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ENVIRONMENTAL MANAGEMENT AND HEALTH, AN INTERNATIONAL JOURNAL 6,2

Fate of heavy metals in the leather tanning industrial wastewater using an anaerobic process
Hussein I. Abdel-Shafy, Werner Hegemann and Elke Genschow This pilot anaerobic digester plant compares favourably with aerobic conversion and also produces biogas

Introduction
The anaerobic treatment system has become more important in the last four years at research and commercials levels. These systems have proved to be very promising since they are not only producing a humus-like residue, comparable to the compost produced by the aerobic conversion technique, but also a form of energy as biogas which has a medium calorific value and can be easily upgraded to several forms of valuable energy[1-3]. On the other hand, the leather tanning and finishing industry produces unique and complex industrial wastewaters that result in special problems with regard to treatment, whether discharged directly into receiving waters or into publicly owned treatment works[4,5]. It is well known that most technical advances towards the alleviation of these problems have occured only after legislated regulatory actions which, in many cases, forced industry to develop technology to meet the conceived needs of society. The main source of organic pollution from most tanneries is the beamhouse wastestream[4,5]. Thus, the resulting waste stream contains large quantities of lime, sulphide and both dissolved and particulate hair protein along with lesser amounts of salt, blood, flesh particles and manure[6]. These constituents all contribute to the difficulty of treating tannery wastewater by conventional treatment schemes[7,8]. In addition, the organic fraction of the waste stream is only very slowly biodegradable[9,10].

On the other hand, chromium(III) is widely used as a tanning agent in the leather industry and is an important source of contamination owing to the large volume of exhaust liquid discharged and solid sludge produced [912]. The aim of the present work was to study the effect of the anaerobic process with special reference to the fate of chromium and the other associated heavy metals throughout the process. The elimination rates of these metals were studied with respect to each consecutive steps of the anaerobic process. In addition, the levels of sulphide, sulphate, total organic Kjeldahl nitrogen (TKN) ammonium nitrogen, COD and BOD5 were investigated. The levels of metals in the final effluent, as well as the sludge, in correlation with the other physico-chemical characteristics were also investigated.

Materials and methods

The wastewater used in the present study was brought weekly from one of the tannery industrys plants located in South Germany[9]. An anaerobic pilot plant digester for the treatment of the tannery wastewater was erected at the Technische Universitt Berlin (TU-Berlin) in the Department of Sanitary Engineering (Figure 1). Daily samples were collected for five days a week and mixed together as a composite sample. These samples were:
The authors wish to express their deep gratitude and appreciation to the Deutscher Akademischer Austauschdienst for the fellowship granted to Professor Dr Abdel Shafy throughout this study. The authors also owe a great debt to the Technische Universitt Berlin, Fachgebeit Siedlungswasserwirtschaft for the facilities provided.

Environmental Management and Health, Vol. 6 No. 2, 1995, pp. 28-33 MCB University Press Limited, 0956-6163

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Figure 1. The anaerobic pilot plant digester for the

treatment of tannery industrial wastewater
Biogas

Raw wastewater and the sludge after stabilization (before subjection to the anaerobic reactor). G Final wastewater and the produced sludge after treatment the anaerobic reactor. The physical and chemical characteristics of the wastewater samples were carried out according to DINnorms[13].
G

el.

Influent

Stirring tank

Fixed film bed reactor

Influent

For the heavy metals investigation, the sludge samples were oven dried for 24 hours at 105C. All wastewater samples along with a known weight of the sludge samples were acid digested using nitric acid, followed by hydrogen peroxide according to USEPA[14]. Metal concentrations were determined using a Varian atomic absorption spectrometer, model SpectrAA-400 equipped with a GTA-96 graphite tube atomizer, attached to IBM personal computer AT (programmed for VarianSpectrAA-300/400). The studied metals were Cr, Cd, Pb, Ni, Cu, Fe and Zn. Each result for each sample is the average of ten sequential readings. Blank and double distilled water were used. All the results presented here were the average of all the studied samples.

G G G

Raw wastewater and the sludge before acidification. Raw wastewater and the sludge after acidification using concentrated hydrochloric acid. Raw wastewater and the sludge before stabilization.

Results and discussion

The characteristics of the tannery raw wastewater are given in Table I. The guideline characteristics of the discharged wastewater according to German requirements are also given in Table I. The levels of heavy

Table I. The characteristics of the tannery raw industrial wastewater (i.e. before the anaerobic treatment) and the guideline
characteristics of the discharged wastewater Tannery wastewater Minimum Maximum 2,100 500 100 0.1 310 300 27,500 3,800 2,600 600 850 650 ATV Average 8,700 1,100 950 70 580 380 Minimum 410 NL NL 0 NL 4 Maximum 4,000 NL NL 4,800 NL 200

Parameters COD (mg/l) DOC (mg/l) Sulphate (mg/l) Sulphides (mg/l) TKN (mg/l)
+ NH4

n 55 50 50 50 40 40

(mg/l)

Notes: COD = chemical oxygen demand DOC = dissolved organic carbon TKN = total organic nitrogen (Kjeldahl method) + NH4 = ammonium nitrogen NL = not listed n = number of samples Source: [15]

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Table II. Level of metals in the raw wastewater and the sludge (before acidification)
Sample RWW (mg/l) SLG (in RWW) (mg/kg dry wt) SLG/RWW (mg/l) Notes: n = number of samples RWW = raw wastewater BDL = below the minimum detection limits (0.01mg Pb/l) SLG = sludge wt = weight SLG/RWW = the level of metal in the sludge correlated to its presence in the RWW n 21 21 21 Cr 6.37 12,795.0 2,008.8 Cu 0.12 24.3 202.5 The mean values Fe Cd 0.56 347.3 620.2 0.03 4.8 160.0 Ni 0.09 14.0 155.6 Pb BDL 30.5 Zn 0.373 107.0 286.9

metals in this wastewater and the sludge are given in Table II. From these results it can be seen that the studied wastewater is characterized by a high load of both organic matter and ammonium nitrogen. In addition, the level of chromium in the wastewater was far over the permissible level[15]. At the same time metals were mainly concentrated in the sludge. Such concentration can be arranged according to the following descending order: Cr > Fe > Zn > Ni > Cu > Pb > Cd. The levels of metals in the sludge in correlation to their levels in the wastewater were calculated and given in Table II. This precipitation of metals from wastewater into the sludge is due mainly to the use of a sulphide-lime pulping method for the removal of hair and cleaning the animal hides prior to tanning[4]. The high concentrations of lime produced wastewater pH values well above levels considered acceptable for

biological treatment, namely between 8 and 11. Therefore, it was essential to decrease the pH of the examined wastewater to 6 using concentrated HCl. Level of metals in the resulted wastewater and the sludge after acidification are given in Table III. It may be noted that the level of metals increased remarkably in the wastewater, and decreased in the produced sludge, for instance, chromium increased in the wastewater from 6.4mg/l to 33.7mg/l, and decreased in the sludge from 12,795.0 to 6,295.8mg/kg as dry weight. Correlation between the level of metals both in wastewater and sludge before and after acidification are shown in Figures 2 and 3 respectively. The studied anaerobic process included stabilization of wastewater (Figure 1). The fate of metals before and after stabilization is given in Table IV. The obtained results show that Cr decreases from 11.4mg/l to 6.7mg/l.

Table III. Level of metals in the raw wastewater and the sludge after the addition of acid to pH6 (concentrated hydrochloric acid)
Sample RWW (mg/l) Maximum Minimum Average SLG (mg/kg) as dry weight Maximum Minimum Average Cr 80.01 12.82 33.72 8,861.3 3,855.8 6,295.8 Cu 0.39 0.01 0.13 36.5 7.5 15.9 Fe 7.36 0.09 1.82 258.8 91.5 140.5 Cd 0.07 0.05 0.06 3.8 2.1 3.1 Ni 0.23 0.12 0.19 20.0 8.5 12.4 Pb 0.60 0.03 0.21 35.3 5.5 22.7 Zn 2.16 0.13 1.07 164.5 34.8 94.2

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Figure 2. Correlation between the levels of heavy metals in the raw wastewater before and after acidification
(mg/l) 100

Figure 3. Correlation between the levels of heavy metals in

the raw sludge before and after acidification
(mg/kg dry weight) 100,000

10

10,000

1,000

0.1

100

Chromium Copper

Iron

Cadmium

Nickel

Lead

Zinc

Chromium Copper

Iron

Cadmium

Nickel

Lead

Zinc

Key:

Before

After acidification

Key:

Before

After acidification

Table IV. Level of metals in the wastewater before and after stabilization in the anaerobic system (mg/l)
Sample Wastewater before stabilization Maximum Minimum Average Wastewater after stabilization Maximum Minimum Average Cr 34.18 1.41 11.41 10.65 0.94 6.66 Cu 0.16 0.03 0.06 0.15 BDL 0.06 Fe 0.91 0.17 0.55 0.70 0.09 0.44 Cd 0.07 0.05 0.06 0.07 0.04 0.05 Ni 0.20 0.10 0.17 0.19 0.10 0.16 Pb 0.59 0.02 0.23 0.63 BDL 0.25 Zn 1.11 0.17 0.41 1.62 0.07 0.49

Table V. The characteristics of the final wastewater effluent

after anaerobic treatment Parameters COD (mg/l) Sulphate (mg/l) Sulphide (mg/l) tR (d) BR (COD) (kg/m3/d) n 55 50 50 Average 1,980 161 420 4.2 2.61

However, slight change did occur for the rest of the associated metals. Finally, the wastewater was subjected to the fixed film bed reactor for anaerobic treatment and biogas production (Figure 1). The characteristics of the final wastewater effluent are shown in Table V. Levels of metals in this final wastewater and the sludge are given in Table VI. The correlation between the level of metals in both wastewater and sludge in the influent and effluent of the anaerobic treatment pilot plant is shown in Figure 4. The percentages of the elimination of metals in the wastewater in relation to the raw wastewater are shown in Figure 5. The overall results revealed that the studied anaerobic pilot plant did improve the quality of the tannery

Notes: COD = chemical oxygen demand tR = retention time/day BR (COD) = COD load (kg/m3/day) n = number of samples

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ENVIRONMENTAL MANAGEMENT AND HEALTH, AN INTERNATIONAL JOURNAL 6,2

Table VI. Level of metals in the final effluent of wastewater and the sludge
Type FWWE (mg/l) Maximum Minimum Average FSLGE (mg/kg) Maximum Minimum Average Notes: FWWE = final wastewater effluent FSLGE = final sludge effluent BDL = below the minimum detection limits Cr 1.02 0.37 0.67 15,795.0 6,227.5 13,192.5 Cu 0.15 BDL 0.06 38.0 20.4 27.7 Fe 0.64 0.08 0.34 419.5 228.5 347.8 Cd 0.07 0.03 0.05 5.5 2.0 3.2 Ni 0.39 0.10 0.15 22.5 6.0 13.7 Pb 0.73 BDL 0.21 38.7 19.9 27.8 Zn 0.76 0.09 0.29 141.1 78.0 110.1

Figure 4. Correlation between the levels of metals in

wastewater and in sludge in influent to and effluent from pilot anaerobic treatment plant
(mg/l) 100 (mg/kg dry weight) 100,000

Figure 5. Percentage of metal elimination in wastewater after anaerobic treatment

Per cent 100 90 80 70

10,000 10

60 50 40

1,000 1 100

30 20 10 0 Chromium Iron Nickel Zinc

Copper

Cadmium

Lead

0.1 10

0.01 Chromium Copper

1 Iron Cadmium Nickel Lead Zinc

Key:

Influent

Effluent

Influent

Effluent

wastewater in order to meet the legislative guideline characteristics. Thus, the anaerobic treatment system proved to have the advantage of a high organic load, low energy consumption, small amount of sludge produced and simple equipment[16,17]. Hence, it has great potential as an economical and effective approach to wastewater treatment. Furthermore, the results show that a remarkable elimination has been achieved in the levels of chromium

and the other associated metals in the treated effluent. On the other hand, a significant increase of the same metals was observed in the produced sludge. The level of chromium in the exhausted sludge reached 13,192.5 mg/kg. According to German regulations chromium should not exceed 900mg Cr/kg as dry weight (Table VII). Lack of knowledge of the threshold values and of the long-term effects of Cr[18,19] strongly militate against the use of such tannery sludges as manure in agriculture[20]. Furthermore, the possibility that organic ligands and/or acid conditions increase Cr(III) mobility in the soil[21], and that manganese oxides allow its oxidation to the more toxic and mobile Cr(VI) forms is further evidence that the use of these sludges in agriculture should be restricted. Finally, this sludge contains some other toxic metals, including Pb and Cd up to 27.8 and 3.2 mg/kg, respectively, as dry weight. Recovery of chromium from tannery sludges[11,20] is strongly recommended.

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Table VII. German guideline regulations for the levels of

heavy metals in the sludge (mg/kg dry weight) Metal Pb Cd Cr Cu Ni Ag Zn Source: [15] Guideline level 900 10 900 800 200 8 2,500

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8. Jackson-Moss, C.A. and Duncan, J.R., Anaerobic digestion at high sulfate concentrations, Journal of the Am. Leather C. Association, Vol. 85, 1990, pp. 376-82. 9. Genschow, E. and Hegemann, W., Untersuchungen zr anaeroben Reinigung von Gerbereiabwasser, Wasser/Abwasser, Vol. 134 No. 5, 1993, pp. 262-8. 10. Visser A., Gao, Y. and Letting, G., Effects of short-term temperature increase on the mesophilic anaerobic breakdown of sulfate containing synthetic wastewater, Wat. Res., Vol. 27 No. 4, 1993, pp. 541-50. 11. Margarida Alves M. et al., Chromium removal in tannery wastewaters polishing by Pinus sylvestris, Bark. Wat. Res., Vol. 27 No. 8, 1993, 1333-8. 12. Nasr, F.A. and Abdel-Shafy, H.I., Biodegradation of sewage sludge: toxic effects of heavy metals, Environmental Management and Health International Journal, Vol. 3 No. 4, 1992, pp. 18-25. 13. Herausgegeben von der Fachgruppe Wasserchemie in der Gesellschaft Deutscher Chemiker in Gemeinschaft mit dem Normenausschu Wasserwesen (NAW) in das Deutsches Institut fur Normung e.V. (DIN), published in Deutsche Einheitsverfahren zu Wasser-, Abwasser- und Schlammuntersuchung , VCH, Weinheim, New York, Basel, Berlin, Wien, Zrich, No. 29, 1993. 14. US Environmental Protection Agency, Methods for Chemical Analysis of Water and Wastewater, Office of Technology Transfer, Washington DC, 1974. 15. Klrschlammverordnung (AbfKlV), Bundesgesetzblatt, Jahrgang 1992, Vol. 1 No. 15, April 1992, p. 3. 16. McInerney, M.J. Bryant, M.P. and Pfennig, W., Arch. Microbiol., Vol. 122, 1971, pp. 129. 17. Boone, D. and Bryant, M.P. Appl. Environ . Microbiol., Vol. 40, 1980, pp. 622. 18. Adriano, D.C., Chromium in Trace Elements in the Terrestrial Environment, Springer, New York, NY, 1986, pp. 58-76. 19. Anderson, R.A., Essentiality of chromium in humans, Sci. Total. Environ., Vol. 86, 1989, pp. 75-81. 20. Macchi, G., Pagano, M., Pettine, M., Santori, M. and Tiravanti, G., A bench scale study on chromium recovery from tannery sludge, Wat. Res., Vol. 25 No. 8, 1991, pp. 1019-26. 21. Imai, A. and Gloyna, E.F., Effect of pH and oxidation state of chromium on the behavior of chromium in the activated sludge process, Wat. Res., Vol. 24 No. 9 , 1991, pp. 1143-50.

Hussein I Abdel-Shafy is Professor at the Water Pollution Research and Control Department, National Research Centre, Dokki, Cairo, Egypt. Werner Hegemann is Head of Sanitary Engineering Department and Elke Genschow is a Research Engineer at the Sanitary Engineering Department both at the Technische Universitat, Berlin, Germany.