liu.seSearch for publications in DiVA
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Leaching and Transformation of Flame Retardants and Plasticizers under Simulated Landfill Conditions
Linköping University, The Tema Institute, Department of Water and Environmental Studies. Linköping University, Faculty of Arts and Sciences.
2008 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Läckage och transformation av flamskyddsmedel och mjukgörare under simulerade deponiförhållanden (Swedish)
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 [en]
DEHP, BBP, tetrabromobisphenol A, TBBPA, TBBPA-DAE, TBBPA-DBPE, TBBPA-DHEE, Proban, Pyrovatex, Melamine
National Category
Environmental Sciences
Identifiers
URN: urn:nbn:se:liu:diva-15204ISBN: 978-91-7393-790-0 (print)OAI: oai:DiVA.org:liu-15203DiVA: diva2:113677
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
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. Investigation of sorption phenomena by solid-phase extraction and liquid chromatography for determination of some ether derivatives of tetrabromobisphenol A
Open this publication in new window or tab >>Investigation of sorption phenomena by solid-phase extraction and liquid chromatography for determination of some ether derivatives of tetrabromobisphenol A
(English)Manuscript (Other academic)
Abstract [en]

Observed sorption and chromatographic behaviour served as a starting point for examination of four ether derivatives of the flame retardant tetrabromobisphenol (TBBPA). To date, there is little or no information about these compounds in the scientific literature. The targets in the present study had calculated log Kow values of 6.0–10, indicating a rather hydrophobic nature. A broad range of different types of solvents were used in order to elucidate the mechanisms of sorption on one hydrophilic surface (silica) and two hydrophobic surfaces (polystyrene divinylbenzene polymers). Also, three chromatographic columns (C18, C8, and dual C18-based) were evaluated. In general, the most hydrophilic and the most hydrophobic derivatives (dihydroxyethyl- and di(2,3-bromopropyl), respectively) were more easily desorbed from the studied surfaces by the selected solvents.Regardless of the experimental test conditions applied, the lowest recovery was seen for dimethoxy-TBBPA, followed by TBBPA itself. Also, this study claims that the polar character of the dual-phase column was not as pronounced as asserted by the manufacturer.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-15206 (URN)
Available from: 2008-10-23 Created: 2008-10-23 Last updated: 2010-01-14Bibliographically approved
3. Effects of Temperature and Landfill Ageing on leaching and Degradation of Phtalates from a Poly(vinyl chloride) Carpet under Simulated Landfill Conditions
Open this publication in new window or tab >>Effects of Temperature and Landfill Ageing on leaching and Degradation of Phtalates from a Poly(vinyl chloride) Carpet under Simulated Landfill Conditions
Show others...
(English)Manuscript (Other academic)
Abstract [en]

 

Phthalic ether esters are a group of chemicals used in the manufacture of PVC plastics, often as plasticizing additives, hence they may leach from the material and/or finished products before, during and after their use. This article presents results from laboratory-scale investigations of the fates of di-2-ethylhexyl phthalate (DEHP) and benzyl-butyl phthalate (BBP) under simulated landfill conditions, in custom-designed incubation units filled with model municipal solid waste. More specifically, the effects of temperature and landfill degradation phase on both the leaching and degradation potential of the two phthalates from a PVC carpet were examined, by measuring them in samples from units maintained at 20, 37, 55 and 70°C as they progressed through anaerobic acidogenic and methanogenic landfill phases. The results show that both BBP and DEHP leached from the carpet. For DEHP there was a clear temperature effect, and the highest losses were observed at 70°C, while for BBP slight increases in losses with temperature were observed from 20 to 55°C, and from 55 to 70°C, but the largest losses were seen at 37°C, probably due to biodegradation. Further degradation of the leached phthalates occured at all temperatures. Apparent degradation products observed included phthalic acid (PA) and mono (2-ethylhexyl)-, monobutyl- and monobenzyl-phthalate. In all cases the biological degradation of the phthalates occurred mainly after the systems switched to methanogenic conditions. The rate-limiting step of degradation in the 20 and 37°C units seemed to be the transformation of the monoesters, which tended to accumulate more than PA, while at 55 and 70°C PA accumulated to a higher extent.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-15207 (URN)
Available from: 2008-10-23 Created: 2008-10-23 Last updated: 2010-01-14Bibliographically approved
4. Leaching of Flame Retardants from products deposited in Landfills
Open this publication in new window or tab >>Leaching of Flame Retardants from products deposited in Landfills
(English)Manuscript (Other academic)
Abstract [en]

Materials in many products in daily use are amended with chemicals to give them desired properties, e.g. flame retardants (FRs) used to reduce the risks of products catching fire. However, potential risks posed by some of these chemicals, including FRs, to the environment and human health have raised concerns. Hence, there is a need for more knowledge regarding the fate of FRs, notably in landfills, where many FR-containing products are deposited. This article presents analyses of FRs and derivatives in leachates sampled during laboratory-scale simulations of landfills containing various FR-containing products progressing through typical landfill ageing phases. The FRs represented substances used both reactively, i.e. bound to the flame-protected material and additively, i.e. without any covalent bonding to the product.The phosphorus-based Pyrovatex-FR and the brominated tetrabromobisphenol A (TBBPA) were used to represent the reactive FRs, and the nitrogen-based melamine and phosphorus-based FR of Proban the additive FRs. Residual FRs from the treatment of the materials were probably the main contributors to the leachates from all products. Their durability, i.e. ability to withstand laundry washes, was reflected in their leaching abilities, while the different landfill conditions were of minor importance, except for melamine (of which approximately 10% of the amount present in the test product leached and mineralised to carbon dioxide and ammonia, mainly during the period when the landfill models passed from acidogenic to methanogenic conditions). The other additively applied FR in Proban leached first during the later part of the incubation (between 80 and 112 weeks), in accordance with its laundry resistance. Substantial proportions of the residual chemicals in Pyrovatex-treated materials are generally lost during the first washing. Accordingly, early losses of the chemicals used in this treatment were detected during the landfill simulation. Elevated phosphate concentrations were also detected in simulations with the Pyrovatex- and Proban-treated products, suggesting that the FRs generated in these treatments were degraded during or after release to the leachate. Small amounts of TBBPA were observed at the end of the incubation, and no TBBPA degradation products were observed, but debromination (which is likely to occur during anoxic stages) would lead to the formation of bisphenol A.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-15210 (URN)
Available from: 2008-10-23 Created: 2008-10-23 Last updated: 2013-06-12Bibliographically approved
5. Investigation of the transformation potential of some ether derivatives of tetrabromobisphenol A and dimethyl ether of bisphenol A under methanogenic conditions
Open this publication in new window or tab >>Investigation of the transformation potential of some ether derivatives of tetrabromobisphenol A and dimethyl ether of bisphenol A under methanogenic conditions
(English)Manuscript (Other academic)
Abstract [en]

This study focused on transformation of the flame retardant tetrabromobisphenol A (TBBPA) and ether derivatives thereof during incubation under methanogenic conditions using landfill waste as inoculum. Bisphenol A dimethyl ether was also investigated in that context. Glass wool was placed in the incubation flasks to increase the surface area for adsorption of target compounds and thereby maximize exposure to the microbial population. A uniform analytical protocol for extraction of the silica surface and the aqueous phase was developed to suit all the targets. Overall recoveries were lowest for the dimethylated ethers and highest for TBBPA-dihydroxyethylether. TBBPA decreased to below detection limit within 35 days, but neither BPA nor the methyl ether of TBBPA was confirmed as a transformation product. The dimethylated ethers of BPA and TBBPA disappeared within 14 and 51 days, respectively, and BPA, but not TBBPA, proved to be a transformation product. No losses were observed for the most hydrophobic target TBBPA-dibromopropyl ether during the time frame of the transformation study (i.e., 51 days).

National Category
Environmental Sciences
Identifiers
urn:nbn:se:liu:diva-15208 (URN)
Available from: 2008-10-23 Created: 2008-10-23 Last updated: 2013-06-12Bibliographically approved

Open Access in DiVA

fulltext(643 kB)801 downloads
File information
File name FULLTEXT02.pdfFile size 643 kBChecksum SHA-512
95d906df8f3d7ffa5e55772c445a63cdc982d131b733db040301b9f453dbf90d65c7740f553fbd14a56c02f0a53572ccb63abcd93d469e8b39a1cd64134dc917
Type fulltextMimetype application/pdf
cover(784 kB)180 downloads
File information
File name COVER02.pdfFile size 784 kBChecksum SHA-512
d6d38e0e0324ceb19563ca986fd692c4016a3fbad0d7126e91b4fcf43b56a5d11fd6701eb8ab1a696a4c7d6383024c47a5dc01a158ce5ad18f44f873f8f9243c
Type coverMimetype application/pdf

Authority records BETA

Hörsing, Maritha

Search in DiVA

By author/editor
Hörsing, Maritha
By organisation
Department of Water and Environmental StudiesFaculty of Arts and Sciences
Environmental Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 801 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 3055 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf