10 shows a summary of the sulfuric acid concentration results.
The UF step did not affect the effluent acidity, as expected. Similarly,
the NF process was capable of efficiently separating metals (retained in
the retentate) from the acid, which was 93 % permeated. Finally, the
RO step was capable of concentrated the acid about 2.5 times, with a
purity of 0.00058 g impurity / g acid, and generated a permeate with
low acid concentration, that could be used as industrial reuse water. In
this way, the POX effluent volume of 63 m3 h−1 produced and treated
can be applied in the mining industry, reducing water consumption.
Another relevant point to be analyzed was the demand for lime to
neutralize the generated streams: UF, NF, and RO retentates and RO
permeate. Since RO permeate showed pH values around 2.5 and low

7
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Fig. 2. RO permeate flux, applied effective pressure, conductivity, and H2SO4 permeate concentration as functions of SG membrane RR (Operation variables were
2.4 L min−1 feed flow rate, 10 bar transmembrane pressure, and 25 ± 2 °C temperature).

solute concentrations, it could be directly reused without pH adjust-
ment in some stages of gold mining (e.g., adjusting the slurry con-
centration after the POX process). The high sulfuric acid concentration
in the RO retentate, along with the low fraction of impurities, allows for
its direct reuse in the production process (e.g., in the acid pretreatment
stage, which is used to avoid inhibition of the oxidation process under
pressure, or in the actual adjustment of the acidity during the pressure-
oxidation process).
Therefore, only the UF and NF retentate streams would require a
neutralization step. Table 11 compare the lime demand and the
estimated cost to neutralize POX effluent in the required streams. In this
context, it is noteworthy that the metals within the NF concentrate can
still be recovered before neutralization, reducing the demand for lime
and making it possible to obtain valuable by-products. Furthermore, if
neutralization with precipitation is used for conditioning the con-
centrate, sludge generation (and consequently its disposal) would be
greatly minimized by first removing valuable metals, since the volume
of lime required for neutralization would be much smaller, approxi-
mately 41 % lower compared to regular process.

Table 9
SG reverse osmosis membrane performance - rejection of metals and ions for different RR (grey scale: observed rejection).

8
R.L. Ramos, et al. Journal of Environmental Chemical Engineering 8 (2020) 104056

Table 10
Sulfuric acid mass balance in the assessed route and potential acid recovery.
Sample pH H2SO4 (g L−1) Recovery (RR) (%) Acid permeation (%) Acid purity (g impurity / g acid) Acid concentration ratio

UF Feed 1.01 5.8 80 100 0.63 1

Permeate 1.01 5.8
Retentate 1.01 5.8
NF Feed 1.01 5.8 40 93.5 0.0015 0.96
Permeate 1.01 5.4
Retentate 1.01 6.2
RO Feed 1.02 5.4 50 6.5 0.00058 2.5
Permeate 2.5 0.38
Retentate 0.9 14.2

Table 11 Appendix A. Supplementary data

Lime demand for each stream requiring a neutralization step.
Stream Lime Demand (kg m−3) Estimated Cost (U$ m−3)
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jece.2020.104056.
POX effluent 9.7 1.45
UF retentate 0.96 0.14 References
NF retentate 4.72 0.71

*cost of lime: U$ 0.15 per kg.
4. Conclusions
The UF-NF-RO integrated route allows the POX effluent reclama-
tion. The RO permeate could be used as reuse water, the NF retentate
rich in metals could be further processed for recovery of these by-
products, and a RO retentate with sulfuric acid 2.5 times more con-
centrated and with low impurity content (0.00058 g L−1) could be re-
circulated for pre-acid treatment or reused to control acidity in the POX
process. Thus, besides being able to recovery byproducts, the proposed
route also reduces the lime demand, approximately 41 %, for neu-
tralizing the remaining streams and the hazardous waste production.
Among the membranes evaluated, the DK and SG, as NF and RO
membranes respectively, showed the highest potential for application
in POX effluent treatment, since it demonstrated a combination of the
desired characteristics: high rejection, permeate flux, chemical stabi-
lity, and low fouling potential. The results show that careful membrane
selection is a critical part of designing processes, particularly when
membranes are exposed to aggressive situations and a high rejection is
desired.
CRediT authorship contribution statement
Ramatisa L. Ramos: Conceptualization, Methodology, Formal
analysis, Visualization, Investigation, Writing - original draft, Writing -
review & editing. Luiza B. Grossi: Methodology, Formal analysis,
Visualization, Investigation, Writing - original draft. Bárbara C. Ricci:
Formal analysis, Visualization, Supervision. Míriam C.S. Amaral:
Formal analysis, Visualization, Supervision, Project administration,
Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to thank to the Coordination of
Improvement of Higher Education Personnel (CAPES), the National
Council for Scientific and Technological Development (CNPq), and the
Foundation for Research Support of the State of Minas Gerais
(FAPEMIG).
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