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Impacts of Temperature on the Leaching of Organotin Compounds From Poly(vinyl chloride) Plastics: A Study Conducted Under Simulated Landfill Conditions
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
Department of Waste Management, Technical University of Hamburg-Harburg, D-21079 Hamburg, Germany.
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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.

Place, publisher, year, edition, pages
2007. Vol. 13, no 4, 176-188 p.
National Category
Environmental Sciences
Identifiers
URN: urn:nbn:se:liu:diva-12773DOI: 10.1002/vnl.20131OAI: oai:DiVA.org:liu-12773DiVA: diva2:17021
Available from: 2007-12-04 Created: 2007-12-04 Last updated: 2009-04-23Bibliographically approved
In thesis
1. Leaching and Transformation of Flame Retardants and Plasticizers under Simulated Landfill Conditions
Open this publication in new window or tab >>Leaching and Transformation of Flame Retardants and Plasticizers under Simulated Landfill Conditions
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Läckage och transformation av flamskyddsmedel och mjukgörare under simulerade deponiförhållanden
Abstract [en]

Many products used in our everyday life contain chemicals added to give them specific properties. Flame retardants (FRs) are added to prevent or retard fires in textiles, plastics etc., while plasticizers are supplied to make plastics more flexible. Through their widespread applications chemicals from both groups are emitted and spread in the environment during usage and disposal. For a long time these products were mainly disposed of in landfills, and in many areas they still are. Thus, since some of these chemicals also pose potential environmental risks and health hazards, there is a need to elucidate their fates during exposure to the landfill environmentThe objectives of this thesis were to investigate the leaching and transformation of FRs and plasticizers from products in which they are used under simulated landfill conditions. To assess the importance of changes in these processes as landfills progress through recognised ageing phases (accompanied by large transitions in both physico-chemical and biological conditions) it was desirable to simulate the changes that typically occur in landfills within a short time period, of 1-2 years.. This was achieved using the newly developed intermediate-scale (3 litre) Modular Environmental Test System (METS).The METS were employed in two studies. The first was an investigation of the leaching and degradation of plasticizers from PVC carpet material incubated at different temperatures (20, 37, 55 and 70°C) prevailing in landfills. Plasticizers subjected to this investigation were the phthalates di-2-ethylhexyl phthalate (DEHP) and benzyl-butyl phthalate (BBP), both of which were found to leach from the carpet. The leaching of DEHP and BBP generally increased with increases in the incubation temperature. However, the most rapid leaching of BBP occurred at 37°C, probably due to high microbial activity at this temperature. Both DEHP and BBP were shown to be degraded within the landfill environment and the degradation potential was highest during the methanogenic landfill phase. In the second METS study the leaching of FRs used in both reactive and additive applications (i.e. chemically bonded to and merely blended with the material, respectively) was characterised. The epoxy oligomer tetrabromobishpenol A (TBBPA) and the phosphorus-based Pyrovatex FRs were selected as representatives for the reactive FRs, while the nitrogen-based melamine and phosphorus-based Proban FRs were selected to represent additive classes. During the incubations, which lasted more than two years, the leaching from melamine was shown to be affected by the landfill phase development. The leaching from the Pyrovatex-treated material and the TBBPA epoxy oligomer seemed to result almost entirely from the washout of unreacted manufacturing residuals. This was also probably true for the FR in the Proban-treated material, although it is durable (despite being additively applied) and thus seemed to leach more slowly (manifested as an increase in phosphate levels in the leachate towards the end of the monitoring period).Finally, due to the paucity of knowledge regarding the fate of ether derivatives of TBBPA (which are also used as FRs) an anaerobic degradation assay was performed. The method employed for this assay was a modified, small-scale ISO standard method. In order to evaluate the degradation assay a uniform analytical protocol was developed. The degradation survey showed that losses of TBBPA, TBBPA-dimethyl ether and bisphenol A dimethyl ether occurred, but no losses of the most hydrophobic compound, TBBPA-dibromopropyl ether, were observed.

Abstract [sv]

Många av de varor och produkter vi kommer i kontakt med dagligen innehåller kemikalier, som tillsats för att materialen i produkterna skall få specifika egenskaper. Till dessa sk funktionella kemiska föreningar hör till exempel flamskyddsmedel och mjukgörare. Den förra förhindrar att produkter fattar eld eller minskar omfattningen av brand. Mjukgörare ingår fr a i plaster för att dessa skall bli smidiga och formbara. Eftersom stora mängder av dessa substanser används eller har använts i produkter i samhället har de spridits till många miljöer. Produkterna hamnar ofta på soptipp, då de inte används mer eller är utnötta. Eftersom flera av dessa substanser innebär risk för hälsa och miljö, är det påkallat att utreda hur de beter sig i soptippsmiljön.Syftet med detta avhandlingsarbete är att undersöka eventuell frisättning och omvandling av dessa två typer av funktionella kemikalier i deponimiljö. Sedan tidigare vet man att sådan frisättning kan var starkt kopplad till åldern och därmed utvecklingen av den kemiska och fysiska miljön förändrats fr a genom tillväxten av mikroorganismer i soptippen. För att komma åt att studera frisättningen under de för deponier karakteristiska utvecklingsfaserna utvecklades en metod (Modualr Environmetal Test System; METS) för att simulera faserna över relativt kort tid (ca 1-2 år). I avhandlingen presenteras två studier, där METS utnyttjats: 1) Frisättning av mjukgörare från en PVC-matta i relation till temperaturer, som uppträder i soptippar (20-70oC) samt 2) Läckage av olika flamskyddsmedel i reaktiv respektive additiv användning studerades för olika applikationer. Vid reaktive applikation är flamskyddsmedlet kovalent bundet till polymeren i produktmaterialet, medan det additivt använda flamskyddsmedlet är inblandat i materialet.Två ftalater (di-2-etylhexyl ftalat, DEHP och bensyl-butyl ftalat (BBP), visade sig läcka från mattan, vilket ökade med högre temperature. De frisattes dock som mest vid 37oC, vilket sannolikt beror på den höga mikrobiella aktiviteten vid denna temperatur. Båda ftalterna bröts ned i soptippsmiljön och hastigheten var störst i den metanogena fasen.En epoxyoligomer (tetrabromobishpenol A TBBPA) och Pyrovatex, som bygger på en fosforförening, användes som modeller för reaktiva flamskyddsmedel. Melamin, som klassas som ett kvävebaserat flamskyddsmedel, fick tillsammans med Proban (fosforbaserat) represen-tera de som används additivt. Medan en frisättning av melamin kunde relateras till utvecklingen av deponimiljön simulerad i METS, så verkar den observerade frisättningen av kemikalierna från de reaktivt behandlade Pyrovatexmaterialet och från epoxipolymeren TBBPA förr ha en fysikalisk-kemisk grund oberoende av utvecklingsfaserna i tippmodel-lerna. Flamskyddsmedlen tvättades helt enkelt ut ur de behandlade produkterna. Probanbehandlingen, som motstår förhållandevis många tvättar trots att det används additivt, visade sig läcka långsamt utan en direkt koppling till fasutvecklingen i METS.Kunskaperna om vad som händer med TBBPA:s eterderivat i deponier är i stort sett obefintliga. Flera av dessa derivat används också som flamskyddsmedel. Därför genomfördes en anaerob nedbrytningsstudie av dessa substanser. För att kunna göra denna studie behövdes en omfattande anpassning och utveckling av metodik, vilket resulterade i ett nytt protokoll för analys av dessa ämnen i olika matriser. Studien visade minskning av koncentrationerna av TBBPA, TBBPA-dimetyleter och bisfenol A dimetyl eter, vilket kan tas som ett tecken på att en transformation och/eller nedbrytning skett. Då dessa föreningar kan omvandlas till mer toxiska substanser bör de undersökas vidare.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2008. 55 + papers 1-5 p.
Series
Linköping Studies in Arts and Science, ISSN 0282-9800 ; 455
Keyword
DEHP, BBP, tetrabromobisphenol A, TBBPA, TBBPA-DAE, TBBPA-DBPE, TBBPA-DHEE, Proban, Pyrovatex, Melamine
National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-15204 (URN)978-91-7393-790-0 (ISBN)
Public defence
2008-10-03, Val, Campus Valla, Linköpings universitet, Linköping, 10:15 (Swedish)
Opponent
Supervisors
Available from: 2008-10-28 Created: 2008-10-23 Last updated: 2014-09-19Bibliographically approved
2. Microbial Transformation of Organotin Compounds under Simulated Landfill Conditions
Open this publication in new window or tab >>Microbial Transformation of Organotin Compounds under Simulated Landfill Conditions
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Mikrobiell omsättning av tennorganiska föreningar under simulerade deponiförhållanden
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
Organotin compounds, landfill simulation, PVC
National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-10278 (URN)978-91-85895-13-7 (ISBN)
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

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Björn (Fredriksson), AnnikaHörsing, MarithaKarlsson, AnnaEjlertsson, Jörgen

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