B18

PROCEEDINGS
OF THE
XIIth INTERNATIONAL MINERAL
PROCESSING SYMPOSIUM
6-8 OCTOBER 2010, CAPPADOCIA-NEV2EH1R, TURKEY

Edited by
zcan Y. GLSOY, 2. Levent ERGN, N.Metin CAN and 1lkay B.EL1K
Hacettepe University, Department of Mining Engineering

Extraction of Silver from Waste X-ray Films by Thiosulphate Leaching

G0"[0"[c|e."C0"F0"Dc3"cpf"J0"Fgxgek"
Dept. of Mining Engineering, Karadeniz Technical University, 61080, Trabzon, Turkey

ABSTRACT:

In this study, the recovery of silver from waste X-ray films (0.7% Ag) by
ammoniacal copper thiosulphate leaching was studied. The experiments were designed using
Taguchi L9 (33) experimental design. The effects of concentration of thiosulphate, (0.005-0.5
M S2O32-), copper (0.005-0.5 M Cu2+), and ammonia (0.005-1 M NH3) on the extent of silver
recovery from X-ray films were investigated at three levels. The experimental data were
analysed using a statistical software. The findings revealed that the concentration of ammonia
(NH3) and thiosulphate (S2O32-) were statistically the most significant factors affecting the
recovery of silver, while the effect of concentration of copper (Cu2+) was found to be
insignificant over a reaction period of 0.5 h.

INTRODUCTION
Silver is often found with gold and sulphide minerals in the nature and can be extracted,
largely as a by-product, from gold and base metal sulphide ores. Due to the rapid depletion of
natural silver resources and high silver demand, the secondary silver resources have recently
become ever important (Zhouxiang et al., 2008). Silver demand has increased about 5% in
recent years and 25% of silver demand is obtained by recycling of silver wastes including
rjqvqitcrjke" ycuvgu" *Pcmkdq0nw." 3;;:+0 Owing to its high photosensitivity and electrical
conductivity, silver is extensively used in photography and electrical industry. Approximately
40-50% of the silver production is consumed for radiography and photographic films and
papers (Bayram, 1997). Most of the X-ray (radiography) films (>94-98%) are used in medical
applications (Khunprasert, 2008).
X-ray and photographic films may contain appreciable amounts of silver in the form of
silver halide e.g. AgBr. X-ray films typically contain about 4.85 g/m2 Ag (Kodak, 1998).
During the photoprocessing silver halide is reduced to metallic silver on exposure to light (1)
and the remaining silver halide is dissolved by thiosulphate into the waste solution (2) during
the developing and fixing processes (Kodak, 1999).

AgX light

Ag 0

(1)

AgX - 2S2O32/ Ag(S2 O) 32/ - X

(2)

It was claimed that during photo-processing ~60% of the silver remains on the film while
~40% transfers to the solution (Khunprasert, 2008). Waste X-ray films may contain 0.7-2%
uknxgt"d{"ygkijv"kp"vjg"gownukqp"qp"vjg"rqn{guvgt"hkno"dcug"*[c|e"gv"cn0."422;="Pcmkdq0nw"gv"
al., 2003). Despite the importance of photographic wastes as a secondary silver resource
(Bayram, 1997), only a small portion of silver is recycled/recovered from these wastes (Syed et
al., 2002). Recovery of silver from waste films/solutions is of importance not only for
economic considerations, but also for environmental pollution. Silver is one of the most toxic
ogvcnu" tgiwncvgf" d{" tgiwncvqt{" dqfkgu" *Dc3." 422;+0" Rtqxkfgf" vjcv" rjqvqitcrjke" ycuvgu"
including X-ray films and processing solutions are unsafely disposed of, they may cause soil

741

and water pollution. Silver from waste films can be recovered by hydrometallurgical (leaching)
and pyrometallurgical (incineration) processes (Kunda, 1992). Incineration has several
disadvantages including the generation of toxic gases and relatively low recovery of silver
(<95%) (Khunprasert, 2008; Shankar et al., 2010). Almost complete recovery of silver (>99%)
can be achieved by leaching (Garcia, 1986; Marinkovic, 2006, Khunprasert, 2008). Various
tgcigpvu"kpenwfkpi"e{cpkfg"*Ictekc."3;:8="Infcp."4227+."uqfkwo"j{ftqzkfg"*Pcmkdq0nw"gv"cn0."
2003), nitric acid (Abdel-Aal and Farghaly, 2007; Khunprasert, 2008) and oxalic acid
(Marinkovic, 2006) were investigated for the extraction of silver.
Thiosulphate (S2O32-) is an alternative leaching reagent for the recovery of silver/gold
due to its relatively non-toxic nature (Ayata and Yildiran, 2006; Grge, 2006; Muir and
Aylmore, 2004). Thiosulphate leaching of silver/gold is conducted in ammoniacal solutions in
the presence of cupric copper (Cu2+) as catalyst (3) (Yen et al., 2001). Thiosulphate can form
strong silver-thiosulphate complexes (e.g. Ag(S2O3)23-, logK=13.5) in wide Eh-pH intervals
(Muir and Aylmore, 2004). Ammonia (NH3) stabilises copper(II) by forming copper(II)
tetraamine complex (Cu(NH3)42+, logK=12.5) and hence controls the decomposition of
thiosulphate through the reduction of Cu(II) to Cu(I) (Muir and Aylmore, 2004). Ammoniacal
copper-thiosulphate reagent system can be used suitably in the leaching of metallic silver from
the waste films. Although many researches investigated various reagents for leaching of silver
from waste films, to the knowledge of the authors ammoniacal copper-thiosulphate leaching of
photographic wastes has not been reported. Recently, Zhouxiang et al. (2008) used silver-free
waste fixing bath solution (which contains thiosulphate) in the leaching of silver from X-ray
films. The overall reaction for the dissolution of silver in ammoniacal copper-thiosulphate
system has been proposed as follows:

Ag 0 - 5S2 O 32/

( aq ) -

Cu ( NH 3 ) 24- ( aq )

Ag(S2 O 3 ) 32/ ( aq ) - 4 NH 3 ( aq ) - Cu (S 2 O 3 ) 53/ ( aq )

(3)

In this study, the recovery of silver from waste X-ray films by thiosulphate (S2O32-)
leaching in the presence of copper (Cu2+) and ammonia (NH3) was studied. Taguchi L9 (33)
experimental design was adopted for the study. The effects of concentrations of thiosulphate,
copper and ammonia on the extraction of silver from X-ray films were investigated at three
levels. A statistical software was used to evaluate the experimental data for the contribution
and significance of these factors.

EXPERIMENTAL
Material and Method

Reagent grade sodium thiosulphate (Na2S2O3.5H2O) and copper sulphate (CuSO4.5H2O)

were used in the study. Ammonia solution (NH3, 25%) was used as the stock solution. All
solutions were prepared using deionised-distilled water.
Waste X-ray films were cut into 0.5x0.5 cm2 pieces and prepared as 5 g portions prior to
use in the experiments. Silver content of waste films was determined to be 0.7% Ag by weight.
Leaching tests were performed in 250-ml Erlenmeyer flasks. Leach solutions (100 ml) were
prepared at the required strengths of thiosulphate (0.005-0.5 M S2O32), copper (0.005-0.5 M
Cu2+), and ammonia (0.005-1 M NH3) before the addition of the waste films (5 g). The flasks
were then placed in a temperature controlled (25C) orbital shaker operating at 180 rpm. Over
the experimental period, the top of the flasks were kept covered. Samples were taken at certain
intervals and residual silver was analysed. After the leaching period, film residues were filtered
and dried. They were then digested in hot concentrated nitric acid (65% HNO3) to determine
their silver content. Silver analysis was performed by an atomic absorption spectrophotometer
(Perkin Elmer AAnalyst 400). Replicate tests showed that relative standard deviation (RSD) of
vjg"gzrgtkogpvcn"fcvc"ycu"7'0"

742

Experimental Design

Taguchi design was adopted as a methodology for experimental design in this study (Roy,
2001). The effects of initial concentration of thiosulphate (0.005-0.5 M S2O32-), copper (0.0050.05 M Cu2+) and ammonia (0.005-1 M NH3) on the extent of removal of silver from synthetic
solutions were investigated within Taguchi L9 (33) orthogonal array (Tables 1 and 2). Minitab
(2004) statistical software was used to perform ANOVA and evaluate the main effects of
parameters.

Table 1. Factors and their levels adopted for the experimental design
Parameters

(A) [S2O32-], M
(B) [Cu2+], M
(C) [NH3], M

Level 1

Level 2

Level 3

0.005
0.005
0.005

0.25
0.025
0.5

0.5
0.05
1

Table 2. Taguchi L9 (33) array implemented for the study

Exp. no

(A)
[S2O32-], M

1
2
3
4
5
6
7
8
9

1
1
1
2
2
2
3
3
3

Parameters
(B)
[Cu2+], M

(C)
[NH3], M

1
2
3
1
2
3
1
2
3

1
2
3
2
3
1
3
1
2

RESULTS AND DISCUSSION

Recovery of silver (%) for each run for different leaching periods (0.5-48 h) was presented
in Table 3. The extensive extraction of Ag occurred in all the runs except the first run.
However, in the 7th run, the silver extraction was most rapid i.e. ~93% at 0.5 h (Table 3). Mean
values for the recovery of Ag (%) for parameters at each level were shown in Table 4. Delta
values, which show the relative significance of the factors, were also calculated as the
difference between maximum and minimum mean values (Table 4). Concentration of NH3
appeared to be the most significant factor affecting the leaching process (Table 4).

743

Table 3. Recovery of Ag (%) during the leaching period 0.5-48 h

Exp.
(A)
no [S2O32-], M

1
2
3
4
5
6
7
8
9

0.005
0.005
0.005
0.25
0.25
0.25
0.5
0.5
0.5

(B)
[Cu2+], M

(C)
[NH3], M

0.5 h

Recovery of Ag (%)
1h 2h 3h

48 h

0.005
0.025
0.05
0.005
0.025
0.05
0.005
0.025
0.05

0.005
0.5
1
0.5
1
0.005
1
0.005
0.5

4.3
35.1
69.5
89.1
89.2
27.0
93.1
30.2
70.5

2.2
43.2
80.5
89.4
94.6
33.5
95.3
41.3
73.6

1.6
99.9
99.9
99.8
100
99.7
99.9
99.3
99.6

3.3
53.7
85.8
97.6
102
45.6
96.3
49.6
79.3

0.8
63.5
89.5
96.7
96.8
59.7
93.0
53.3
91.0

Table 4. Mean values of recovery of Ag at 0.5 h for parameters at each level

and delta statistics for parameters
Parameters
(A) [S2O32-], M
(B) [Cu2+], M
(C) [NH3], M

Recovery of Ag (%)
Level 1 Level 2 Level 3

Delta
(Max.-Min.)

Rank

36.30
62.17

68.43
51.50

64.60
55.67

32.13
10.67

2
3

20.50

64.90

83.93

63.43

Statistical evaluation of the experimental data was performed by analysis of variance

(ANOVA) for the data at 0.5 h. (Table 5). The significance level of parameters was determined
based on P values. The P value indicates the probability that the test statistic will take on a
value that is at least as extreme as the observed value of the statistic when the null hypothesis
(H0+"jqnfu"vtwg"*Oqpviqogt{."4223+0"Kh"R"xcnwg"ku"nqygt"vjcp"vjg"xcnwg"qh"cnrjc"*g+"fgvgtokpgf"
for the significance test, then the effect of parameter on the process is significant. In this
regard, the calculated P values (Table 5) revealed that effect of concentration of NH3 in the
tcpig"vguvgf"ycu"uvcvkuvkecnn{"ukipkhkecpv"cv";7'"*g?2027+"yjkng"U2O32-"ycu"qpn{"cv";2'"*g?203+"
confidence level. The contributions of NH3 and S2O32- to the response i.e. silver extraction
were found to be 74.1% and 21.5%, respectively (Table 5). However, the contribution of
copper in this range of concentration was minimal as ANOVA data suggested. Contributions
values also reflect the relative importance of each factor (Table 5).

Table 5. Results of ANOVA for the parameters for Ag recoveries at 0.5 h

Source of
deviation

(A) [S2O32-], M
(B) [Cu2+], M
(C) [NH3], M
Residual Error
Total

Degree of
freedom

Sum of
squares

Mean
squares

2
2
2
2
8

1848.1
173.4
6357.4
202.4
8581.3

924.07
86.69
3178.71
101.19

F value

P value

9.13
0.86
31.41

0.099
0.539
0.031

Contribution
(%)
21.5
2.0
74.1
2.4
100

Figure 1 presents the effect of parameters on silver recovery (%) based on the mean values
from Table 4. The increase in the concentration of NH3 leads to an increase in silver recovery
(Fig. 1). This could be ascribed to the stabilising role of NH3 on Cu(II) resulting in the

744

80
60
S2O3

40
20
0
Level 1

Mean values for the recovery of Ag (%)

Mean values for the recovery of Ag (%)

Mean values for the recovery of Ag (%)

prevention of decompositon of S2O32- and its lixiviant effect on silver (Muir and Aylmore,
2004). Increasing the concentration of S2O32- from 0.25 M to 0.5 M i.e. 2nd to 3rd level, was
found to have limited effect on the recovery of Ag. In other words, the concentration of
thiosulphate at 0.25 M was sufficient for high levels of the extraction of silver.

Level 2

80
60
Cu+2

40
20
0

Level 3

Level 1

Level 2

Level 3

90
70
NH3

50
30
10
Level 1

Level 2

Level 3

Figure 1. The effects of parameters on the recovery of Ag (%) at 0.5 h

S2O3 level

Recovery
of Ag
(%)
< 30
30 - 60
60 - 80
80 - 90
90 - 95
> 95

1
1

NH3 level
2

(a)
(b)
Figure 2. Surface (a) 2-and contour (b) plots of recovery of silver (%) versus levels of
concentration of S2O3 and NH3.
745

Simultaneous effect of statistically significant parameters i.e. NH3, S2O32- parameters on

the response (Ag recovery, %) can be seen from the surface and contour plots (Fig. 2).
Accordingly, to achieve high Ag recoveries (>90-95%), levels of NH3 and S2O32- should be
selected at concentrations greater than 2nd level i.e. >0.5 M NH3 and 0.25 M S2O32- (Fig. 2).
The concurrent decrease in the concentrations of S2O32- and NH3 results in low recoveries of
Ag (Fig. 2).
Leaching kinetics is also of importance on the recovery of Ag (Fig. 3). ANOVA was
applied for different leaching periods (0.5-48 h) and P values were presented in Table 6. It can
dg"uggp"vjcv"tgcevkqp"vkog"jcu"c"ukipkhkecpv"korcev"kp"vjcv."cu"vjg"ngcejkpi"rtqitguugf"k0g0"cv"3"
h, the effect of concentration of thiosulphate on the process became statistically insignificant
even at 90% confidence level (Table 6). The effect of the concentration of ammonia was also
found to be statistically significant only at 0.5-3 h.

Recovery of Ag (%)

100
80

6th run
8th run

60
40
20
0
0

10

20

30

Time in hours

40

50

Figure 3. Effect of time on the recovery of Ag (%)

Table 6. P values of parameters for leaching periods at 0.5-48 h
Parameters
2-

(A) [S2O3 ], M
2+

(B) [Cu ], M
(C) [NH3], M

0.5 h

1h

2h

3h

48 h

*>g?203+
0.539

0.171

0.179

0.185

0.502

0.960

0.933

0.512

0.501

*>g?2027+

*>g?203+

*>g?203+

*>g?203+

0.495

0.099

0.031

0.052

0.066

0.076

Multiple linear regression method was used to establish a mathematical model (4) for Ag
extraction at 0.5 h (Table 1). The model was found to be statistically valid at 99.9% confidence
ngxgn" *R?20222>g?20223+" ykvj" c" tgitguukqp" eqghhkekgpv" *T2) of 95.8%. A verification
experiment was performed to test the validity of the model at concentrations of S2O32-, Cu2+
and NH3 of 0.25 M, 0.05 M and 1 M, respectively (Fig. 4).

Recovery of Ag (%) = 70.6 [S2O32-] + 42.5 [Cu2+] + 70.4 [NH3]

746

(4)

Recovery of Ag, % (Model)

100
80
60
40
20

Verification run

0
0

20

40

60

80

Recovery of Ag, % (Experimental)

100

Figure 4. A plot of experimental vs calculated values from the regression model for the
extraction of silver

CONCLUSIONS
This study has shown that ammoniacal copper thiosulphate system can be readily used for
the leaching of silver from waste X-ray films with almost complete recovery of silver. The
effects of concentration of thiosulphate, ammonia and copper on the extent of recovery of
silver from waste X-ray films were demonstrated using Taguchi L9 (33) experimental design.
The concentrations of NH3 and S2O32- are the most significant parameters as confirmed by
statistical evaluation of the experimental data. Concentration of Cu2+ was shown to be
insignificant in the range tested.

ACKNOWLEDGEMENT
The authors would like to express their sincere thanks and appreciation to the Research
Foundation of Karadeniz Technical University for the financial support (Project No:
2006.112.008.1).

REFERENCES
Ayata, S., and Yildiran, H., 2006. Silver extraction from argentite by thiosulphate leaching, JFS,
Vol 29, pp. 16-31.
Dc3." C0F0." 422;0" Tgeqxgt{" qh" uknxgt" htqo" ycuvg" Z/tc{" hkno" uqnwvkqpu" d{" rtgekrkvcvkqp." D0Ue0"
Thesis, Karadeniz Technical University, Trabzon, Turkey, (in Turkish).
Dc{tco."G0."3;;90"Mvcj{c"3220[n"Io3"Ocfgpk"13ngvoguk"xg"Egxjgt"Jc|tncoc"Vgukuk"xg"Cvm"
Dctcl."D0Ue0"Vjguku."Mctcfgpk|"Vgejpkecn"Wpkxgtukv{."Vtcd|qp."Vwtmg{"*kp"Vwtmkuj+0"
Abdel-Aal, E.A., and Farghaly, F.E., 2007. Preparation of silver powders in micron size from
used photographic films via leachingcementation technique, Powder Technology, Vol. 178,
No. 1, pp. 51-55.
Garcia, R.M., 1986. The recovery of silver from photographic film: a study of the leaching
reaction with cyanide solution for industrial use, Hydrometallurgy, February, Vol. 16, No. 1,
pp. 395-500.
Grge, D., 2006. Extraction of gold from Kaletas gold ore by thiosulphate leaching, B.Sc.
Thesis, Karadeniz Technical University, Trabzon, Turkey (in Turkish).
Gldan, G., 2005. Recovery of silver from waste X-ray films and solutions, B.Sc. Thesis,
Karadeniz Technical University, Trabzon, Turkey (in Turkish).

747

Khunprasert, P., Grisdanurak, N., Thaveesri, J., Danutra, V., Puttitavorn, W., 2008. Radiographic
film waste management in Thailand and cleaner technology for silver leaching, Journal of
Cleaner Production, January, Vol 16, No 1, pp. 28-36.
Kodak, 1998. Sources of silver in photographic processing facilities, Eastman Kodak Company ,
Publication No: J-210, 8 pp.
Kodak, 1999. Recovering silver from photographic processing solutions, Eastman Kodak
Company, Publication No: J-215, 11 pp.
Kunda, W., 1995. Photographic fixer regeneration, United States Patent.
Montgomery, D.C., 2001. Design and Analysis of Experiments, John Wiley&Sons Inc., New
York 684 pp.
Marinkovic, J., Korac, M., Kamberovic, Z., Matic, L., 2006. Recycling of silver from exposed Xray films, Acta Metallurgica Slovaca, Vol. 12, pp. 262-268.
Minitab, 2004. Minitab Inc., Statistical Software, Release 14.12.0
Muir, D.M., and Aylmore, M.G., 2004. Thiosulphate as an alternative to cyanide for gold
processing issues and impedients, Mineral Processing and Extractive Metallurgy, April, Vol.
113, No. 1, pp. 2-12.
Pcmkdq0nw."P0."3;;:0"Tgeqxgt{"qh"uknxgt"htqo"vjg"wugf"rjqvqitcrjke"hkno"cpf"rtgrctcvkqp"qh"pgy"
rjqvqitcrjke"hkno0"Rj0F0"Vjguku."Wpkxgtukv{"qh"Gig."1|okt0""
Pcmkdq0nw." P0." Vquecn." F0." cpf" Pk3nk." I0." 42250" C" pqxgn" uknxgt" tgeqxgt{" ogvjqf" htqo" ycuvg"
photographic films with NaOH stripping, Turk J. Chem., Vol. 27, pp. 127-133.
Roy, R.K., 2001. Design of Experiments Using The Taguchi Approach: 16 Steps to Product and
Process Improvement, Wiley-Interscience, New York, 560 pp.
Shankar, S., More, S.V., Laxman R.S., 2010. Recovery of silver from waste X-ray film by
alkaline protease from conidiobolus coronatus, Kathmandu University Journal of ScienceEngineering and Technology, March, Vol. 6, No. 1, pp. 60-69.
Syed, S., Suresha, S., Sharma, L.M., Syed, A.A., 2002. Clean technology for the recovery of
silver from processed radiographic films, Hydrometallurgy, January, Vol. 63, No. 1, pp. 277280.
[c|e."G0[0."Fgxgek."J0."cpf"Dc3."C0F0."422;0"Wprwdnkujgf"fcvc0"
Yen, W.T., Deschenes, G., Aylmore, M., 2001. Thiosulphate leaching as an alternative to
cyanidation: A Review of the Latest Developments, 33rd Annual Operators Conference of
the Canadian Mineral Processors, January, 2001, Ottawa, Ontario.
Zhouxiang, H., Jianying, W., Ma, Z., Jifan, 2008. A method to recover silver from waste x-ray
films with spent fixing bath, Hydrometallurgy, February, Vol. 92, No.1, pp. 14-151.

748