Asian Journal of Chemistry; Vol. 23, No.

1 (2011), 67-70

Recovery of Silver from Waste Radiographic Films by Chemical Leaching

VOLKAN ARSLAN1,*, METIN UCURUM2, HUSEYIN VAPUR3 and OKTAY BAYAT3

1
General Directorate of Mineral Research & Exploration, Adana, Turkey
2
Department of Mining Engineering, Nigde University, Nigde, Turkey
3
Department of Mining Engineering, Cukurova University, Adana, Turkey

*Corresponding author: Tel:/Fax: +90 322 3386119; E-mail: [email protected]

(Received: 21 October 2009; Accepted: 21 August 2010) AJC-8988

The major sources to recover silver are photo-processing solutions, spent rinse water, scrap film and scrap printing paper. As much as
80 % of the total silver processed for black and white positives and almost 100 % of the silver processed in colour work will end up in the
fixer solution. The waste radiographic films used in the experiments were taken from Cukurova University, Balcali Hospital, Adana,
Turkey and cut into small pieces. The film pieces (1-9 g) were boiled with 100 mL of various quantities of oxalic acid, nitric acid and
sodium hydroxide solutions for about 2.5, 5.0, 7.5 and 10 min at boiling temperature (≅ 97 ºC). The aim of the study is to recover silver
from waste radiographic films by HNO3 leaching. To optimize the results of the experimental work, variance analysis was used. The
statistical tests (F-tests) showed that nitric acid gave the best results compared with the other agents. Under optimum leaching conditions
(radiographic films quantity, 50 g/L; nitric acid concentration, 30 g/L; stirring speed, 180 rpm; leaching time, 15 min) 89 % silver
recovery was obtained.

Key Words: Waste radiographic films, Silver recovery, Acid leaching, Variance analysis, F-Test.

INTRODUCTION of the silver consumed annually in the world is used in photo-

graphic and radiographic applications. Small operations such
There was a little study on the recycling of silver from as local doctors' and dentists' offices, veterinary clinics and 1
the radiographic films and its environmental effects in Turkey. h film developers consume the bulk of this silver during the
The recovery of silver process depends on heating the films photographic/radiographic developing process. Once used, the
with oxalic acid, nitric acid and sodium hydroxide solutions majority of this silver ends up as waste, typically as sediment
to boiling temperature to separate the inorganic component in our nation's waterways or as solid waste in landfills.
from the polymer substrate. Silver, a precious metal, is used Although this silver could easily be recovered and recycled,
in photo film because of its photosensitive properties. Film the current regulatory environment makes disposal an easier,
development causes photographic waste of spent fixer and rinse less costly option for this small generator3-6.
water containing 1000-10000 and 50-200 mg Ag/L, respec- The photographic processing industry has four options in
tively, in the form of silver-thiosulphate complexes1. Silver in silver recovery i.e., electrolytic plating, metallic replacement,
the photographic industry is recovered from two main sources ion exchange and chemical precipitation7. Four factors limit
i.e., photographic solutions and scrap films. Basically, two the extent to which photographic processing solutions can be
types of solutions are used in the photographic industries. They recovered, regenerated, or reused. The ability to collect the
are the fixer and bleach solutions. The fixer solutions consist solutions efficiently, dilution by water or other solution carried
of chemical substances which have the ability to dissolve over from the preceding processing step, exhaustion of some
sensitized salts on films on which photographic images could of the chemical components in the solutions contamination of
be developed. Fixer solutions dissolve the opaline silver the solutions by reaction products or carryover2. Globally, large
compounds on the film and cause the picture to remain quantities of silver are not recycled or recovered, as most of
unchanged when exposed to light. Bleach solutions are used the methods are not cost effective, thus creating important
to rinse the negatives on which the photographic images are economic, management and ecological consequences. The
formed. The photographic wastes comprise mainly fixer and ever-growing ecological considerations and stringent laws are
bleach solutions contain high concentrations of dissolved driving the whole world to a system of increased recovery,
silver and other chemicals such as sulphates and nitrates2. Much regeneration and recycling of industrial wastes. Moreover, the
68 Arslan et al. Asian J. Chem.

principle focus of recycling effort has been post-consumer reagents (nitric acid, sodium hydroxide and oxalic acid) were
products. Industries constitute a formidable source of pollution used of commercial grade for leaching. The first step, the best
and radiographic industries produce large amounts of solid reagent was determined with means using to same test condi-
and liquid wastes. The wastes consist primarily of two compo- tions (acid concentration: 20 g/L; radiographic film quantity:
nents-organic and inorganic that makes regeneration and/or 50 g/L; temperature: 97 ºC; mixed time: 10 min at 180 rpm
recycling worthwhile. Organic wastes can be further catego- stirring speed).
rized into small molecules, such as hydroquinone and large Secondly, the concentration of the best reagent was
molecules consisting of polymer substrate. The inorganic determined. In this step, the film pieces (5 g) were boiled with
component consists of metallic and non-metallic parts. The 100 mL of various quantities (5, 10, 20, 30 and 50 g/L) reagents
latter comprises mainly fixer and bleach solution containing solutions for about 10 min at boiling temperature at ca. 97 ºC.
high concentrations of sulphates and nitrates. The metallic part After that, the effect of pulp density was investigated. For this
consists of silver, the recovery of which is of paramount aim, the film pieces (1, 3, 5, 7 and 9 g) were boiled with 100
importance. Table-1 shows methods to recover silver from mL of 30 g/L nitric acid solution for about 10 min at boiling
processed radiographic films15. Reagents were discovered temperature at ca. 97 °C. Finally, the film pieces (3 g) were
dissolution of silver halides in photographic fixing process boiled with 100 mL of 30 g/L nitric acid solution for 5, 10, 15,
using ammonium thiosulfate (ATS) and sodium thiosulfate 20 and 25 min at boiling temperature of about 97 ºC for the
solutions (STS) as fixing baths in 183721. Conventional fixing determination of optimum stirring time. The completion of
of AgX in photographic and medical X-ray films has been the peeling process is indicated by the disappearance of the
extensively used in the photo-industry for more than 2 centuries. black colour of the film and appearance of clear blue of the
The dissolution of silver halides by thiosulfates and thiocyanates polyester or triacetate film. The sludge was separated by
are usually rapid and do not need any catalytic influence. Hence filtration, dried and further subjected to melting to recover pure
they are highly soluble in these lixiviant and are considered to silver. The determination of the silver content of the processed
be thermodynamically stable at slightly alkaline pH22. radiographic films was carried out by atomic adsorption spectro-
photometer (AAS). The resultant Ag2SO4 was measured
TABLE-1 potentiometrically with solution of NaCl.
METHODS TO RECOVER SILVER FROM PROCESSED
RADIOGRAPHIC FILMS RESULTS AND DISCUSSION
Temperature pH Ref.
Method Reagents used Reliability of the data depends upon the reproducibility.
of operation Range No.
Inorganic chemicals Hence replicates (n = 4) were carried out and the means and
FeCl3 (10–26% standard deviations of 4 tests at the same conditions (acid concen-
1 35-40 2 8
w/v) tration: 20 g/L; radiographic film quantity: 50 g/L; temperature:
2 FeCl3 Not reported n.r. 9 97 ºC; stirring time: 10 min) are presented in Table-2. The
3 NaOH (1% w/v) 5-50 Alkaline 10 results showed that the silver recovery, 72.30 % Ag recovery,
Boiling could be achieved using nitric acid. Ajiwe and Anyadiegwu23
4 NaOH (in ethanol) Alkaline 11
solution
studied that recovered silver from X-ray films by dissolving
Room
5 H2O2/NaCN – 12 the silver compounds with concentrated nitric acid. They stated
temperature
EDTA-Fe , 3+ that silver recovery by internal electrolysis gave better recovery.
6 – – 13
(NH4)2S2O8 Similar results were in conformity with the reports of Loto24.
Organic chemicals
1 RCONH2+HNO3 60-100 Acidic 14 TABLE-2
2 Oxalic acid 97 Acidic 15 RESULTS OF SELECTED REAGENTS
Biological chemicals USED FOR SILVER RECOVERY
Oxalic acid Sodium
Bacillus Zimet- Test No Nitric acid (%)
1 70 Min.salts 16 (%) hydroxide (%)
11262 1 1.49 71.68 7.00
Streptomyces 2 1.65 71.81 6.72
2 15-70 (wash) 6-9 17
grisens 3 1.72 72.99 6.86
Gelatin 4 1.53 72.70 7.00
3 decomposing n.r. n.r. 18 Mean 1.60 72.30 6.90
microorganisms SD*
0.11 0.65 0.14
Mechanical chemicals *SD: Standard deviation
1 High shear 60-93 – 19
Mechanical + chemicals The analysis-of-variance statistical technique was adopted
High shear + to facilitate interpretation of the experimental results. Total
1 60-93 alkaline 20
NaOH sums of squares for reagents (12405.345) test, reported in
Table-3 was partitioned into a sum of squares due to the effect
of the different reagents used, (among reagents) and a sum of
EXPERIMENTAL
squares due to the experimental error involved in the test
The processed radiographic films (with an average content (within reagents). The different effect of the reagents on the
of 6.85 g of silver/kg) were procured from Cukurova University selectivity was represented by the different silver recovery
Hospital, Turkey and cut into small pieces. Three different averages15-27.
Vol. 23, No. 1 (2011) Recovery of Silver from Waste Radiographic Films by Chemical Leaching 69

TABLE-3 100
ANALYSIS OF VARIANCE FOR REAGENTS 90
Source of Sum of Degrees of Mean 80
F
variation squares freedom square
Among reagents 12404.000 2 6202* 70

% (%)
Within reagents 1.345 9 0.149** 41500 60

Recovery
Total 12405.345 11
50
*MS1, **MS2.
40
The variance MS1 is associated to these averages, while 30
the variance MS2 represents the experimental error involved 20
in the experiments and was calculated by pooling the variances 10
Ag recovery
coming from each test of 6 replicates of each reagent tested.
0
These two variances are obtained by dividing the sum of the
0 1 2 3 4 5 6 7 8 9 10
squares by the associated degrees of freedom. The null Pulp
Pulpdensity (%%w/v)
Density, w/v
hypothesis H0 -to be proved or otherwise-is that all the silver Fig. 1. Effect of pulp density on the silver recovery
recover ratio averages µ belong to the same statistical popu-
lation, that is H0: µ1 = µ2 = µ3 for reagents. The alternative Effect of acid concentration: The effect of various nitric
hypothesis is that they do not belong, so the reagents behave acid concentrations on the silver recovery was investigated.
in a different manner regarding selectivity. In this case it is In Fig. 2, it is seen that the silver recovery initially increased
said that a statistical difference exists among the reagents. If with increasing acid concentration reached to the optimum
MS1 differs significantly from MS2, i.e., the ratio MS1/MS2 value around 30 g/L. The improved silver recovery was observed
is significantly different from 1, the null hypothesis H0 is when the pH was lowered from pH 7.5 to 3.0 at 30 g/L nitric
rejected and the effect of the reagents, as a whole, differs one acid in the solution. This indicated that improved silver reco-
from another. The ratio between the two variances MS1 and veries could be achieved under acidic conditions. Very small
MS2 constitutes a ratio between the explained variance due to changes in the content of silver recovery were observed when
the reagents and the unexplained variance generated by the
nitric acid was added extra 20 g/L. Therefore, 50 g/L gave
experimental error and follows an F-statistic28.
approximately the same value as 83.94 % silver recovery.
The critical threshold value of F with the appropriate
degrees of freedom, associated with the numerator and the 100
denominator, at a given level of confidence, is found in an 90
F-table. If the computed value of the F statistic is smaller than
80
that obtained from the F-table, there is no evidence that the
two variances are different. Hence the difference of the silver 70
% (%)

recovery ratio averages obtained by the different reagents is 60

only due to experimental error and the null hypothesis cannot
Recovery

50
be rejected. If the computed value of F is greater, it means that
the null hypothesis has to be rejected and a statistical difference 40
exists in the performance of the reagents. Statistical significance 30
is decided by the level of probability associated with F. If it is 20
desired to be on safer ground regarding acceptance of the
10 Ag recovery
hypothesis that the reagents act differently, it is necessary to
choose a higher level confidence and as a consequence the 0
calculated F should be higher to pass the test. In the work 0 10 20 30 40 50 60
reported here the level of confidence was established at 95 %, Nitric
Nitricacid
Acidconcentration (g/L)
Concentration, g/L
Fig. 2. Effect of nitric acid concentration on the silver recovery
that is the level of confidence commonly used as a threshold
for statistical decision-making. Its adoption means that the
Effect of leaching time: In order to determine the effect
experimenter does not want to be wrong more than once in 20
of the leaching time on the silver recovery, a series of experi-
times, hence the risk of falsely rejecting the null hypothesis is
5 % at most. The high value of F (41500) reported in Table-3 ments were conducted at 3 % w/v pulp density and 30 g/L
shows that the null hypothesis cannot be accepted, hence it nitric acid concentration. As it was seen in Fig. 3, the silver
can be stated that the reagents on the whole have a different recovery increased with increasing leaching time. There was
effect on the recovery of silver and experimental results indicated no effect on silver recovery over the 15 min leaching time.
that nitric acid was the best reagent studied for silver recovery. Therefore, the optimum leaching time was determined 15 min.
Effect of pulp density: The leaching efficiency for silver Conclusion
recovery from the radiographic films was pulp density depen- (a) The recovery of silver from processed radiographic
dent. Under higher pulp density conditions (3 % w/v), the re- films can be easily carried out by treatment with nitric acid
covery reaches its maximum value as seen in Fig. 1. After solution. It is a low cost reagent, the process is simple and the
that, it is approximately stable case. Therefore, in further tests, consumption is low. Nitric acid is commonly used for silver
3 % w/v was used the best pulp density values. recovery.
70 Arslan et al. Asian J. Chem.
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