management situation and statistical analysis

Journal of Environmental Management 95 (2012) S154eS157

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Used battery collection in central Mexico: Metal content, legislative/management situation and statistical analysis José Antonio Guevara-García a, *, Virginia Montiel-Corona b,1 a

Laboratory of Research in Bioinorganic and Bioremediation (LIByB), Department of Basic Sciences, Technology and Engineering, Universidad Autónoma de Tlaxcala, Campus Apizaco, P.O. Box 140, 90300 Apizaco, Tlaxcala, Mexico b Department of Biotechnology and Bioengineering, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, P.O. Box 14-740, México D.F. 07000, Mexico

a r t i c l e i n f o

a b s t r a c t

Article history: Received 29 September 2009 Received in revised form 1 September 2010 Accepted 9 September 2010 Available online 8 October 2010

A statistical analysis of a used battery collection campaign in the state of Tlaxcala, Mexico, is presented. This included a study of the metal composition of spent batteries from formal and informal markets, and a critical discussion about the management of spent batteries in Mexico with respect to legislation. A six-month collection campaign was statistically analyzed: 77% of the battery types were “AA” and 30% of the batteries were from the informal market. A substantial percentage (36%) of batteries had residual voltage in the range 1.2e1.4 V, and 70% had more than 1.0 V; this may reflect underutilization. Metal content analysis and recovery experiments were performed with the five formal and four more frequent informal trademarks. The analysis of Hg, Cd and Pb showed there is no significant difference in content between formal and informal commercialized batteries. All of the analyzed trademarks were under the permissible limit levels of the proposed Mexican Official Norm (NOM) NMX-AA-104-SCFI2006 and would be classified as not dangerous residues (can be thrown to the domestic rubbish); however, compared with the EU directive 2006/66/EC, 8 out of 9 of the selected battery trademarks would be rejected, since the Mexican Norm content limit is 20, 7.5 and 5 fold higher in Hg, Cd and Pb, respectively, than the EU directive. These results outline the necessity for better regulatory criteria in the proposed Mexican NOM in order to minimize the impact on human health and the environment of this type of residues. Ó 2010 Elsevier Ltd. All rights reserved.

Keywords: Batteries Campaign Metal Management Mexico

1. Introduction Environmental pollution produced by disposal of Spent Cells and Batteries (SCB) is a major concern due to the fast growing portable electronic equipment industry that generates thousands of tons of dangerous residues per year. Based on 1992 and 1998 studies, household batteries accounted for approximately 90% of the Hg and 52% of the Cd in Municipal Solid Wastes (MSW) in the US, though that level is projected to decline greatly as manufacturers remove mercury from alkaline batteries (Richard and Woodbury, 1992, 1998). In the EU, the environmental risks related to the disposal of the Cd batteries were assessed in the draft Targeted Risk Assessment Report, ‘‘Cadmium (oxide) as used in batteries’’ (TRAR, 2003). According to the report, the Cd emissions of portable NiCd batteries due to landfill were calculated at 131e655 kg of Cd per year. In 2006, the European Commission * Corresponding author. Tel./fax: þ52 241 4172544. E-mail address: [email protected] (J.A. Guevara-García). 1 Student graduated from the M.Sc. program. 0301-4797/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.jenvman.2010.09.019

required a closed cycle system for all the SCB (Directive 2006/66/EC, 2006) with the purpose of reduce the quantity of spent batteries and accumulators and to set targets for collection and recycling. The US Department of Health and Human Services’ Agency for Toxic Substances and Disease Registry states that the metals in batteries can have serious health effects if not managed correctly. Hg at high levels can damage the brain, kidneys and a developing fetus. Pb can harm the nervous system, kidneys and reproductive system. Cd can damage the lungs and kidneys, and irritate the digestive tract. Exposure to large amounts of Zn can cause stomach cramps, anemia and changes in cholesterol levels. And each metal can have a direct harmful effect on the environment (ATSDR, 2010). The first legal precedent for regulation of SCB in México arose in 1988 with the general law of the ecological balance and the protection of the environment (LGEEPA). This law classifies the SCB as potential dangerous residues given the toxicity risk of some of its components, although the inadequate handling of SCB has continued being a common practice. Mexico’s National Institute of Ecology (INE) estimates that from 1960 to 2003, the following residues have been deposited in MSW: 145,918 ton of MnO2;

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1232 ton of Hg; 22,063 ton of Ni; 20,169 ton of Cd and 77 ton of Li compounds (Castro-Díaz and Díaz-Arias, 2006). The Mexican Association of Manufacturers and Commercial Dealers of Batteries (Amexpilas) claims their batteries do not pollute the environment and have made efforts to convince public opinion only informal batteries (which have questions regarding legal registrations and corresponding business procedures) are polluting (Vega-Vieyra, 2006). The total market (single use and rechargeable) is approximately 650 million batteries per year. This corresponds to about 500 and more than 200 million dollars per year for formal and informal batteries, respectively (Aguilar and García-Camargo, 2006). In 2006, the federal government made public the proposed Mexican Official Norm (NOM) NMX-AA-104-SCFI-2006. There are important differences between the EU directive 2006/66/ EC and the proposed Mexican NOM: the maximum permissible levels for Hg, Cd, and Pb are 20, 7.5, and 5 times, respectively, higher than the EU directive, and approved legal batteries are permitted to be discarded in landfills. Since the article was first submitted, the Mexican Republic Senate urged the Secretariat of Environment and Natural Resources to implement a comprehensive management program of SCB, and requested that the head of the Department of Environment and Natural Resources report the situation of the proposal PROY-NMXAA-104-SCFI-2006, asking for its publication if it had completed the consultation process (Mexican Senate, 2009). However, the proposal has not advanced, and some specialists are afraid that the legislation, rather than encouraging the recycling of batteries with the responsible participation of consumers, producers and local authorities, became a disincentive to do so (Cortinas de Nava, 2009). Other Latin-American countries have similar situations: official policies and regulations only establish limits to the potentially hazardous metal content used on batteries’ composition but do not mandate the participation of producers and importers. In Argentina, an environmental organization demanded the publication of a law which provides for extended producer responsibility, but it was delayed in the Senate (Greenpeace-Argentina, 2010). In Colombia, the proposed law No. 69 (2009) of the Republic Senate contemplates repurchase of batteries, and electrical and electronic waste by the manufacturers (Gladis, 2009). In Brazil, the CONAMA regulations (2001) prohibited the marketing of batteries with concentrations higher than the stipulated limits of Hg, Cd and Pb, but batteries with lower content can be landfilled. A broader and potentially more effective regulation was established by the Brazilian State of Rio Grande do Sul, where law 11.187 (1998) prohibits the disposal of any material containing heavy metals together with MSW (Soares Tenório, 2003). In this work, an official program to collect SBC in Central Mexico was used to: 1) conduct a statistical evaluation of the incidence of informal commerce batteries compared to the formal ones; 2) study the residual voltage of SBC to help assess optimal use of this energy source and the potential inclusion of residual energy recovery as part of recycling technology; and 3) study the metal composition of used batteries from formal and informal market to determine if there is a significant difference in their metal content. The objective of this paper was to use these results to evaluate the potential effectiveness of proposed Mexican NOM by classifying both types of SCB (formal and informal market) under this NOM and the EU directive 2006/66/EC.

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Fig. 1. Statistical results for the used batteries collection campaign. Above: Distribution by type of battery; Below: Cake plot for market of origin of type “AA” batteries. A cake plot for distribution of trademarks (formals and informals) can be consulted in the Supplementary material.

(area of 52.449 Km2 and 83,748 inhabitants). A collection point was installed in every one of the eleven auxiliary municipal presidential offices. The exhausted portable batteries from the collection points were concentrated and separated in trademarks, models, and the market of origin (formal or informal). Residual voltage of random selected batteries type “AA” from the four major trademarks was measured. Statistical analysis was made with the program Origin V6.1. The collected batteries reflected what the local population voluntarily brought to the collection centers. Although we did not

2. Materials and methods 2.1. Compilation of spent batteries The collection of spent batteries was carried out from June 2007 to January 2008 in the city of Tlaxcala and its municipal territory

Fig. 2. Distribution of voltages frequency for Duracell type “AA” batteries collected.

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J.A. Guevara-García, V. Montiel-Corona / Journal of Environmental Management 95 (2012) S154eS157

Table 1 Metal composition (%) for the electrolyte paste/graphite mixture in batteries.a Trademark

Zn

Formal market batteries Duracell Eveready Kodak Heavy duty Panasonic

Mn

27.79 21.75 16.46 26.06 17.60

    

4.46 0.20 8.11 19.04 0.65

22.61 12.52 38.30 36.82 26.80

    

0.53 0.15 3.00 1.06 0.07

0.58 0.31 0.84 0.88 0.65

    

0.03 0.01 0.01 0.02 0.02

0.17 0.30 0.46 0.11 0.68

    

0.07 0.02 0.12 0.06 0.31

0.44 0.10 0.27 0.52 0.42

    

0.12 0.01 0.06 0.07 0.07

Informal market batteries Power cell Glip 2000 Tectron Rocket

21.32 17.24 13.01 21.12

   

5.52 2.82 0.11 3.32

25.09 27.34 21.70 25.05

   

0.83 0.67 0.97 0.89

0.62 0.64 0.51 0.60

   

0.03 0.02 0.01 0.03

0.32 0.46 0.32 0.47

   

0.07 0.34 0.14 0.071

0.66 0.21 0.11 0.50

   

0.30 0.01 0.01 0.09

ANOVA analysis for formal and informal market groups f 0.29 p 0.60 a

Hg

0.22 0.64

Cd

0.25 0.62

0.01 0.92

Pb

0.01 0.90

Every entry represents the arithmetic media of nine determinations and is presented with 1 standard deviation.

evaluate how this might reflect the actual proportions of various batteries that were purchased, we have no reason to believe that the collected batteries over-represent the proportion of informal market batteries or that differences between our sampling and the actual purchased batteries would significantly alter the conclusions of this study. 2.2. Analysis of metal content 90 spent size “AA” batteries (alkaline and Zn/C) were selected at random from nine brands: five formal and four informal market type. The batteries were manually dismantled, and the electrolyte paste and the graphite electrode were recovered and quantified and then ground by hand with a mortar and sieved using a 500 mm standard sieve. From the electrolyte/graphite dust mixture, 10 mg was digested in 10 mL of concentrated nitric acid (Fluka TraceSelect for trace analysis) using a PTFE Parr microwave acid digestion bomb 4782 (45 mL) and digested according to the USEPA Method 3052 (USEPA, 1995a). The solutions were analyzed for Zn, Mn, Hg, Cd, and Pb content according to the USEPA Method 6010B (USEPA, 1995b), using a PerkineElmer ICP-OES, model Optima 2000DV equipped with hydride generator. Conditions for experiments: axial plasma, 1500 W forward power, 15 L/min argon coolant flow, 1.5 L/min argon nebulizer flow, 1.8 mL/min sample pumping rate with a 1 min preflush time. The analyses were performed in five replicates of the same digest. The water used in the solutions was reagent grade from a Millipore Simplicity/SimPak water purification device. 3. Results and discussion 3.1. Battery collection campaign statistics A total of 15,752 spent batteries, almost 1.5 tons, were collected. Type “AA” had the highest incidence of consumption and informal market batteries almost reached 30% of the total “AA” type (Fig. 1). Trademarks of greater incidence were Duracell (18%), Tectron (informal) (15.9%), Sony (14.2%), and Panasonic (12.4%). The residual voltage of 700 batteries type “AA” selected at random from the four highest incidence trademarks was determined. In Fig. 2, the distribution of residual voltage in the collected Duracell “AA” batteries is shown. It was observed that 36% of the batteries had a residual voltage in the range 1.2e1.4 V, whereas 70% of the batteries had voltages greater than 1.0 V. Findings were similar in the other three brands (Supplementary material).

It is to note that residual voltage did not follow a normal frequency distribution. Nowadays, batteries’ energy is used in electronic devices of high current demand in most cases. Discharge reaction takes place in the outer zones of the electrode, where mass transport is fastest. With an increasing demand, the electrode reactions take place within the electrode structure, leading to diffusion overpotential, poorer electron transfer kinetics and to concentration polarization (Hamann et al., 2007). Batteries cannot supply sufficient power after a while and the user likely discard them. An estimate of 420 million type AA batteries would be commercialized in Mexico every year (NMX-AA-104-SCFI-2006), 189 million of them would contain sufficient residual energy available for other applications, projecting our statistical data. Recovery of residual energy from SCB have not been taken into account until now (Bernardes et al., 2004; Ferella et al., 2008) and could be economically attractive. 3.2. Analysis of metal content The Zn, Cd, Hg, Mn, and Pb composition of the electrolyte/ graphite dust mixture of the nine battery trademarks analyzed is shown in Table 1. An ANOVA analysis for formal and informal market group batteries shown there is no difference between the two groups at 95% significance level. Therefore, there is no support for the argument that pollution comes only from informal market batteries. Legal market batteries normally have a robust housing seal, generally of steel, which reduces the probability of internal material release for more than 10 years. The informal market batteries are less robustly sealed e cardboard covered with plastic and their components can be released more easily in a shorter time frame. Some studies in countries with inadequate standards indicates that direct disposal of spent household batteries into MSW landfills increase the heavy metal contents in the landfill leachate (Panero et al., 1995; Puetpaiboon et al., 2001; Sohn et al., 2002; Selvapathy and Madhavan, 2003; Karnchanawong and Limpiteeprakan, 2009). Hence, the battery wastes have to be considered as hazardous wastes and should not be mixed with the municipal solid waste, a prevision observed in the EU Battery Directive Extended Impact Assessment (2003) (Kierkegaard, 2007). 4. Conclusions Based on electrolyte paste/graphite content, under the proposed Mexican NOM regulations, all nine battery trademarks analyzed meet the permissible limit levels and would be considered as

J.A. Guevara-García, V. Montiel-Corona / Journal of Environmental Management 95 (2012) S154eS157

having no dangerous residues. However, eight of nine of the battery trademarks would not meet the EU directive 2006/66/EC standard, which for the reasons described previously, better controls human health and environmental contamination risks. These results stress the urgent need to review the proposed Mexican NOM to prevent the disposal of formal and informal market SCB, stimulate R&D in recycling technology, require that manufacturers and commercial dealers participate in the collection and recycling of SCB, and establish goals for collection, recycling, and to reduce the levels of toxic metals in batteries. Acknowledgements To Dr. Timothy Landry for his technical advice and valuable discussion. To Ing. Ramiro de la Cruz, head of Tlaxcala Attorney’s Office of Protection to the Environment (PROFEPA), for his valuable collaboration. VMC acknowledge the fellowship from CONACYT to M.Sc. studies, Reg. No. 227771. Appendix. Supplementary material Supplementary data related to this article can be found online at doi:10.1016/j.jenvman.2010.09.019. References ATSDR, 2010. Agency for Toxic Substances and Disease Registry. http://www.atsdr. cdc.gov/ 4770 Buford Hwy NE, Atlanta, GA 30341. Website (page last updated 02.06.10.). Aguilar, J.A., García-Camargo, E., 2006. PILAS: Las tiro o las acopio? Revista del Consumidor. Procuraduría Federal de Protección al Consumidor (PROFECO). www. profeco.gob.mx/revista/publicaciones/adelantos_06/pilas_ago06.pdf, pp. 67e70. Website (last access date August 2010): Bernardes, A.M., Romano Espinosa, D.C., Soares Tenório, J.A., 2004. Recycling of batteries: a review of current processes and technologies. J. Power Sources 130, 291e298. Castro-Díaz, J., Díaz-Arias, M.L., 2006. In: INE (Ed.), La contaminación por pilas y baterías en México. http://www.ine.gob.mx/ueajei/publicaciones/libros/438/ cap5.html Website (last access date: August 2010). Cortinas de Nava, C., 2009. Para lograr un México limpio y sin basura. http://www. pvem.org.mx/haciab1.htm Website (last access date August 2010). 2006/66/EC of the European Parliament and of the Council of 8, 2006. Official Journal of the European Union. EU Battery Directive Extended Impact Assessment, 2003. http://www.aeanet.org/ governmentAffairs/gajg_EU_batteries_impactassessment.asp Website (last access date June 2010).

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