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Microbial Transformation of Organotin Compounds under Simulated Landfill Conditions
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
2007 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Mikrobiell omsättning av tennorganiska föreningar under simulerade deponiförhållanden (Swedish)
Abstract [en]

Mono- and di-alkyltins are used extensively as heat stabilizers for processing of poly vinyl chloride (PVC). Tin mercaptide stabilizers are some of the most effective PVC stabilizers available. The main applications for tin stabilizers are building/construction products, such as pipes, fittings, siding and profiles (windows etc.), packaging and flexible PVC plastics. Most PVC products have been and are subjected to landfilling, when their use is terminated. The structure of the polymer itself and the substances used as additives have been a concern for environmental authorities in many countries since long, which also includes their presence in landfills. In the case of the organotin stabilizers their leaching out from (PVC) plastics into the leachate phase of landfills with the risk for further transport to ground and surface waters is in focus.

The main objectives of this thesis take their start in this background and, thus, included the elucidation of whether organotin compounds (OTs) in stabilized PVC products contribute to the pool of OTs observed in landfill leachates and if these compounds are degradable by the microorganisms developing under anaerobic landfill conditions.

To reach these aims and the research questions raised the forwarded PVC materials were added to muniscipal solid waste (MSW) processed in containers used to simulate the ageing of landfills under forced conditions. These include traditional landfill simulation reactors (LSRs) at a scale of ca 100 L and also at a smaller scale ca 5 L constructed for the purpose of this study, i.e. the modular environmental test system (METS). The latter were used to investigate temperature effects on the possible release of OTs from different types of PVC materials. The capacity by microorganisms in landfill environments were used to investigate their capacity to degrade or transform organotin stabilizer compounds focused on in this thesis. Differences in this capacity in relation to the ageing of landfills and exposure to the alkyltin stabilizers were studied with microorganisms sampled from LSRs spiked with PVC over time and from landfill site.

Access to sensitive and reliable equipment and analytical protocols for the analysis of OTs and their transformation intermediates and end products are prerequisites for this kind of studies. This necessitated an adoption and adaptation of analytical methods for the low concentrations occurring in the environment. Two methods were established and well served the requirements.

Indeed OTs migrated out from especially flexible PVC materials, while rigid PVC was less prone for OT release as judged from the METS simulations. The METS studies showed that the OT release increase substantially at higher temperatures and especially so when the temperature was higher than the glass transition of the PVC.materials.

The organotin stabilizers were transformed, partly or completely degraded, by anaerobic microorganisms derived from landfill environments. Upon prolonged exposure to OTs leaching from PVC in LSR simulations the microorganisms displayed a higher efficiency in degradation of the leached OTs. The microorganisms would methylate inorganic tin and metyltin present in the MSW material as well as perform dealkylation depending on the tin concentrations prevailing. During these studies it was discovered that the organotin stabilzers were inhibiting the methanogens and fermentative bacteria, which lead to a retardation of the anaerobic mineralisation of the MSW in the assays. An in depth study revealed that the OTs themselves but also their ligands and degradation products from these together effected the inhibition.

However, given the extent of leaching in relation to the water flows in landfills, the concentrations will mainly be too low to pose any risks to the surrounding environment.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2007. , 52 + papers 1-5 p.
Series
Linköping Studies in Arts and Science, ISSN 0282-9800 ; 415
Keyword [en]
Organotin compounds, landfill simulation, PVC
National Category
Environmental Sciences
Identifiers
URN: urn:nbn:se:liu:diva-10278ISBN: 978-91-85895-13-7 (print)OAI: oai:DiVA.org:liu-10278DiVA: diva2:17026
Public defence
2007-12-14, Elysion, Hus T, Campus Valla, Linköpings Universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2014-09-10
List of papers
1. Impacts of Temperature on the Leaching of Organotin Compounds From Poly(vinyl chloride) Plastics: A Study Conducted Under Simulated Landfill Conditions
Open this publication in new window or tab >>Impacts of Temperature on the Leaching of Organotin Compounds From Poly(vinyl chloride) Plastics: A Study Conducted Under Simulated Landfill Conditions
Show others...
2007 (English)In: Journal of Vinyl and Additive Technology, ISSN 1083-5601, Vol. 13, no 4, 176-188 p.Article in journal (Refereed) Published
Abstract [en]

The aim of the study was to investigate whether organotin-stabilized poly(vinyl chloride) (PVC) products could contribute to the pool of organotins observed in landfill leachates, and if the possible release could be related to different temperatures and landfill degradation phases. Small-scale anaerobic reactors filled with generic household waste, a mixture of inocula, and different PVC plastics were used in the study and incubated at 20, 37, 55, and 70°C. The reactor units incubated at temperatures of 20-55°C underwent the anaerobic degradation phases that are characteristic for the aging of landfilled waste material. There were, however, differences in the duration of the phases as well as in the total biogas production among the units. Under methanogenic conditions greater losses of organotin compounds were observed as compared to acidogenic conditions. It was shown that the release of organotin stabilizers increases considerably at temperatures above the glass transition of the PVC products. A dealkylation from di- into monoalkyltin species was observed, as well as a possible methylation of inorganic tin. However, the main part of the organotins was adsorbed into the solid waste matrix.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-12773 (URN)10.1002/vnl.20131 (DOI)
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2009-04-23Bibliographically approved
2. Effects of an organotin stabilizer on anoxic degradation of organic matter
Open this publication in new window or tab >>Effects of an organotin stabilizer on anoxic degradation of organic matter
2003 (English)In: Journal of Water Management and Research / Vatten: Tidskrift för vattenvård, ISSN 0042-2886, Vol. 59, 271-277 p.Article in journal (Refereed) Published
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-12774 (URN)
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2009-04-28
3. Transformation of methyltin chlorides and stannic chloride under simulated landfill conditions
Open this publication in new window or tab >>Transformation of methyltin chlorides and stannic chloride under simulated landfill conditions
2011 (English)In: Waste Management & Research, ISSN 0734-242X, E-ISSN 1096-3669, Vol. 29, no 12, 1327-1336 p.Article in journal (Refereed) Published
Abstract [en]

There is increasing concern regarding the fate of methyltins in the environment, particularly since large amounts of polyvinyl chloride (PVC) plastics are deposited in landfills. The potential transformation of methyltin chlorides and stannic chloride in landfills was investigated, by incubating the target substances at concentrations relevant to landfill conditions (100 and 500 mu g Sn L(-1)). The amounts of methane formed in all treatment bottles, and controls, were measured to evaluate the general microbial activity of the inocula and possible effects of methyltins on the degradation of organic matter. The methyltins and stannic chloride were found to have no significant inhibitory effects on the activity of landfill micro-organisms, and the methanol used to disperse the tin compounds was completely degraded. In some experimental bottles, the methanol degradation gave rise to larger methane yields than expected, which was attributed to enhanced degradation of the waste material. Alkyltin analyses showed that monomethyltin trichloride at an initial concentration of 500 mu g Sn L(-1) promoted methylation of inorganic tin present in the inoculum. No methylation activities were detected in the incubations with 100 mu g Sn L(-1) methyltin chlorides (mono-, di- or tri-methyltin), but demethylation occurred instead. Levels of soluble inorganic tin increased during the incubation period, due partly to demethylation and partly to a release of tin from the waste inocula.

Place, publisher, year, edition, pages
Sage Publications, 2011
Keyword
Landfill; methylation; methyltin chlorides; municipal solid waste; polyvinyl chloride; transformation
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-12775 (URN)10.1177/0734242X10397088 (DOI)000297518600011 ()
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2012-01-12
4. Degradation of Organotin Stabilizers
Open this publication in new window or tab >>Degradation of Organotin Stabilizers
Manuscript (Other academic)
Identifiers
urn:nbn:se:liu:diva-12776 (URN)
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2010-01-13
5. Environmental analysis of organotin compounds in municipal solid waste by use of gas chromatography and atomic emission detection
Open this publication in new window or tab >>Environmental analysis of organotin compounds in municipal solid waste by use of gas chromatography and atomic emission detection
Manuscript (Other academic)
Identifiers
urn:nbn:se:liu:diva-12777 (URN)
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2010-01-13

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