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Trends in Food Science & Technology 20 (2009) S23eS26

Review

Application of chlorine dioxide for filler hygiene e A viable alternative
Ch Kunzmanna,* and H Schutzb,1 ¨
Versuchs- und Lehranstalt fur Brauerei Berlin (VLB), ¨ Seestraße 13, 13353, Berlin, Germany b ¨hrke GmbH, Siemser Landstraße 127, 23569 Jurgen Lo ¨ Lubeck, Germany (Tel.: D49 30/45 08 0 28 2; e-mail: ¨ kunzmann@vlb-berlin.org)
a

Here, only reference values for chlorite and chlorate of 0.7 mg/l are indicated, which under practical conditions for a chlorine dioxide dosage would correspond to slightly more than 1 mg/l (Guidlines for drinking-water quality, 2004; Kunzmann & Ahrens, 2007). Chlorite and chlorate are disinfection by-products. The formation of trihalomethanes (THM), which are dangerous to health, as well as the formation of absorbable organic halogen compounds on the waste water side are suppressed as much as possible. Also, the disinfection efficiency is essentially independent of the pH value, these are the essential advantages compared to the classical application of active chlorine containing agents like chlorine gas or hypochlorites. Chemistry of chlorine dioxide and the influence of water quality Chlorine dioxide acts as an oxidative biocide and does not chlorinate. Compared to chlorine, no chlorine compounds are formed to activate organic CH or NH compounds and this is reflected in an almost completely suppressed generation of THMs (Disinfectants and disinfectant By-Products, 2000; Hoigne & Bader, 1994). Compared to other oxidising substances like ozone, however, chlorine dioxide is more selective. In comparison with ozone, there is neither a reaction with bromide towards bromate nor with ammonium (Hoigne & Bader, 1994). However, if there are different inorganic substances or substances which can be oxidised organically, chlorine dioxide, like all oxidising disinfectants, is subjected to a more or less intense degradation which strongly fluctuates depending on the water quality (Kunzmann & Ahrens, 2007). For an understanding of the degradation behaviour and a decay of chlorine dioxide respectively, the reactions in Fig. 1 are particularly interesting: If there are oxidisable substances like Fe2þ, Mn2þ, NOÀ 2 or different phenolic compounds, chlorite (List of the preparation materials and disinfection methods according to x 11
ClO2 + NOM* + e- → ClO2- + NOM*(ox.) ClO2- + 4 H+ + 4e- → Cl- + H2O 2ClO2 + 2 H2O → ClO2- + ClO3- + 2H+ 4ClO2- + 2 H+ → 2 ClO2 + Cl- + ClO3- + H2O [1] [2] [3] [4]

In recent years, chlorine dioxide has proved itself as a reliable disinfectant for water disinfection. With increasingly stringent hygienic requirements for product and food production, water disinfectants are increasingly applied in production sectors, e.g. surface disinfection of fillers or in CIP. In the following contribution, the application of chlorine dioxide for filler hygiene as a new cleaning and disinfection system will be described. The basis for this report is a research project undertaken by the Jurgen Lohrke GmbH ¨ ¨ in collaboration with VLB Berlin, during which comprehensive laboratory and pilot projects were carried out in industrial companies. Recently, chlorine dioxide has been established in the beverage sector as a disinfectant. It is primarily used because of an effective storage effect in combination with a lower risk of formation of disinfection by-products compared with chlorine substituting disinfectants for process water disinfection. For this use, a maximum addition of 0.4 ppm is allowed according to the German potable water legislation. After disinfection, the important issue is not to exceed or fall below the residual contents of chlorine dioxide of 0.2 ppm and 0.05 ppm respectively (List of the preparation materials and disinfection methods according to x 11 Drinking Water Ordinance 2001, 2007). According to the WHO, there is no reference value for chlorine dioxide.

*NOM = sum of the oxidisable inorganic and organic substances.
* Corresponding author. 1 Tel.: þ49 451/29 30 7 55. E-mail: hartmut.schuets@loehrke.com.
0924-2244/$ - see front matter Ó 2009 Published by Elsevier Ltd. doi:10.1016/j.tifs.2009.01.040

Fig. 1. Decay mechanisms of chlorine dioxide in case of presence or absence of degrading water substances respectively.

Different salt compositions of the water do not have important influence on the decay of the disinfectant. Degradation of the disinfectant during rinsing amounted to approx. Concentrations of 5 ppm which were produced according to the hydrochloric acid and chlorite method were applied for packaging disinfection. was applied for the validation of aseptic plants as a spore suspension. 2). a filling volume of 330 ml and a residual concentration of chlorine dioxide in the dripping water which is allowed according to the WHO standard. Kunzmann.025 mg/l in the product could be assumed. Only the ‘‘near-water’’ product with lemon taste showed a noticeable negative change in taste with an absolute concentration of 0. H. colour and pH value were not observed. Within the scope of an application in water disinfection as well as in the case of a stacking with surface disinfection. As a second test organism. Relating to a maximum assumed remaining dripping water amount of 1. disinfectant residues in the adhered water or dripping water respectively which cannot be avoided technically can remain in the bottles. in the sequence of reactions presented above. alkalinity and contamination. Chlorite itself also has an oxidative potential. this concentration was multiplied by the safety factor of 5 so that a concentration of 0. In the panel it was described as earthy and musty. After the bottles had been rinsed. The disinfection by-products chlorite and chlorate could not be found in the product. Schu / Trends in Food Science & Technology 20 (2009) S23eS26 ¨tz Drinking Water Ordinance 2001. Influence of possible residual concentrations on beverages During rinsing of bottles. In the sample basin. it has negative influences on the efficiency of such an application. Under conditions which are similar to potable water. and was found to be extremely resistant against disinfectants compared to other test organisms and thus deemed suitable for testing the application of chlorine dioxide. 2007). compared with oxidisable water substances. Disinfecting effect In laboratory tests. These two sample approaches were compared with a zero sample without the addition of chlorine dioxide and a sample with a maximum legal residual concentration in respect of the initial water of 0. ¨ 1980). Influences on turbidity. .2 mg/l. and it is also subject to degradation. The filler front table was continuously rinsed with 0. 2007) is generated from chlorine dioxide according to equation (1) and plays a much more important role in potable water disinfection than it does in surface disinfection. In microorganism reduction tests. the end products are chloride and chlorate. with application concentrations of 5 mg/l chlorine dioxide without additional temperature influence. 2002): Microorganism reductionðRÞ ¼ logðinitial concentrationÞ À logðfinal germ numberÞ In practical tests. i. the chloride concentration over a period of 16 h amounted to between 20 and 30 mg/l. the disinfecting effect with particular emphasis on the short contact time of <10 s between disinfectant and packaging during rinsing of PET bottles was examined. In an acidic environment. chloride and chlorate (equation (3)). Within the scope of triangle test assessments. the medium logarithmic germ reduction (R) is defined as (VDMA.e. For further concentration levels. Measurements of the endogenous antioxidant potential assessed by electron spin resonance spectroscopy showed no significant (endogenous antioxidative potential) (EAP)reduction in the concentration levels which can be put down to residual drip water amounts. neither in fresh samples nor at the end of the expiry date. shall be removed in order to avoid sedimentations on the surfaces. the panel showed no significant deviation to the untreated samples. (vegetative bottom-fermenting Saccharomyces cerevisiae) cells were applied. apple spritzer and a multivitamin fruit juice beverage. Practical applications showed a good stability of the disinfectant in the sample receptacles (see Fig. the temperature influence over 20  C plays a dominating role for the decay and apart from corrosion. this resulted in a calculated absolute concentration of chlorine dioxide of 0.7 mg/l chlorine dioxide. 0. a chlorine dioxide decay of up to 50 percent of the initial concentration could be observed within 1 h. this reaction plays a secondary role. chlorine dioxide in aqueous solution breaks down as shown in equation (3). This solution was not recovered. predominantly iron.2 mg/l chlorine dioxide in the product. the dripping water contained concentrations which conformed to potable water. it takes place within a few minutes (Kunzmann & Ahrens.S24 C. This reaction can be accelerated with light. Here. different concentrations were added to different beverages.005 mg/l in the product. The samples examined were a ‘‘near-water’’ product with lemon taste. The temperature influence thus dominates in high application concentrations. orange lemonade.5 ml (Schußler. The test organism Bacillus subtilis.1 ppm were adhered to. the generated chlorite can thus breakdown to chlorine dioxide. heat. This would be possible if the initial water contained such a residual concentration during production. The chlorine dioxide generated in traces thus re-enters the reaction cycle. These two reactions are particularly important for applications outside of potable water disinfection. Here. Within the scope of an optimised application.5 ppm. If no degrading substances exist. this reaction is the rate-determining reaction under normal water conditions. The MAK values of 0. this degradation takes place much more slowly than with chlorine dioxide and chloride is generated as an end product (equation (2)). Because of a residual drip volume it seems to be technically impossible to enter such a high concentration in the product. Particularly with temperatures above 40  C and an initial solution of 10 mg/l. strongly degrading substances. However. event though it is noticeably lower. when it is additionally necessary to resort to temperature influence in order to support the disinfection effect. In order to avoid possible product damages and legal violations.

the application of any oxidative disinfectant increases the corrosive potential of an aqueous medium. and a sprayed initial concentration of >log 5. the application of chlorine dioxide for filler hygiene was examined. Also. A negative influence on the packaging and their barrier layers respectively was not observed with chlorine dioxide treatment. In order to avoid damage of the material surfaces caused by the application of the disinfectant. reductions for B. higher chloride concentrations could be observed. corrosion of rustproof stainless steel appears in different sectors in the beverage industry. Sensory characteristics of the products were acceptable. e. which normally correspond to twice or three times the volume of chlorine dioxide in the stock solution. The redox potential of the different prepared stock solutions with an equal application concentration in water was identical. as expected. Kunzmann. Examinations on material compatibility Unfortunately. If corrosion appears. strongly reduce the resistance of stainless steel. for that purpose. Diagram of the chlorine dioxide conduct in a PET plant packaging sterilisation. a detailed examination of the water composition is still necessary. the stock solutions showed the highest chlorine dioxide concentrations. H. supported by iron contents and caused by limescale. it may pose risk particularly in biologically sensitive product areas and should thus be avoided by all means. particularly of chloride. concentration of residual disinfectants as well as by-products due to desiccation or degassing with subsequent reverse condensation. Other aspects are often application specific factors which quickly lead to the formation of pitting. such a hygiene measure can be retrofitted with relatively low effort. Besides the corrosion-relevant water parameters like pH. ion concentrations. no excessive concentrations should be applied and desiccation has to be avoided. cerevisiae of more than 4 log were achieved.C. ´ ´ Resume Chlorine dioxide can be applied as sole disinfectant for bottling biologically sensitive beverages and is an efficient alternative for common disinfectants in this application sector. . practical experience shows that particularly calcite precipitating waters. The hygienic condition of the examined fillers with continuous rinsing of the surfaces with 0. higher temperatures. the stock solutions which were produced on the basis of chlorite and hydrochloric acid showed the quickest and most complete chlorite conversion rates. different production methods for chlorine dioxide and chlorine dioxide stock solutions which are partly not allowed for potable water disinfection were examined as to their composition and their corrosive characteristics.g. but which are strongly diluted in the application solutions. subtilis of up to 3 log and for S. 2. and concentrations of free carbonic acid. Furthermore.7 mg/l chlorine dioxide led to good results. However. organism. Here. Particularly when biologically sensitive beverages are to be bottled with a conventional filler. Schu / Trends in Food Science & Technology 20 (2009) S23eS26 ¨tz S25 I IV B V Translation I Well water Rinser basin Bottle rinser Collecting basin V VII ClO2 Zugabe VI VII Cap basin Cap rinser Drain III A II VI II III IV I Brunnenwasser II Rinserbecken III Flaschenrinser IV Sammelbecken V Kappenbecken VI Kappenrinser VII Abfluss A / B Messsonde für CIO2 A/B measuring probe for ClO2 ClO2 Zugabe = ClO2 addition Fig. In terms of the initial solution of a chlorine dioxide application. Process waters which were treated by means of a sodium ion exchanger are thus particularly suitable as initial water for such an application. Furthermore. In particular the combination of high redox potential and high chloride content can be considered as the decisive factor. which is particularly important in the potable water sector. Summary Within the scope of a cooperation project.

A. 45e55. References Disinfectants and disinfectant by-products. & Ahrens. Vol. good biological results as well as excellent handling in a cycle process could be achieved. 12004. VDMA e Fachverbandsschriften Nahrungsmittelmaschinen und Verpackungsmaschinen. [Con:Cept]. Negative influences on the product were not observed during treatment. Pro Inno 2) for supporting the project KA0395101 as well as to Dipl. (1980). 246e247. Recommendations. Geneva: WHO. Kunzmann. J. Kinetics of reactions of chlorine dioxide in water e 1. Environmental Health Criteria 2162000.. Merkblatt: Prufung von Aseptikanlagen ¨ mit Packmittelentkeimungsvorrichtungen auf deren Wirkungsgrad. C. State December 2007. Chlordioxid und Chlorit in der Brauerei. (2007). Geneva: WHO. Ruckstande von Reinigungs. The generation of chlorine dioxide stock solutions via the hydrochloric acid and chlorite method turned out to be the most efficient and most complete method and thus provide the best characteristics for potable water applications. Water Research. 28(1).-J. water assessment in application solutions should generally have a high priority. 2002. . Over: Available from: www.und Desinfek¨ ¨ ¨ tionsmitteln auf festen Oberflachen. In: Guidlines for drinking-water quality. Chemie Ingenieur Technik.S26 C. We also would like to thank the brewery Darguner Brauerei GmbH as well as the Bad Durrheimer Mineralbrunnen GmbHþCo. who contributed significantly to the success of this project. H. Frank Blaume. (FH) Jako Rados and Dr. Hoigne. 6.. List of the preparation materials and disinfection methods according to x 11 Drinking Water Ordinance 2001. Brauwelt. 21. & Bader.de Schußler. Kunzmann. H. Schu / Trends in Food Science & Technology 20 (2009) S23eS26 ¨tz Chlorine dioxide was found to be an optional alternative for other disinfectants in the sector of bottling hygiene. 551e554. Nr. Acknowledgement Special thanks go to the project executing organisation Arbeitsgemeinschaft industrieller Forschungsvereinigungen ‘‘Otto von Guericke’’ (AiF. During the application of oxidising disinfectants.umweltbundesamt.. In practice. (1994). H. where the ¨ major part of the practical tests were carried out.Ing. Rate constants for inorganic and organic compounds. ¨ 52(3).