Applied Energy 100 (2012) 187192

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Silver recovery and chemical oxygen demand (COD) removal from waste xer solutions
Wei-Ting Chen a, Chin-Chi Ma b, Ming-Hsun Lee a, Yung-Chuan Chu a, Lung-Chang Tsai b, Chi-Min Shu b,
a b

Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology (YunTech), Douliou, Yunlin 64002, Taiwan Department of Safety, Health, and Environmental Engineering, YunTech, Douliou, Yunlin 64002, Taiwan

h i g h l i g h t s
" This study focused on the Ag recovery from waste xer solutions by electrolysis. " 99.55% of silver recovery was obtained with electric current of 3 A during 2.5 h. " The purity of silver was 98.62% with electric current of 3 A. " Higher removal efciency of COD by employing distillation was obtained.

a r t i c l e

i n f o

a b s t r a c t
This study focused on the silver recovery from waste xer solutions by electrolysis under different experimental conditions. During an 8 h electrolysis procedure, the silver recovery efciencies were 10.57%, 11.75%, 45.5%, 62.68%, and 83.88% for electric currents of 0.1 A, 0.3 A, 0.5 A, 0.7 A, and 0.9 A, respectively. Thus, the most efcient recovery factor of silver was found for a current of 0.9 A. Additionally, the pH values of the waste xer solutions were adjusted prior to treatment by electrolysis, and the silver recovery was 100% for a solution with pH 8 that underwent electrolysis for 8 h at an electric current of 0.9 A. The recovery efciency of silver was 88.64% for an electric current of 3 A and a duration of 3.5 h, but the recovery efciency of silver decreased to 83.72% for an electrolytic time of 6 h. Furthermore, the recovery efciency of silver increased to 99.55% with a decreased electrolysis time of 2.5 h when the solution was adjusted to pH 8 at an electric current of 3 A. These results suggest that the most suitable experimental conditions were an electric current of 3 A, pH 8, and 2.5 h of electrolysis. The treated waste xer solutions still had high concentrations of chemical oxygen demand (COD) after electrolysis. The addition of 30 mL of sulfuric acid to 1000 mL of waste xer solution resulted in a COD removal efciency of 42%. Furthermore, when the waste xer solutions were treated by distillation to remove COD, the removal efciency of COD was 99.3%. Although a higher COD removal efciency was obtained by employing distillation, the cost of the distillation treatment was more expensive. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 17 February 2012 Received in revised form 24 April 2012 Accepted 8 June 2012 Available online 12 July 2012 Keywords: Silver recovery Waste xer solutions Electrolysis Chemical oxygen demand (COD) Distillation

1. Introduction The demand for energy is increasing because of rapid industrialization and societal growth. Conventional primary energy sources, such as coal, oil, and natural gas, have limited reserves that are not expected to last for an extended period of time. Additionally, the environmental problems associated with these conventional energy sources continue to affect the global ecosystem. To reduce fossil fuel consumption and alleviate environmental problems, renewable energy resources are expected to play a key role in future energy consumption [1]. There are many previous
Corresponding author. Tel.: +886 5 534 2601; fax: +886 5 531 2069.
E-mail address: shucm@yuntech.edu.tw (C.-M. Shu). 0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.apenergy.2012.06.026

studies of energy recovery from waste sources and materials, such as waste heat [2,3], waste tyres [4], and waste solutions. For each of these processes, waste energy can be recovered and reused, and this study evaluates a recovery process to recycle silver from waste xer solutions. Because of their high photosensitivity, beginning in 1837, silver halides were employed in the photographic xing process using ammonium thiosulfate (ATS) and sodium thiosulfate solutions (STSs) as xing baths [5]. Because of the extensive usage of silver halides, photographic manufacturing processes resulted in enormous amounts of waste xer solutions. According to the disposal estimation of waste xer solutions from the Environmental Protection Administration, Executive Yuan (Taiwan), approximately 36,310 tons of waste xer solutions are generated per year from

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photographic manufacturing [6]. These waste xers contain high levels of silver (Ag), where concentrations are typically in the range of 500010,000 mg/L. Furthermore, the waste xer solutions contain substantial quantities of components that can be both toxic and valuable depending on the quality of the raw materials [7]. Thus, for both economic and environmental reasons, it is important to recover valuable components (such as Ag) from waste xer solutions. Conventional xing of silver compounds (AgX) in photographic and medical X-ray lms has been extensively used by the photo-industry for more than two centuries. The xing of silver halides by thiosulfates and thiocyanates is usually rapid and does not need any catalytic inuence. Silver halides are highly soluble in these lixiviants and are considered to be thermodynamically stable at a slightly alkaline pH. The simplied mechanisms for the dissolution of AgCl in thiosulfate solutions are shown in Eqs. (1) and (2) [8].
AgCls 2NH4 2 S2 O3aq ( ) NH4 3 AgS2 O2 aq NH4 Claq 1

and ammonium compounds. These materials account for the high COD concentration of 88,654 mg/L in the solution, excluding the concentration of Ag. EDTA and acetate were the primary cause of the acidic pH of the waste xer solutions, which had a pH of 6.09.

2.2. Analysis of component elements The component elements in the waste xer solutions were analyzed by ICP-AES or AA, which were used to determine the metal ion concentration in the aqueous phase and to analyze the ores. Equal volumes (10 mL) of the aqueous and organic phases were shaken at room temperature (25 3 C) for 5 min to ensure complete equilibration. The two phases were separated, and a suitable aliquot of the aqueous phase was assayed for the metal ion concentration. Three tests indicated that the value of 95% extraction for the metal ion was associated with a variation coefcient of 3% [14].

AgCls 2Na2 S2 O3aq ( ) Na3 AgS2 O2 aq NaClaq

2
2.3. Electrolysis procedures Electrolysis was used to recover silver from the waste xer solutions, where the cathode plate and the anode plate were made of stainless steel and graphite, respectively. To determine the most suitable electrolysis efciency, the electrolysis process was evaluated over a range of settings for a variety of parameters, such as pH, electric current, and electrolysis time.
pH3 SIC

ATS and STS are commonly used as preservatives, hardeners, and buffers in xing baths, which perform various functions in the photographic xing process [8]. This process leads to waste xer solutions that have high levels of silver, which can be recovered using many conventional methods, including electrolysis [9], oxygenation reduction [10,11], and sulde precipitation [12]. The treated waste xer solutions contain high concentrations of chemical oxygen demand (COD) after electrolysis, so it is necessary to remove the high COD concentrations before disposing of the solutions. This study evaluates the recovery of Ag from waste xer solutions, as well as the removal efciency of COD from the treated waste xer solutions. 2. Experimental 2.1. Materials The waste xer solutions, which were obtained from a photographic shop (Kodak) in Douliou, Yunlin, Taiwan, did not receive any pre-treatment, such as electrolysis [9], oxygenation, reduction [10,11], sulde precipitation [12], or ion exchange [13], and they were not mixed with any other chemicals. The concentration of Ag in the waste xer solutions was measured by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) (Optima, 5100 DV) or Atomic Absorption Spectroscopy (AA) (Perkin Elmer, 5100), and the concentrations of Ag were found to be in the range of 27003300 mg/L. Additionally, the waste xer solutions contained a variety of organic and inorganic materials, including as chelating-agents such as EDTA, acetate, thiosulfate, metabisulte,

3,500 3,000

100 90 80

pH4 SIC pH5 SIC pH6 SIC

Silver ion concentration (mg/L)

Recovery efficiency (%)

100 90 70 60 50 40 30 20 10

2,500 2,000 1,500 1,000 500 0

70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 0

pH7 SIC pH8 SIC pH9 SIC pH10 SIC pH3 SRE pH4 SRE pH5 SRE pH6 SRE pH7 SRE pH8 SRE pH9 SRE pH10 SRE

Electrolysis time (h)

Fig. 2. Silver recoveries with an electric current of 0.9 A at various pH values.

3,500

Silver ion concentration (mg/L)

3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 1 2 3 4 5 6 7 8

100 90 80 70 60 50 40 30 20 10 0

Silver ion concentration (mg/L)

Recovery efficiency (%)

0.3 A SIC 0.5 A SIC 0.7 A SIC 0.9 A SIC 0.1 A SRE 0.3 A SRE 0.5 A SRE 0.7 A SRE 0.9 A SRE

2,500 2,000 1,500 1,000 500 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6

Recovery efficiency (%)

0.1 A SIC

3,000

80

SIC SRE

Electrolysis time (h)

Fig. 1. The silver recovery from waste xer solutions by electrolysis with low electric currents.

Electrolysis time (h)

Fig. 3. The silver recovery with an electric current of 3 A.

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189

Silver ion concentration (mg/L)

3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 0.5 1 1.5 2 2.5 3

100 90 80 70 60 50 40 30 20 10 0 3.5

Recovery efficiency (%)

SIC
SRE

Electrolysis time (h)

Fig. 4. The silver recovery with an electric current of 3 A at pH 8.

10,000

100 90
Fig. 6. The appearance of the silver metal.

Silver ion concentration (mg/L)

9,000 8,000 7,000 6,000 5,000 4,000 3,000 2,000 1,000 0

70 60 50 40 30 20 10
0 10 20 30 40 50 60 80 100 120 150 180 210 240

Recovery efficiency (%)

80

SIC SRE

100,000 90,000 80,000 70,000 60,000 50,000 40,000 30,000 20,000 10,000 0

COD concentration (mg/L)

H2SO4
HNO 3

HCl

Electrolysis time (min)

Fig. 5. The purication of silver by electrolysis with an electric current of 0.9 A.

Mass volume (%)

Fig. 7. The COD removal efciency of waste xer solutions with 15% of various acids.

2.4. Removal efciency of COD The COD test is commonly used to indirectly measure the concentration of organic compounds in a water sample, and it provides a useful index of the amount of organic pollutants that are present. Most applications of the COD test are intended to determine the amount of organic pollutants found in a surface water (e.g., lakes and rivers), which makes COD a useful measure of water quality. COD is typically expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution, although older references may express COD as parts per million (ppm) [15]. We did not use conventional COD removal methods, such as activated sludge processes [16], aerobic and anaerobic treatment processes, or coagulation treatment. Instead, we used acid leaching and distillation treatments to remove COD.
Table 1 The COD removal efciency of waste xer solutions with 15% of various acids. Acid volume (%) 0 1 2 3 4 5 COD concentration after mixed with H2SO4 (mg/L) 88,654 81,693 65,667 51,205 54,332 53,550 COD concentration after mixed with HNO3 (mg/L) 88,654 87,166 80,130 74,267 64,495 57,850 COD concentration after mixed with HCl (mg/L) 88,654 83,948 79,846 78,897 77,307 76,717

3. Results and discussion 3.1. Electrolysis of waste xer solutions at a low electric current To obtain the proper electric current for electrolysis, 1000 mL of waste xer solution was treated at a low electric current. We evaluated the process at different electric currents (0.1 A, 0.3 A, 0.5 A, 0.7 A, and 0.9 A), and samples were collected at hourly intervals throughout the duration of the electrolysis procedure. Following this procedure, we used the proper electric current to determine the most suitable pH value for electrolysis by varying the pH of the waste xer solution (with set pH values of 3, 4, 5, 7, 8, 9, and 10), where the original pH of the waste xer solution was 6. Fig. 1 shows that the recovery of silver increases for a specic electric current as the electrolysis time is increased. The recovery

efciencies of silver during the 8 h electrolysis procedure at 0.1 A, 0.3 A, 0.5 A, 0.7 A, and 0.9 A were 10.57%, 11.75%, 45.50%, 62.68%, and 83.88%, respectively. These results show that the most suitable electric current is 0.9 A. We obtained the most suitable pH value for the waste xer solutions from the experiment shown in Fig. 2, which used an electric current of 0.9 A for solutions at varied pH values. The recovery efciencies of silver at pH 3, 4, 5, 6, 7, 8, 9, and 10 were 83.65%, 84.66%, 81.54%, 83.88%, 99.09%, 100%, 98.63%, and 81.20%, respectively. These results show that the most suitable pH value is pH 8. These experiments demonstrate that the most suitable recovery efciency of silver is 100% at 0.9 A and pH 8. The recovery efciency of silver at pH 9 or pH 10 was less than the recovery efciency at pH 8 because a portion of the metal ions were deposited while the pH of the waste xer solutions was adjusted to 9. Furthermore, the phenomenon of metal ion deposition becomes obvious when the pH value is adjusted to pH 10. The co-precipitation of metal ions during electrolysis resulted in a

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Fig. 8. The deposits from waste xer solutions mixed with H2SO4.

Table 2 The COD removal efciency of waste xer solutions mixed with H2SO4 at an electric current of 10 A.

80,000 70,000

40 30
COD 5A

COD concentration (mg/L) 90,313 65,330 58,830 55,320 52,130 49,250 45,810 46,520 47,320

COD recovery efciency (%) 0 27.6 34.8 38.7 42.2 45.4 49.2 48.5 47.6

COD concentration (mg/L) 84,196 44,459 44,259 44,065 33,442 33,836 32,655 33,049 33,442

COD recovery efciency (%) 0 47.2 47.1 47.6 60.3 59.8 61.2 60.7 60.3

60,000 50,000 40,000

COD removal efficiency (%)

COD concentration (mg/L)

Electrolysis time (h)

Without H2SO4

With H2SO4

20 10
0

COD 7A COD 8A COD 10A COD 15A COD RE 5A COD RE 7A COD RE 8A COD RE 10A COD RE 15A

0 1 2 3 4 5 6 7 8

-10 30,000 20,000 10,000 0 -20 -30 -40 0 1 2 3 4 5 6 -50

Electrolysis time (h)

Fig. 10. The COD removal efciency of waste xer solutions mixed with H2SO4 with various electric currents.

100,000 90,000

100 90

COD concentration (mg/L)

COD removal efficiency (%)

80,000 70,000 60,000 50,000 40,000 30,000 20,000 10,000 0

80 70 60 50 40 30 20 10

COD without H2SO4

COD with H2SO4

COD RE without H2SO4

COD RE with H2SO4

for the electrolysis procedure with a current of 3 A and a duration of 3.5 h. The recovery efciency did not increase with additional electrolysis time, and the proper electrolysis time is therefore 3.5 h, as shown in Fig. 3. Fig. 4 shows that when we adjusted the waste xer solutions to pH 8 and then used an electric current of 3 A, the electrolysis time decreased from 3.5 h to 2.5 h, and the recovery efciency of silver increased from 88.64% to 99.55%. Additionally, the purity of silver was 98.31% and 98.62% for an electric current of 0.9 A and 3 A, respectively.

2 3 4 5 6 Electrolysis time (h)

3.3. The purication of silver The silver in the waste xer solutions formed a metal coating on the stainless steel plate during the electrolysis procedures, and we scraped this silver metal from the plate in order to obtain puried silver after an additional purication procedure. The silver metal that was scraped off of the plate was dissolved in a high concentration solution of nitric acid, and we applied an electric current of 0.9 A to obtain high purity silver via electrolysis. Fig. 5 shows that as the electrolysis time increased, the silver concentration in the waste xer solution decreased and the silver recovery efciency increased. The recovery efciency of silver reached 98.85% after 3 h of electrolysis, but then decreased for durations of electrolysis greater than 3 h. The reason for this decrease in recovery efciency is that the stainless steel plate was coated with too much silver metal to allow for additional silver metal to coat the plate. The purity of the silver metal reached 99.9% from the purication process, and the appearance of the silver metal is shown in Fig. 6.

Fig. 9. The COD removal efciency of waste xer solutions mixed with H2SO4 with an electric current of 10 A.

decrease in the recovery efciency of silver. Conclusively, we can obtain the most suitable recovery efciency of silver by employing these suitable experimental parameters for the electrolysis procedure. 3.2. Electrolysis of waste xer solutions at a high electric current (3 A) We employed a high electric current (3 A) instead of the low electric currents previously evaluated (0.1 A, 0.3 A, 0.5 A, 0.7 A, and 0.9 A) to lessen the electrolysis time, as shown in Figs. 3 and 4. A maximum silver recovery efciency of 88.64% was obtained

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191

Fig. 11. The distillation water and waste sludge following distillation.

3.4. The efciency of COD removal Continuous-ow activated sludge reactors were used to treat the photoprocessing wastewaters from two commonly used photoprocesses: Kodak Flexicolor Process C-41 (lm processing) and Kodak Ektacolor Process RA-4 (paper processing). Simulated wastewaters were fed to laboratory-scale reactors at a loading level of 10% (v/v) along with a synthetic base feed. The biodegradation of the base feed was not affected by the photoprocessing wastewaters. In addition, more than 36% of the photoefuent-derived COD was destroyed, primarily as a result of sulte and thiosulfate oxidation. Therefore, the efciency of COD removal by the continuous-ow activated sludge reactors was not suitable [17]. Furthermore, Lin and Yang [18] found that photoprocessing wastewaters that were treated by an electrochemical method resulted in a high efciency of COD removal (approximately 95% of COD) but that the cost of this electrochemical treatment was too expensive to use. However, we used acid leaching and distillation for COD removal and found this method to be an ideal approach to remove COD.

3.4.2. Enhancement of concentration by distillation for COD removal After the silver recovery processes, 1000 mL of treated waste xer solution was distilled and concentrated using a condenser for COD removal, and the distillation water and waste sludge were separated, as shown in Fig. 11. The COD concentration of the waste xer solutions decreased from 88,657.3 mg/L to 579.9 mg/L, and the efciency of COD removal was 99.3%, as shown in Table 3. 4. Conclusions  Samples of waste xer solution (1000 mL) with a silver concentration of 3000 mg/L underwent an 8 h electrolysis procedure at low electric currents. For an electric current of 0.9 A, the silver recovery was 83.88%, which was better than the silver recovery for any of the other electric currents that were studied (0.1 A, 0.3 A, 0.5 A, and 0.7 A). In addition, when the solution was adjusted to pH 8 and then underwent 8 h of electrolysis at an electric current of 0.9 A, the silver recovery increased from 83.88% to 100%. When the electric current was increased to 3 A for a 3.5 h period, the silver recovery was 88.64%. Additionally, when the solution was adjusted to pH 8 and an electric current of 3 A was applied for 2.5 h, the silver recovery reached 99.55% purity. The purity of silver was found to be 98.31% and 98.62% for an electric current of 0.9 A and 3 A, respectively, notwithstanding the recovered silver, which could obtain 99.9% purity after being dissolved in nitric acid and undergoing electrolysis. The proposed ow chart for the treatment of waste xer solutions is shown in Fig. 12.  The efciency of COD removal for waste xer solutions mixed with H2SO4 (100 mL of waste xer solution and 1 mL of H2SO4) is better than the efciency of COD removal of waste xer solutions mixed with other acids. The COD concentration decreased from 88,654 mg/L to 51,205 mg/L after being mixed with 3 mL of H2SO4. The proper efciency of COD removal for the 3 mL H2SO4 mixture was 42.24%.  The waste xer solutions mixed with H2SO4 resulted in a proper efciency of COD removal. Electric currents at 5 A, 7 A, 8 A, 10 A, and 15 A were applied during an electrolysis procedure to remove COD, and an electric current of 8 A provided the most suitable COD removal efciency.  Higher COD removal efciencies were obtained by employing distillation, but the cost of the distillation treatment is more expensive.
Table 3 The COD removal efciency by distillation of the waste xer solution. COD concentration (mg/ L) Waste xer solution Cooling water 88,657.3 579.9 COD removal efciency (%) 0 99.3

3.4.1. Acid leaching for COD removal Small volumes (15 mL) of various inorganic acids (hydrochloric acid (HCl), nitric acid (HNO3), and sulfuric acid (H2SO4)) were added to 100 mL of waste xer solution in order to remove COD. Fig. 7 and Table 1 show that the efciency of COD removal was the best for the H2SO4 treatment. In addition, the COD concentration decreased from 88,654 mg/L to 81,693 mg/L after being mixed with 1 mL of H2SO4 and from 88,654 mg/L to 51,205 mg/L after being mixed with 3 mL of H2SO4. The suitable efciency of COD removal was found to be 42.24% for the case where 3 mL of H2SO4 was used. A 1000 mL waste xer solution that received the addition of 30 mL of H2SO4 resulted in the deposits shown in Fig. 8, and the deposits were assessed to be thiosulfate or organic sulde. We separated the deposits and the waste xer solutions before conducting electrolysis at an electric current of 10 A. Table 2 and Fig. 9 show that the efciency of COD removal from a mixture with H2SO4 is better than the efciency of COD removal without H2SO4 because the hydrogen ions in the mixing solutions are affected by electrolysis. Therefore, the waste xer solutions mixed with H2SO4 resulted in proper efciency of COD removal. Furthermore, various electric currents (5 A, 7 A, 8 A, 10 A, and 15 A) were applied via electrolysis to remove COD. The proper efciencies of COD removal under 5 A, 7 A, 8 A, 10 A, and 15 A were 26.94%, 27.12%, 35%, 32.52%, and 11.45%, respectively (see Fig. 10). Most of the waste xer solutions would vaporize under an applied current of 15 A, resulting in the concentration of the organic materials present in the waste xer solution. This occurrence resulted in an abnormal phenomenon, where the efciency of COD removal did not increase with the increased electric currents.

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Waste fixer solutions

pH=6.09, Ag=2,7003,300 mg/L, COD=88,654 mg/L

Electrolysis
(Deposition: Ag 2S)

Current: 3 A

Annealing process
Rising to 1,000 oC, during 3 h

Waste solution after electrolysis Distillation

(The removal efficiency of COD: 99.3%)

Crude Ag
(Purity: 98.32%)

Dissolved in HNO3
Electrolysis (Current: 0.9 A)

Purified Ag
(Purity: 99.9%)

Fig. 12. The proposed ow chart for the treatment of waste xer solutions.

Acknowledgements This study was guided by the late Professor Hung-Yuan Fang and was carried out by his team of environmental and microbiological researchers. This study could not have been accomplished without his meticulous instruction and positive feedback. References
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