Scientific African 16 (2022) e01137

Contents lists available at ScienceDirect

Scientific African
journal homepage: www.elsevier.com/locate/sciaf

Assessment of the principal factors influencing the silver

cyanidation process by using Plackett-Burman experimental
design
Zakia Zmirli a, Anas Driouich b, Slimane El harfaoui b, Ali Mohssine b,
Hafida Mountacer c, Brahim Sallek a, Hassan Chaair b,∗
a
Laboratory of Advanced Materials and Process Engineering, Faculty of Sciences, University Ibn Tofail, Kenitra, BP 133, Morocco
b
Laboratory of Process Engineering and Environment, Faculty of Sciences and Technology, University Hassan II, Mohammedia, BP 577,
Morocco
c
Laboratory of Environmental Sciences and development, Faculty of Sciences and Technology, University Hassan I, Settat, BP 146, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: For decades, the cyanidation process is frequently used for gold and silver extraction, as
Received 28 October 2021 well as metal extraction as a sub-product of lead, zinc, and copper metallurgy. The present
Revised 17 February 2022
study focuses on the factors that influence silver extraction efficiency, which represents the
Accepted 22 February 2022
rate of silver dissolution in a sodium cyanide solution. The screening design of Plackett and
Burman has been performed to investigate the variables that have the most impact on the
Editor DR B Gyampoh extraction of metal namely temperature, pH, free cyanide concentration, dissolved oxygen
level, pulp density, lead nitrate ratio (Pb(N O3 )2 ratio), and setting time.
Keywords:
To evaluate the meaning of the seven variables, twelve experiments were carried
Cyanidation process
out and the result revealed that for a 95% confidence level, the chosen parameters for
Silver extraction
Screening design the model are meaningful in their whole. The following three factors were significant
Plackett and Burman design (P < 0.05) when it comes to the silver cyanidation process including, setting time, pulp
Fisher-Snedecor test density, and free cyanide concentration. The variance analysis (ANOVA) using a Fisher test
has shown that the setting time was considered to have the most significant effect for
a significance level of 1% (Fstatistics = 22.8328 > Fc = 21.2). Likewise, for a 95% confidence
level, both pulp density and free cyanide concentration have a major influence on the re-
sponse. The Pareto diagram results clearly show that pulp density and setting time repre-
sent 20% of factors that have 80% effect on the silver extraction. Model validation verified
that no statistically relevant distinction was made between the predicted and experimental
results with the determination coefficient R2 = 0.93, this mean that the metal extraction is
better fitted to the model and the predictability of the model is adequate to explain 93%
of the variation in the dependent variable as a function of factor variation.
© 2022 The Authors. Published by Elsevier B.V. on behalf of African Institute of
Mathematical Sciences / Next Einstein Initiative.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)

∗
Corresponding author.
E-mail address: hass.chaair@gmail.com (H. Chaair).

https://doi.org/10.1016/j.sciaf.2022.e01137
2468-2276/© 2022 The Authors. Published by Elsevier B.V. on behalf of African Institute of Mathematical Sciences / Next Einstein Initiative. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Introduction

Silver has been known since ancient times and is one of several metals that were discovered during the early periods
of human history. This metal is soft, malleable, and has a silvery luster. It is considered stable in contact with oxygen
and water, however, a black layer of sulfide is formed when it is attacked by sulfide compounds (in the air). Many industrial
items, such as electronics, photographic film, printed circuit boards (PCBs), and catalysts ( (Ag(Al2 O3 ) and (Au − Ag/(Al2 O3 ) to
reduce nitrogen oxides) require the use of metallic silver. Recent briefs indicate that the silver demands are significant and
growing at 2 to 2.5% per year [1].
Ore processing includes the classic phases of mechanical preparation, namely: grinding, gravimetry, flotation, cyanida-
tion, extraction of silver cement by precipitation, and another intensive cyanidation step. As a result, Scheid concentrated
and precipitated products follow different steps in the melting unit to produce a finished product in the form of silver
anodes, grading 99.5% silver. The latter can be located in many forms in ores, either in metallic form (native), or com-
bined with gold (e.g. electrum) and in various argentiferous minerals, namely tennantite ( (Cu, F e, Ag)12 As4 S13 ), proustite
(Ag3 AsS3 ),pyrargyrite (Ag3 SbS3 )), acanthine/argentite (Ag2 S ) and tetrahedrite ( (Cu, F e, Ag)12 Sb4 S13 ) [2–4].
Among the most commonly known and used methods for producing silver from gold /silver ores is cyanide leaching.
These methods have attracted a considerable amount of attention in the last few years to enhance the extraction cyanidation
process rate [5]. The stoichiometry of the cyanide leaching in the case of sulfide and pure metal can be described as follows
Eqs. (1) or (2). These are just two of many possible reactions that can occur during the cyanidation process [6–12].
−
4AG + 8CN(−aq) + O2(g) + 2H2 O(l ) → 4Ag(CN )2(aq −
) + 4OH(aq ) (1)

−
Ag2 S(S ) + 4C N(−aq) + 2H2 O(l ) → 2Ag(C N )2(aq − −
) + OH(aq ) + HS(aq ) (2)

A great deal of interest has been devoted to the development of an effective pre-treatment for silver and gold to be ex-
tracted from ores and other secondary sources in cyanide leaching due to various obstacles that hinder the process such as
the low leaching rate and the long duration required. Several treatments and pretreatments methods have been described
in the literature to enhance gold/silver extraction by cyanidation process, namely pressure oxidation, bio-oxidation, roasting,
ultra-fine grinding, and modified cyanidation [13–15]. For increasing the dissolving rate of silver and gold, and avoiding a
substantial risk of cyanide’s toxicity to the environment and human health, alternative lixiviants including chloride, thiourea,
and thiosulfate have been studied by several researchers to replace cyanide [16–20]. One of the non-cyanidation processes
that have received the greatest attention is thiosulfate leaching, as it involves non-toxic chemicals and is considered inex-
pensive, thus it is used as a potential alternative to cyanidation [1,19].
Otherwise, various researchers investigated the use of auxiliary oxidants such as calcium peroxide (CaO2 ), hydrogen
peroxide (H2 O2 ), and permanganate (KMnO4 ) to enhance silver and gold dissolving efficiency [21–22]. Regrettably, no such
oxidants has performed successfully, most likely because of their high price and their possible interaction with free cyanide
[23–24]. XIE and DREISINGER [24] have indicated that during the cyanidation process of gold and silver, ferricyanide can be
used as an alternative oxidant, notably in a heap or lixiviation operations in situ in which oxidant availability and reactivity
are critical as the ferricyanide solubility in the cyanide solution is very high. On the other hand, if sulfide minerals such as
chalcopyrite and pyrrhotite exist, they will also interact with ferricyanide, resulting in additional costs for this oxidant [24].
Further leaching studies of metallic minerals in ventilated cyanide solution have demonstrated that various factors in-
fluence this process. Dissolved oxygen concentration and cyanide all play an influential part in the dissolution of silver and
gold [23]. Several research results published in the literature demonstrate that to achieve an acceptable silver extraction
efficiency from silver sulfide minerals using the cyanidation process, a rather high Cyanide concentration, and a lengthy
dissolving cycle is required [12,25–31].
Few studies only were conducted on the silver extraction efficiency using experimental designs. In this study, we have
experimentally investigated and evaluated seven factors that are likely to influence cyanidation through the experimental
designs to study their influences and to improve the cyanidation performance, and optimize NaCN consumption. There are
several types of designs: full factorial designs [32–33] and the response surface designs with a view to process optimization
[34–36].
The design chosen for our study is a screening design rather than a full factorial design. The full factorial designs generate
a high number of experiments (27 = 128 experiments )contrary to 12 experiments obtained by the screening design. Thus, a
Plackett and Burman-type screening design are better recommended [37]. Therefore, the latter is crucial to comprehending
the effects of factors that affect the silver extraction process as they are closely related to the improvement of cyanidation
performance. To achieve this objective, we have proceeded by applying statistical techniques, in this case, to improve the
accessibility of this technique. These approaches, which enable a minimum of experimentation, provide the opportunity to
examine factors from the most to least influencing and also enable the optimization of process settings to achieve the high-
est attainable outcome. Moreover, the minimization of the number of experiments will decrease contact with cyanide and
reduce the exposure to its toxic effects. Indeed, a fast-acting compound, cyanide is conventionally referred to as a poison.
It is rapidly incorporated into the breathing passages and mucosal systems and is also absorbed through the gastrointesti-
nal system and the skin. Oral ingestion of cyanide can be transformed into hydrogen cyanide if it is in direct contact with

2
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Fig. 1. Simplified flowsheet for silver cyanidation.

the gastric juice, the product of this interaction causes intercellular inhibition and intermediate cell death. A rate of 1.5 mg
C N − per kg body weight is considered to be lethal dosage [38].
In the present article, a screening of the factors impacting cyanide processing has been carried out. of silver ore. We
adopted screening designs, the most well-known for 2-level factors are Hadamard or Plackett and Burman matrices [39].
The experiments consist of highlighting the effects of the seven factors on the studied response (Plackett and Burman,1946).
The metal extraction (the dissolution rate of silver) was chosen as a response while temperature, pH, ratio of lead nitrate,
dissolved oxygen concentration, the concentration of free cyanide, pulp density and setting time are the assessed factors by
Plackett and Burman screening design and statistically evaluated by ANOVA [40].

Materials and methods

Silver cyanidation process in the silver ore processing plant

In the ore processing plant, the cyanidation unit (Fig. 1) is fed with the flotation concentrate as well as the reject of
intensive cyanidation. The float concentrate is directed to the thickener where some of its water is removed to adjust the
density. The overflow of thickener is directed to the freshwater basin while the underflow is diluted, then directed to the
silver cyanidation reactor through the tank where the following reagents are added to adjust pH and pre-oxidation in order
to avoid reversal of the complexation reaction of silver with cyanide:

• Lime to keep a basic pH > 9.5 for avoiding the emission of HCN vapor which is very toxic;
• P b(N O3 )2 for sulfur oxidation to avoid silver passivation phenomena (production of thiosulfate SC N − on the silver sur-
face);
• H2 O2 for oxidation.

Samples

In this research, the sample of silver ore used came from a processing factory for silver ore situated in Imiter located
150 km east of Ouarzazate and 29 km from Tinghir city in Morocco.
A large quantity of a sample of the floated concentrate (pulp) was taken to have the same sample in all tests. The pulp
was filtered and the filter cake was then dried in a heated oven (ThermoStable OV-20) at 170 °C while the filtrate was
recovered to be used for density adjustment. The silver in the dried cake was analyzed by Atomic Absorption Spectrometry
(AAS) Method.

Experimental procedure

The entire series of tests were performed at a pilot scale in batch mode within a glass vessel of a total volume of 600 mL
of pulp. The experimental setup for silver cyanidation is schematically illustrated in Fig. 2.

3
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Fig. 2. . Synoptic scheme of the operational unit.

For each test, the temperature inside the reactor was monitored at the environment temperature employing a rotating
heating/cooling bath. The pH, pulp density d p , lead nitrate ratio (P b(N O3 )2 ratio), and dissolved oxygen concentration were
adjusted to the desired level according to the conditions of each design experiment. The pH and dissolved oxygen were
measured by an OHAUS STRATER 3100 pH-meter and Jenway 9500 oximeter, respectively.
Sodium cyanide was used to adjust the free cyanide concentration. After that, the mixture is placed under stirring for
the setting time as given in Table 3.
The sodium cyanide (NaCN ) of 95% purity grade, lead nitrate (99% ) and H2 O2 (30% ) were supplied by Lobachemie. Lime
(90% ) was obtained from Panreac.
The solid’s weight ms (dried cake) and the volume of water Ve to be added to obtain a density according to the chosen
experimental field are calculated according to the following equations:
For ms :
d p = m p /Vp (3)

m p = d p × Vp (4)

ms
Cs = (5)
mp
 
ds dp − 1
Cs = × (6)
dp ds − 1
 
ds dp − 1
ms = m p × × (7)
dp ds − 1

For Ve :
Vp = Ve + Vs (8)

Ve = Vp − Vs (9)

  m 
mp s
Ve = − (10)
dp ds

With:

m p = pulp mass

4
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Table. 1
Parameters influencing Cyanidation, their notations, and units.

Parameter Notation Unit

Free cyanide concentration FCN ppm

Dissolved oxygen concentration O2 dissolved mg/L
pH pH —–
◦
Temperature T C
Setting time Ts h
Lead nitrate ratio (Pb(NO3 )2 ratio) g/tonne
Pulp density m p / Vp dp g/L

ms = solid mass
Cs = rate of solid in pulp
d p = pulp density ( rate of solid in pulp)
ds = solid density (ds = 2.7)
Vp = pulp volume
Vs = solid volume
Ve = water volume

Analytical methods

The samples obtained after all these steps were subsequently filtered and dried in an oven at 170 °C. After that, the dried
cake was analyzed by AAS to determine the metal Extraction (Rm )defined by the following equation:
Si − S f
Rm = (11)
Si
where Si , Sf are the initial and final cake silver composition respectively.

Experimental design

Plackett - Burman design

The selected screening design is a statistical tool based on mathematical methods to reduce the number of experiments
and to determine the influential variables on the studied process for further optimization. Indeed, the present study will
allow determining the power of the effect of each factor based on a Fisher test, in the addition of the p-values comparison
with the α risk (α = 0.05), as well as the use of the Pareto chart for the ranking of the effects and the interactions in
decreasing order, while determining the 20% of the terms representing 80% of effects on the process.
Screening designs based on Hadamard matrixes are widespread, the most widely used is the Plackett-Burman design
[40]. They are a fast and efficient tool allowing the identification of the significant factors among a huge number of variables
while reducing time and preserving convincing information on each parameter [32,41]. It is a fractional factor design and
the main effect of such a design can be simply calculated as the difference between the average of the measurements taken
at the high (+1 )and low (−1 ) levels respectively. This allows the evaluation of each factor’s effect. Once the tests of the
matrix of experiments have been carried out, a statistical analysis of the results is done, which will determine the significant
factors. A high positive or negative coefficient contrast implies that a factor has a high impact on the response, whereas a
coefficient near zero indicates that a factor has little or no effect [42].
In this paper, a Plackett-Burman plan was carried out for twelve experiments to assess the significance of seven process
parameters on silver extraction.

Studied parameters and response

To study the response (metal extraction(Rm )), it is required to investigate the effect of many factors, which considerably
influence this operation Table 1 describes the seven chosen factors in this study, namely: Temperature, pH, free cyanide
concentration, dissolved oxygen concentration, pulp density, setting time, and lead nitrate ratio. These factors are those,
which have a priori a direct influence on the metal extraction, i.e. on the dissolution rate of silver.

Mathematical model
In this study, it was found that the number of variables influencing the metal cyanidation and having an impact on
the selected response is very high. Therefore, it was necessary to conduct a preliminary study to reduce the number of
parameters studied. For this purpose, we opted for the screening design.
The mathematical model adopted is a first-order polynomial model, that can be represented by the equation:
Y = b0 + b1 X1 + b2 X2 + b3 X3 + b4 X4 + b5 X5 + b6 X6 + b7 X7 (12)

5
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Table. 2
Levels of variables used in the Plackett-Burman design.

Factors Unit Coded variables Level (-) Level (+)

FCN ppm X1 1000 3000

O2 dissolved mg/L X2 6 10
pH X3 9.5 12
◦
Temperature C X4 22 30
Ts h X5 3 9
(Pb(N O3 )2 ratio) g/tonne X6 70 200
d p = m p /Vp g/L X7 1250 1400

Xi (i = 1, 2, 3, 4, 5, 6, 7): coded variables, Xi = xi±xxi0 , with xi , x0 :

real variables.

Table. 3
Experimental design according to Hadamard matrix.

Order FCN O2 dissolved pH Temperature Ts Pb(N O3 )2 ratio dp

∗
Logical Rand X1 x1 X2 x2 X3 x3 X4 x4 X5 x5 X6 x6 X7 x7
1 9 1 3000 -1 6 1 12 -1 22 -1 3 -1 70 1 1400
2 3 1 3000 1 10 -1 9,5 1 30 -1 3 -1 70 -1 1250
3 1 -1 1000 1 10 1 12 -1 22 1 9 -1 70 -1 1250
4 2 1 3000 -1 6 1 12 1 30 -1 3 1 200 -1 1250
5 4 1 3000 1 10 -1 9,5 1 30 1 9 -1 70 1 1400
6 5 1 3000 1 10 1 12 -1 22 1 9 1 200 -1 1250
7 12 -1 1000 1 10 1 12 1 30 -1 3 1 200 1 1400
8 8 -1 1000 -1 6 1 12 1 30 1 9 -1 70 1 1400
9 11 -1 1000 -1 6 -1 9,5 1 30 1 9 1 200 -1 1250
10 10 1 3000 -1 6 -1 9,5 -1 22 1 9 1 200 1 1400
11 7 -1 1000 1 10 -1 9,5 -1 22 -1 3 1 200 1 1400
12 6 -1 1000 -1 6 -1 9,5 -1 22 -1 3 -1 70 -1 1250

Xi : coded factor; xi : real factor;

∗
: randomized.

Where:

 Y is the response function (silver extraction).

 The X1 , X2 , X3 , X4 , X5 , X6 , and X7 are the independent variables.
 The term b0 is the mean critical response value.
 The terms b1 , b2 , b3 , b4 , b5 , b6 , and b7 are the factor effects of X1 , X2 , X3 , X4 , X5 , X6 , and X7 respectively.

Statistical analysis
The Fisher test (F-test), combined with the probability (p-value) equal to 0.05 were employed to evaluate the variance
analysis (ANOVA). Similarly, the coefficient of determination R2 is used to assess the model validation, while comparing the
predicted values with the calculated values [43]. The statistical software JMP 11 is used for the experimental regression
analysis [35].

Definition of experimental fields

The experimental fields of the seven parameters selected have been established based on preliminary experiments. Every
variable was controlled at two points, coded as (-1) for the lower levels and (+1 ) for the higher level. The factors selected
and their experimental fields are given in Table 2.

The experimental matrix

For each test and before the experiment, a sheet must be filled indicating the conditions of the factors to be respected.
it is preferable to randomize trials to limit the possible disruptive influence of uncontrolled factors.
The depicted matrix of the experiments in Table 3 is a Hadamard matrix, depending on the selected arrangements, it
consists of twelve experiments by using a Plackett- Burman screening design [40] This design allows us to determine the
"weight" of each factor and to estimate the most relevant factors of the seven factors at two levels in a minimum number
of experiments.

Results and discussion

After conducting the twelve experiments in combinations selected by the Plackett-Burman screening design and carefully
assessing their responses, the experimental values of metal extraction in the designed experiments are reported in Table 4.
The experimental data of silver extraction in the tests were investigated by the statistical software JMP 11 [44].

6
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Table. 4
Experimental design and results for metal extraction.

Factors Response
Exp FCN O2 dissolved pH Temperature Ts Pb(N O3 )2 ratio dp Metal Extraction (%)

1 +1 -1 +1 -1 -1 -1 +1 50.31%
2 +1 +1 -1 +1 -1 -1 -1 67.15%
3 -1 +1 +1 -1 +1 -1 -1 50.31%
4 +1 -1 +1 +1 -1 +1 -1 56.28%
5 +1 +1 -1 +1 +1 -1 +1 61.19%
6 +1 +1 +1 -1 +1 +1 -1 68.31%
7 -1 +1 +1 +1 -1 +1 +1 30.86%
8 -1 -1 +1 +1 +1 -1 +1 56.28%
9 -1 -1 -1 +1 +1 +1 -1 66.84%
10 +1 -1 -1 -1 +1 +1 +1 57.53%
11 -1 +1 -1 -1 -1 +1 +1 32.74%
12 -1 -1 -1 -1 -1 -1 -1 42.57%

Table. 5
Analysis of variance (ANOVA).

Source of variation Degree of freedom Sum of squares Square of average Fexp p-value Signifiance

Model 7 2447575.6 349654 7.4215 0.0356

∗
Residual 4 188454.9 47114
Total 11 2636030.5

Fexp : Fisher-Snedecor Experimental

∗
: Significant to 95% (F0,05 (7, 4 ) = 6.09): critical Fisher-Snedecor according to the table) [46].

Analysis of variance (ANOVA)

To show that the factors selected for the model are significant as a whole, a variance analysis (ANOVA) is performed
(Table 5). From this analysis, it can be seen that the operational results are fully covered by the model [45]. Indeed, the
p-value which is equal to 0.0356 is less than 0.05.
The metal extraction experimental factor of Fisher-Snedecor of F(Fexp = the model variance/ the residual vari-
ance = 7.4215) whereas according to the table of Fisher-Snedecor, the value of critical F factor [45] is equal to
(Fα (ν1 , ν2 ) = F0,05 (7, 4) = 6.09) .These data show that the Fexperimental (Fexp = 7.4215) value is above the statistical Fisher
factor of a factor (Fc = 6.09) [47]. Consequently, for a 95% level of confidence, thus, the factors retained for the design are
meaningful in their entirety.

Graphical analysis of factors effects

Fig. 3 illustrated the profiles for the estimated response effect of the variables on the silver extraction efficiency.
This plot of factors effects illustrates that the variables affecting the silver extraction are free cyanide concentration,
temperature, setting time, lead nitrate rate, and pulp density however pH and O2 dissolved have a negligible effect on the
metal extraction. When the value of one of the factors increases from a minimum value to a higher value and the response
value increases, it means that the factor has a positive effect on the response. Therefore, from Fig. 3, it appears very well
that free cyanide concentration, temperature, setting time have a positive effect on the response while lead nitrate rate and
pulp density have a negative effect on the silver extraction.

Coefficient’s estimation and statistical study of the effect of the factors studied

The model’s seven parameter values, their significance, and their effects on the model’s performance are summarized in
Table 6. In this table, the F-value and the p-value are related to each coefficient. The "F" values are used to evaluate the
meaning of the coefficients of each parameter for a significant level higher or equal to 95%, and the p-values are set as
the minimum significance level resulting in that the null hypothesis H0 is rejected. (H0 : The factor is not influential). The
higher the Fisher "F" value, the significance of the coefficients is determined by the p-value, the smaller the p-value the
more significant the term [48].
The results shown in Table 6 confirm that three factors setting time, pulp density, and free cyanide concentration, sig-
nificantly affect the response. These findings are consistent with the literature which reports that to achieve an adequate
amount of silver recovery from the silver sulfide minerals by cyanidation, a higher concentration of cyanide and a lengthy
dissolving cycle are necessary for the leaching process [12,25–31].
On the one hand, the factor identified as having the most meaningful impact on the response has a statistical Fstatistics
value (22.8328 for the setting time) it is considered superior to the F theoretical value (F0.01 (1, 4 ) = 21.2)) using Fisher’s test
for a significance level of 1%. On the other hand, for a confidence level of 95%, pulp density and free cyanide concentration

7
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Fig. 3. Profiles of predicted values of factors on the silver extraction efficiency.

Table. 6
Effects test and the estimation of the coefficient.

Model term Coefficientbi Sum of squares Fstatistics Prob. > F Signification

Constant 54.950833 - - -
∗
FCN 5.1684416 423988.3 8.9993 0.0399
O2 dissolved -0.100774 161.2 0.0034 0.9562 NS
pH 0.3043582 1470.2 0.0312 0.8684 NS
Temperature 1.3562718 29194.7 0.6197 0.4752 NS
∗∗
Ts 8.2326876 1075736.2 22.8328 0.0088
(Pb(N O3 )2 ratio) -2.849764 128899.8 2.7359 0.1735 NS
∗
dp -6.799167 732680.8 15.5513 0.0169

NS: Not significant [46].

∗∗
: Significant to 99% (F0.01 (1, 4 ) = 21.2);
∗
: Significant to 95% (F0.05 (1, 4 ) = 7.71) ;

significantly affect the response, since their Fstatistics values (15.5513, 8.9993 respectively) are greater than the critical Fisher
value (F0.05 (1, 4 ) = 7.71) [47].
One notable observation to take up from Table 6’s findings is that density has the most negative effect (Effect esti-
mates = - 6.799167) on the silver extraction. This is in agreement with the observations by Cilek et al. [49] who found that
the most pronounced reducing effect on the silver extraction is induced by the pulp density (d p ) (14.9% ) obtained from the
direct cyanidation. However, similar findings have been noted for the silver and gold cyanidation process [50–51].

Modelisation

The determination of the selected statistical model coefficients leads to creating a regression model equation that de-
scribes the response ’metal extraction’ as a function of the most important components. In this equation, only significant
model terms and their estimated coefficients are considered.
Therefore, for a 5% threshold of meaning, the formula of the model is as follows:

Rm = 54.95 + 8.23Ts + 5.17 FCN − 6.8dp (13)

With (b0 = 54.95)is a constant not depending on any factor.

Classification of coefficient estimated according to Pareto diagram

In order to pinpoint the 20% of the factors that have an 80% effect on the metal extraction, we have employed the Pareto
diagram (Fig. 4). The Pareto technique classifies the terms that reflect the most significant proportion of the examined

8
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Fig. 4. Classification of sorted coefficients according to Pareto diagram.

Table. 7
Residuals, experimental and predicted values of silver extraction %.

Logical Order Silver extraction Experimental % Silver extraction predicted % Residual

1 50.31 46.70 3.60

2 67.15 62.67 4.48
3 69.35 66.51 2.84
4 56.28 57.55 -1.27
5 61.19 65.67 -4.48
6 68.31 71.15 -2.84
7 30.86 33.56 -2.7
8 56.28 55.91 0.36
9 66.84 63.23 3.60
10 57.53 57.025 0.505
11 32.74 30.03 2.70
12 42.57 49.385 -6.815

character based on the percentages of studied criteria [52]. The results of the Pareto diagram (Fig. 4) show that only pulp
density and setting time account for 20% of the factors that influence silver extraction by 80%. It is evident from Fig. 4 that
for enhancing the silver dissolution in the cyanide solution, it is necessary to act on pulp density and setting time.

Validation of the model

The expected values, the observed results, and their residuals were calculated by statistical software JMP 11 software
[44] are presented in Table 7.
Considering the experimental error of the chemical analysis (Residual), It was discovered that there is no statistically
significant difference between the experimental and projected values, as evidenced by minimal residual values. We were
able to confirm the validity of the established model according to these findings.
The plot of observed values as a function of predicted values for the response ‘the metal extraction’ is presented in Fig. 5.
Fig. 5 illustrates that the points are in the confidence interval and proximity of the first bisector. The p-value for Rm
regression is lower than 0.05. Thus, the correct correlation between the anticipated and observed (experimental) values for

9
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

Fig. 5. Graphical representation of observed values as a function of predicted values.

the response ’metal extraction’ may be reliably concluded with a very high coefficient of determination R2 in the order of
93 %. To put it another way, the established model can account for 93 %of the variation in metal extraction.

Conclusion

Through the present work, we have sought to highlight factors influencing the silver cyanidation process. For this pur-
pose, the application of the Plackett-Burman design has enabled us to identify those three factors namely: free cyanide
concentration, pulp density, and setting time are significant factors influencing silver extraction.
An appropriate analysis of variance is used to validate the model (ANOVA). Similarly, a Fisher test with a significant
threshold greater than or equal to 95 % was employed to assess the significance of each parameter’s regression coefficients.
The factor considered to have the most important impact on the response is setting time since its statistical Fisher value
(22.8328) was higher than the critical value of Fisher (F0.01 (1, 4 ) = 21.2) for a confidence level of 99% according to the F-
test. Moreover, for a 95% confidence level, pulp density and free cyanide concentration significantly affected the response,
as their Fstatistics values (15.5513, 8.9993 respectively) were greater than the Ftheoretical (F0.05 (1, 4 ) = 7.71).Using the Pareto
diagram, it was concluded that only pulp density and setting time represent 20% of the factors that affect silver extraction
by 80%.
A good agreement was found between the experimental and predicted values of the responses by the generated model
with the p-value for Rm regression lower than 0.05 and 93% for the coefficient of determination R2 .
As perspectives, and since the most variables impacting the silver cyanide process have been determined, the future work
will focus on optimizing this process by a composite design to improve the metal extraction efficiency while ensuring the
rationalization in terms of time and chemicals used in the process.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

10
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

References

[1] L. Xiao, P.W. Han, Y.L. Wang, G.Y. Ful, Z. Sun, S.F. Ye, Silver dissolution in a novel leaching system: Reaction kinetics study, Int. J. Miner. Metall. Mater.
26 (2) (2019) 168.
[2] J. Marsden, I. House, The Chemistry of Gold Extraction, Society for Mining, Metallurgy, and Exploration, USA, 2006.
[3] O. Celep, A.D. Bas, E.Y. Yazici, I. Alp, H. Deveci, Improvement of silver extraction by ultrafine grinding prior to cyanide leaching of the plant tailings of
a refractory silver ore, Miner. Process. Extr. Metall.Rev. 36 (4) (2015) 227.
[4] J. Rajala, G. Deschênes, Extraction of gold and silver at the Kupol mill using CELP, in: World Gold Conference, The Southern African Institute of Mining
and Metallurgy, South Africa, 2009, p. 35.
[5] Y.L. Li, J. Liu, W.S. Guan, Cyanidation of gold clay ore containing arsenic and manganese, Int. J. Miner. Metall.Mater. 17 (2) (2010) 132.
[6] M.I. Jeffrey, P.L. Breuer, The cyanide leaching of gold in solutions containing sulfide, Miner. Eng. 13 (10-11) (20 0 0) 1097.
[7] G. Senanayake, Gold leaching in non-cyanide lixiviant systems: critical issues on fundamentals and applications, Miner.Eng 17 (6) (2004) 785.
[8] G. Senanayake, The cyanidation of silver metal: review of kinetics and reaction mechanism, Hydrometallurgy 81 (2) (2006) 75.
[9] G. Senanayake, A review of effects of silver, lead, sulfide and carbonaceous matter on gold cyanidation and mechanistic interpretation, Hydrometallurgy
90 (1) (2008) 46.
[10] C. Gamarra, A. Alarcon, T. Canchanya, M. Garcia, G. Pareja, C. Segura, J.C.f. Rodriguez, Ultrasound-assisted leaching as a greener method in mineral
processing: improved silver extraction from a sulfide-based mineral concentrate without increasing cyanide consumption, I+i Investigacion aplicada e
innovation 10 (2016) 15.
[11] M. Khalid, F. Larachi, Impact of silver sulfides on gold cyanidation with polymetal sulfides, Trans Nonferrous Met. Soc. China 28 (2018) 542.
[12] F. Habashi, A Textbook of hydrometallurgy, Metallurgie Extractive Quebec Publications, Canada, 1999.
[13] X. Qiu, Z. Hu, B. Song, H. Li, J. Zou, A novel process for silver extraction from a refractory Au–Ag ore in cyanidation by pretreatment with sulfating
leaching using pyrite as reductant, Hydrometallurgy 144-145 (2014) 34.
[14] V.V. Kar, Panchanadikar, Use of ultrasound in microbial leaching of nickel from laterites, Ultrason. Sonochem. 2 (1) (1995) S5.
[15] J.L. Luque-Garcia, M.D. Luque de Castro, Ultrasound: a powerful tool for leaching, Trends Anal. Chem. 22 (1) (2003) 41.
[16] R. Briones, G.T. Lapidus, The leaching of silver sulfide with the thiosulfate–ammonia–cupric ion system, Hydrometallurgy 50 (3) (1998) 243.
[17] M.F. Almeida, M.A. Amarante, Leaching of a silver-bearing sulfide by-product with cyanide, thiourea, and chloride solutions, Miner. Eng. 8 (3) (1995)
257.
[18] J.E. Dutrizac, The leaching of silver sulfides in ferric ion medi, Hydrometallurgy 35 (3) (1994) 275.
[19] H.F. Zhao, H.Y. Yang, L.L. Tong, Q. Zhang, Y. Kong, Biooxidation-thiosulfate leaching of refractory gold concentrate, Int. J. Miner. Metall. Mater. 27 (8)
(2020) 1075.
[20] C.B. Sun, X.L. Zhang, J. Kou, Y. Xing, A review of gold extraction using non-cyanide lixiviants: Fundamentals, advancements, and challenges toward
alkaline sulfur-containing leaching agents, Int. J. Miner. Metall. Mater. 27 (4) (2020) 417.
[21] M. Cruells, A. ROCA, F. PATIÑO, E. SALINAS, I. RIVERA, Cyanidation kinetics of argentian jarosite in alkaline media, Hydrometallurgy 55 (2) (20 0 0) 153.
[22] A. Nugent, K. Brackenbury, J. Kinner, AuPLUS systems for the treatment of gold ores using hydrogen peroxide and calcium peroxide, World Gold 91
(1991) 173.
[23] F. Xie, D. Dreisinger, J. Lu, The novel application of ferricyanide as an oxidant in the cyanidation of gold and silver, Minerals Eng. 21 (15) (2008) 1109.
[24] F. Xie, D.B. Dreisinger, Use of ferricyanide for gold and silver cyanidation, Trans. Nonferrous Met. Soc. China 19 (2009) 714.
[25] R.M. Luna, G.T. Lapidus, Cyanidation kinetics of silver sulfide, Hydrometallurgy 56 (2) (20 0 0) 171.
[26] O. Celep, I. Alp, H. Deveci, M. Vicil, Characterization of refractory behaviour of complex gold/silver ore by diagnostic leaching, Trans. Nonferrous Met.
Soc. China 19 (3) (2009) 707.
[27] M. Khalid, F. Larachi, A. Adnot, Cyanidation of gold associated with silver minerals in sulfide mineral matrices, Chem. Eng. Technol 41 (7) (2018) 1282.
[28] Y. Zhang, Z. Fang, M. Muhammed, On the solution chemistry of cyanidation of gold and silver bearing sulfide ores. A critical evaluation of thermody-
namic calculations, Hydrometallurgy 46 (3) (1997) 251.
[29] F. Habashi, Kinetics and mechanism of gold and silver dissolution in cyanide solution, Montana Bureau of Mines and Geology Bulletin, 59, Montana,
USA, 1967.
[30] J.B. Hiskey, V.M. Sanchez, Mechanistic and kinetic aspects of silver dissolution in cyanide solutions, Journal of Applied Electrochemistry 20 (3) (1990)
479.
[31] H.K. Lin, J.L. Oleson, D.E. Walsh, Behavior of gold and silver in various processing circuits at the Fort Knox Mine, Mining, Metallurg. Explor. 27 (4)
(2010) 219.
[32] Y.R. Abdel-Fattah, H.M. Saeed, Y.M. Gohar, M.A. El-Baz, Improved production of Pseudomonas aeruginosa uricase by optimization of process parameters
through statistical experimental designs, Process Biochem. 40 (4) (2005) 1707.
[33] A. Mohammad zadeh, M. Ramezani, A.M. Ghaedi, Synthesis and characterization of Fe2O3-ZnO- ZnFe2O4/carbon nanocomposite and its application to
removal of bromophenol blue dye using ultrasonic-assisted method: Optimization by response surface methodology and genetic algorithm, J. Taiwan
Inst. Chem. Eng. 59 (2016) 275.
[34] N. Rhazi, H. Hannache, M. Oumam, A. Sesbou, B. Charrier, A. Pizzi, F. Charrier-El Bouhtoury, Green extraction process of tannins obtained from Moroc-
can Acacia mollissima barks by microwave: modeling and optimization of the process using the response surface methodology RSM, Arabian J. Chem.
12 (8) (2019) 2668.
[35] S.D. Priyadharshini, A.K. Bakthavatsalam, Optimization of phenol degradation by the microalga Chlorella pyrenoidosa using Plackett-Burman design
and response surface methodology, Bioresour. Technol. 207 (2016) 150.
[36] S.J. Kalil, F. Maugeri, M.I. Rodrigues, Response surface analysis and simulation as a tool for bioprocess design and optimization, Process Biochem. 35
(6) (20 0 0) 539.
[37] L. Levin, F. Forchiassin, A. Viale, Ligninolytic enzyme production and dye decolorization by Trametes trogii: application of the Plackett-Burman exper-
imental design to evaluate nutritional requirements, Process Biochem. 40 (3-4) (2005) 1381.
[38] Cyanide [Technical Document-Chemical/Physical Parameters], Health Canada,1979.
[39] K.J. Horadam, Hadamard Matrices, and Their Applications, Princeton University Press, Princeton, New Jersey, 2007.
[40] R.L. Plackett, J.P. Burman, The design of optimum multifactorial experiments, Biometrika 33 (4) (1946) 305.
[41] K.M. Ghanem, A. El-Ahwany, A. Farag, D. Ghanem, Optimization the degradation of chloroxylenol by free and immobilized klebsiella pneumoniae d2,
Int. J. Curr. Adv. Res. 6 (2017) 7082.
[42] R.H. Myer, D.C. Montgomery, Response Surface Methodology: Process and Product Optimization Using Designed Experiments, Wiley, New York, 2002.
[43] D.J. Sheskin, Handbook of Parametric and Nonparametric Statistical Procedures, Chapman and Hall/CRC, New York, 2003.
[44] SAS Institute Inc, JMP 10 Basic Analysis and Graphing, Second Edi, USA, 2012.
[45] K.H. Esbensen, D. Guyot, F. Westad, L.P. Houmoller, Multivariate data analysis, Practice: An Introduction to Multivariate Data Analysis and Experimental
Design, Aalborg University, Esbjerg, Denmark, 2002.
[46] W.C. Guenther, Analysis of variance, Prentice-Hall, USA, 1964.
[47] L. Eriksson, E. Johansson, N. Kettaneh-Wold, C. Wikström and S. Wold, Design of Experiments: Principles and Applications, MKS Umetrics AB, Sweden,
2008.
[48] J. Goupy, Les plans d’expériences, Ed. Techniques Ingénieur, 2006.
[49] E.C. Cilek, H. Ciftci, S.G. Karagoz, G. Tuzci, Extraction of silver from a refractory silver ore by sono-cyanidation, Ultrasonics-Sonochem. 63 (2020)
p104965.

11
Z. Zmirli, A. Driouich, S. El harfaoui et al. Scientific African 16 (2022) e01137

[50] O. Bayat, H. Vapur, F. Akyol, C. Poole, Technical Note: Effects of oxidizing agents on dissolution of Gumuskoy silver ore in cyanide solution, Miner. Eng.
16 (4) (2003) 395.
[51] M.S. Oncel, M. Ince, M. Bayramoglu, Leaching of silver from solid waste using ultrasound assisted thiourea method, Ultrason. Sonochem 12 (3) (2005)
237.
[52] A. Driouich, F. Chajri, S. El Alami El Hassani, O. Britel, S. Belouafa, A. Khabbazi, H. Chaair, 2020. Optimization synthesis geopolymer based mixture
metakaolin and fly ash activated by alkaline solution, J. Non-Cryst. Solids 544 (2020) 120197.

12