The Behaviour of PVC in Landfill -...

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1. Objectives of the study:

The aim of this study, which is to cover the fifteen Member States of the European Unions, is to:

a) provide a survey of existing analysis and research as regards the behaviour of PVC in landfills

b) evaluate the environmental impacts of PVC waste after final disposal in landfills. Both theshort term and long term behaviour of rigid and flexible PVC in landfills shall be investigated.The aerobic and anaerobic degradation of both PVC and the additives to PVC shall beassessed as well as the release of additives and breakdown products to soil, groundwater andthe atmosphere.

c) perform both practical analysis on selected landfill sites representative for landfills in theCommunity as well as lysimeter studies. In both the practical analysis on landfill sites and thelysimeter studies, the differences of parameters such as e.g. precipitation, pH, temperatureand geology of soil and underground throughout the Community shall be considered andtaken into account. In the context of a), b) and c) the environmental effects of landfilling PVCmust be estimated.

d) estimate quantities of PVC landfilled as well as the costs of landfilling PVC waste, includingthe environmental costs covering the fifteen Member States of the European Union.

in the context of the European Community Waste Management Policy.

2. Contractor’s tasks:

In the context of 1a), the contractor shall identify and evaluate existing national and internationalstudies on the behaviour of PVC in landfills.

In the context of 1b), the contractor shall analyse both the short term and long term behaviour of rigidand plasticised PVC in landfills. Based on this practical research, the contractor shall assess both theanaerobic and the aerobic degradation of PVC as well as the release of additives to soil, groundwaterand the atmosphere.

In the context of 1c), the contractor shall select landfill sites which are representative for existing andfuture1 European landfill sites from both north and south of the Community. The contractor shallperform studies on the selected landfill sites as well as lysimeter studies. In all studies the influence ofthe variety of parameters (pH, temperature, geology of soil/underground, precipitation, microbialactivity, availability of oxygen and light etc.) must be assessed and evaluated in order to predict theenvironmental effects of emissions (mainly leachate and gas) to all media.

In the context of 1 d), the contractor shall assess existing and estimate future societal andenvironmental costs of landfilling of plasticised and rigid PVC in the fifteen Member States using theanalysis and results achieved under a), b) and c) above.

1 For future landfills compliance with the Commission Proposal for a Council Directive on the landfill of waste should be

assumed.

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3. Schedule of work:

The study must be completed within twelve months from the date of signature of the contract.

An outline of the work shall be submitted within three weeks of the date of the signature of thecontract.

An interim report shall be submitted not later than six months from the date of signature of thecontract.

A draft final report shall be submitted not later than eleven months from the date of signature of thecontract.

A final report shall be submitted not later than twelve months from the date of signature of the contract.

4. Selection criteria:

a) Experience as evidenced by the composition of the proposed team (curricula vitae of teammembers including a reference list of relevant previous projects). This should also show thatthe team is technically capable of carrying out an analysis of the behaviour of PVC in selectedlandfills which are representative for the 15 European Member States.

b) Tenders should have demonstrable experience in the areas that are part of the call for tender.

c) Tenders should be individuals or legal entities (giving registration numbers from officialregisters).

d) Evidence of tender’s financial standing, by furnishing (extracts from) financial statements ofthe last three years.

e) Tenders must be independent entities without any relation economically or politically to thePVC industry, to other plastic industries or to the chlorine industry.

5. Award criteria:

1. Understanding: this criterion serves to assess whether the tenders have fully understood allthe aspects of the services required for the contract, as presented under point 3, as well as ofthe content of the final product.

2. Methodology: the offers will be assessed according to whether the methods they propose foranalysing, reviewing and assessing documents and figures are in conformity with the needs ofDG XI.E.3.

3. Availability: this criterion relates to the rapid availability of the contractor after the start of thecontract and to its further availability during the course of the contract.

4. Points: A maximum of 35 points will be attributed to criterion 1 a maximum of 35 points will beattributed to criterion 2 and a maximum of 30 points will be attributed to criterion 3. Selectedcompanies will have to score a minimum of 25�points per criterion with a minimum total of 80points. Price will be considered in the award decision to determine the best value for moneywhen selecting between technically comparable bids.

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Table to accompany text Chapter 3

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In general data on PVC waste arisings are not specifically compiled by Member States as a matter ofroutine within the context of national waste statistics. However, in some Member States information onPVC waste arisings and amounts of PVC waste being landfilled is available. Data required from otherMember States is depending on information provided by national and international organisations fromwithin the PVC industry. Additional information is compiled from international studies and statistics.

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PVC waste arisings amount to 40,000t in Sweden, PVC waste for landfill derives from the followingwaste streams (Swedish EPA report no. 4672, 1996):

waste streams PVC waste (tonnes)

building and demolition waste 8,600

cables 6,000

packaging 3,300

cars 3,000

electrical/electronic products 1,300

other products 5,500

total amount being landfilled 27,700

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The following figures on PVC waste arisings for the Netherlands (RIVM, 1996) are based on roughestimates. Only municipal solid waste is analysed every year.


municipal solid waste 38,000

retail, trade and services 10,000

industrial waste 3,5000

building and demolition 6,000

cables 15,000

cars 5,000

agriculture 1,500

total PVC waste arisings 80,000

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For Austria the figures are reported as follows (UBA Studie Bd 98, 1998):


building and demolition 20,000

electrical/electronic 4,000

cars 4,000

industrial waste 3,200

packaging 3,000

others 11,000


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In Denmark the total amount of PVC waste is estimated 58,000 t (DEPA Oplæg, 1997), PVC inconstruction waste amounts to between 11,000 - 14,000 t from which approximately 10-15 % isrecycled (DEPA report no. 79, 1997).

In a more recent report from the Danish Environmental Protection Agency DEPA ‘Strategy on thePVC-area, Status and future initiatives, June 1999’, Danish Environmental and Energy Ministry, thefollowing estimates on the amounts of PVC waste are published:


construction 11,000

packaging 4,000

others 19,000


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Data on the amount of PVC waste being landfilled were sought from Member States and othersources. The amounts of landfilled PVC waste varies between 50 and 90% of the total PVC wastearisings for those countries who have provided information. Only in Denmark the landfilled amount ofPVC comprises 30% or less from the total. The table below gives an overview on reported amounts ofPVC being landfilled.

Table 1: Reported and estimated amounts of PVC waste being landfilled

Year of data reported PVC waste being landfilled(tonnes)

Denmark 1999 9,740-11,970

Finland 1998 25,000-30,000

France 1998 150,000

Germany 1995 329,000

Greece 1998 11,000

Ireland 1998 13,300

Sweden 1996 27,700

The Netherlands 1996 45,000

United Kingdom 1998 195,000

Sources of data: Germany - Arbeitsgemeinschaft PVC und Umwelt 1998Austria - Umweltbundesamt Studie Bd 98 1998Denmark* - DEPA Oplæg 'Industrial waste and selected waste streams' 1997Denmark** - DEPA ‘Strategy on the PVC-area, Status and future initiatives, June 1999

Danish Environmental and Energy MinistryFrance - AdemeFinland - Finnish Plastics Industries FederationSweden - EPA report no. 4594Netherlands - data differs depending on different sources: VROM (1996) 46,000t-

86,000t, RIVM (1996) 45,000t, PVC Industry (1995) 28,000tGreece - Sigma PlanUK - Carl Bro UK (own estimation)Ireland - Carl Bro UK (own estimation)Luxembourg - Administration de l'Environnement Division des Déchets

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Available PVC waste arisings (EuPC)

EuropeFinished product

Start ofapplication

Averagelife time

1998 1999 2010 2020

Total PVC 1.945 23 2.593.301 2.670.957 3.443.614 4.540.774

Building products 1.945 33 790.534 828.096 1.276.309 1.819.644

Electrics, electronics 1.950 21 224.058 236.000 344.814 449.007

Automotive 1.950 12 371.566 389.230 442.593 491.886

Agriculture 1.950 10 22.391 22.942 20.309 17.031

Medicine 4 21.160 21.723 25.216 29.871

Furniture 1.950 17 36.781 39.628 77.750 125.193

Household 1.945 11 596.964 625.823 834.057 1.111.619

Packaging 1.945 1 529.847 507.515 422.566 496.523

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PVC waste is generally being disposed of in landfills as part of the municipal solid waste stream ortogether with commercial waste. The up to date collected information regarding the costs are those forlandfilling municipal solid waste and show a wide range of tariffs. There are a number of factors whichinfluence the prices or tariffs for landfills such as i.e. standard of the landfill, competition betweendifferent disposal routes, type and nature of waste being accepted. No influence on prices or tariffscould be related or is expected due to the presence of PVC in municipal solid waste being landfilled.

Figure 3.4: Costs for landfilling

Range of costs in Euro/t

Member States Landfilling of MSW tax

Austria min 62, max 153, average 115Belgium (only Flanders)

min 2,4 - max 65,8average 33,8

Denmark min 14 - max 71, average 32 tax 50

Finland 20 -80 tax 20

France

Germany 18-106 1, 27-280 2

GreeceIreland min 10 - max 25 tax 13, VAT17.5%

ItalyLuxembourgThe Netherlands 42-96 tax 14

PortugalSpain 8-13 3

Sweden construction waste: min 2 - max 117, average14mixed industrial waste: min 2 - max 190,

average 16-35United Kingdom average 21 (+/-14) 14 ECU tax due to increase to

21 ECU by 2005Vat 17,5%

notes: 1 new Bundesländer2 old Bundesländer3 based on information from Catalonia region

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Development in municipal waste/household waste by treatment method in EU in 1985-90 and 1995

Country Year Composting Incineration Landfill Recycling Other Total Unit Source Footnote

Austria 1996 360 431 887 879 218 2775 1000 tonnes 8 2

Belgium 1994 92 499 903 135 1629 1000 tonnes 2 5

Denmark 1995 298 1466 501 330 15 2610 1000 tonnes 2,9 2

Finland 1994 70 50 1500 700 2320 1000 tonnes 2

France 1993 1482 9759 10025 72 21338 1000 tonnes 2 2

Germany 1993 2216 7214 20886 8628 1124 40068 1000 tonnes 12 2

Greece 1992 0,73 2970 226 3196,73 1000 tonnes 2

Ireland 1995 1432 118 1549,962 1000 tonnes 2

Italy 1995 1400 24000 25400 1000 tonnes 2

Luxembourg 1995 8 126 78 87 299 1000 tonnes 2

Netherlands 1996 1300 2600 1750 1910 7560 1000 tonnes 6 2

Portugal 1994 420 3060 3480 1000 tonnes 2,11

Spain 1994 1770,1 625 11901 14296,3 1000 tonnes 2

Sweden 1994 100 1300 1200 500 3100 1000 tonnes 2 2

U K 1995 100 2200 22000 1900 100 26300 1000 tonnes 5 3

Total EU 1995 8136,1 26996 103713 14973 1529 155346,992 1000 tonnes 1 1

Sources:

Source 1 ETC/W

Source 2 OECD, Environmental Compendium 1997



Source 5 Letter from Department of the Environment, Transport and ther regions, UK.170898. (MunicipalWaste Management 1995/96, Department of the Environment, Transport and the Regions, UK 1997.)

Source 6 RIVM (letter to the EEA from Huib Verhagen 100898)

Source 7 Administration de l’Environment, Luxembourg and letter to the EEA from Julia Georgi, EPALuxembourg (100898)

Source 8 Federal Waste Management Plan Austria, 1998

Source 9 Letter to the EEA of 170898 and Waste Statistics 1996, Environmental Review number 4, 1998

Source 10 Letter of 010998 from the Greece Ministry of Environment, Physical Planning and Public works to theEEA.

Source 11 Letter to the EEA of 160998 from Instituto dos Residuos, Portugal adn letter to the ETC/W 7th ofOctober 1998

Source 12 Federal Environmental Agency/Statistical Office, Germany. (Letter to the EEA of 151098)

Footnotes

Footnote 1 For some countries the figures only include treatment and disposal of household waste. The totalquantity of municipal waste treated and disposed is therefore less than the quantity of municipalwaste stated in the table "waste by sector".

Footnote 2 Household waste only

Footnote 3 The figures include only England and Wales. Scotland has a total of 2,99 million tonnes MSW (0,1million tonnes recycled, remainder landfilled.) Northern Ireland has a total of 0,7 million tonnes,virtually all landfilled

Footnote 5 includes for 1994 only Walonia

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Detailed descriptions to accompany text Chapter 6

CONTENTS

1 Analysis of PVC materials2 Identification and investigation of PVC from landfill3 Investigation of the behaviour of PVC in a waste

treatment plant in technical scale4 Lysimeter tests5 Analysis of emissions from lysimeters6 Leaching tests7 Microbiological investigations8 Investigation of toxicological effects of landfilled PVC

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1 Optical investigations by scanning electron microscope of the materials were carried out in co-operation with Prof. Dr. Klaus-Peter Schmitz, department for biomedical techniques at UniversityRostock, faculty of medicine. Because of the very good equipment, the scanning electronmicroscope PHILIPS XL 30 ESEM, no particular pretreatment of the samples was necessary. Toclean the materials an ultrasound bath was used for 15 minutes.

2 At one sample (PVC VI) the influence of the ultrasound treatment to the material wasinvestigated. No changes at the surface could be detected using the scanning electronmicroscope. It can be concluded that the pretreatment in ultrasound bath of the PVC has noinfluence on the results of microscopy. No false interpretation of the behaviour of the PVC underlandfill simulating conditions is possible because of it.

3 The samples were about 8x8 mm in area and were given on adhesive sample-holders into theinstrument. The resulting pictures describe a representative part of the material. That wascontrolled through discovering a greater part of the sample surface at the online monitor.Interpretation of the pictures was carried out with a polymer specialist from the department forbiomedical techniques, Dr. Behrendt.

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4 The mechanical investigations of the PVC-materials consist of the examination of tensile strengthaccording to DIN EN ISO 527.

5 The investigations were carried out in co-operation with Prof. Dr. Klaus-Peter Schmitz,department for biomedical techniques at University Rostock, faculty of medicine. The equipmentZwick Z 2.5 with the tensile dynamometer KAP-Z 0-500 N was used. The evaluation was donewith testXpert V 4.01. Every examination of one material includes at least five singlemeasurements being evaluated to a mean value. From the examination of tensile strength theparameters tensile strength and limit of tensile strain can be derived.

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6 The molecular weight distribution of the samples was determined using gel permeationchromatography at Polymer Standards Service GmbH Mainz. The samples were dissolved overnight in tetrahydrofurane, 5 mg/ml, and filtrated through a 0,45 µm filter. Thereafter 50 µl of thesolutions were injected through the autosampler TSP AS 3000 in the gas permeationchromatograph with the columns PSS-SDV, 5µ, 10³ Å, ID 8.0 mm x 300 mm; PSS-SDV, 5µ, 105

Å, ID 8.0 mm x 300 mm and PSS-SDV, 10µ, 107 Å, ID 8.0 mm x 300 mm. The elution was donewith tetrahydrofurane, 1 ml/min, and the concentration was determined with the TSP UV 2000Shodex differentialrefraktometer RI 71 at 254 nm. The instrument was calibrated according touniversal calibration using polystyrol standards in the area of molecular weight between 374 and2.180.000 g/mol. The evaluation was done with PSS-WinGPC v. 4.02 basing on the stripes-method.

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7 The contents of plasticiser of the raw materials and of the materials taken from the old landfill wasanalysed by the company Oxeno with extensive experience in analysis of PVC. The sampleswere dissolved in tetrahydrofurane. After filtration the tetrahydrofurane was vaporised from thecleaned solution. The residue consist only of tetrahydrofurane-soluble components, i. e. PVC-polymer, plasticiser and organic additives.

8 The contents of chlorine was measured by X-ray-fluorescence-analysis. This value is the basis tocalculate the content of PVC. The difference between 100 % and the parts of PVC is accordinglythen determined as the content of plasticiser.

9 The resulting value may not be seen as the real content of plasticiser, since. It is always too highin value. The rest from filtration residue should be included in the calculation. But, for ourconsideration the results are sufficient since no possibility for comparison with analysis beforelandfilling of the materials does exist.

10 Some further analysis of the contents of additives in the raw materials was carried out by VestolitGmbH. The identifying of the plasticisers was performed with infrared spectroscopy. To determinethe contents of PVC, plasticisers and heavy metals the same methods as described above wereused. The extend of the investigations was to analyse additional heavy metals not identified inprevious analyses

11 The loss of plasticisers from the PVC-materials and PVC-foils during all studies was analysed atUniversity Rostock using gas chromatography. Therefore from all materials to be analysed apiece of 1 cm² in area was extracted in 5 ml acidic acid ethyl ether for 24 hours. 1 µl of the extractwas injected into the gas chromatograph. The used equipment was a gas chromatograph PerkinElmer 8500.

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12 Analysis of stabilisers as heavy metals contained in the samples before incubation was carriedout by the companies Bärlocher and NORDUM. The variation of measured contents cannot beexplained, but may result from different analytical methods.

13 The contents of stabilisers of the raw materials and of the materials taken from the old landfill wasanalysed by the company Bärlocher. The elementary heavy metals were analysed by X-ray-fluorescence-analysis. Special sample preparation was not necessary. In order to the measuredvalues and the experiences of the laboratory the most likely stabiliser system was determined.

14 The loss of stabilisers from the PVC-materials during lysimeter studies in comparison to the rawmaterials was analysed by the laboratory NORDUM Umwelt + Analytik, Institute for environmentand analysis GmbH & Co KG. A sample of 0,1g PVC was broken down in 2ml HNO3 (65%) for 20minutes in the microwave oven (PMD from Kürner) at energy level 10. The obtained solution wasdiluted with water of highest purity getting 25ml mixture. Based on DIN EN ISO 11885-E22 thecontent of heavy metals was analysed by ICP-OES in the equipment JY 24 (jobin Yvon, ISA).

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15 PVC-samples were taken from a landfill with biological pre-treatment. The municipal waste wasmixed with sludge before waste treatment and dumping. The pre-treatment was carried out withthe Kaminzug-method. This method is based on aeration of the waste pit through drain pipes. Anatural air stream is induced by rising warm air in the pit through pipes. It supplies the pitcontinuously with fresh air. Afterwards the waste was dumped in 1977 at the landfill ofSchwäbisch-Hall, one of the most investigated landfills in Germany2. Samples were taken from anamount of this waste taken out during 1998.

16 First identification of PVC was carried out in accordance with the Beilstein-method. In this methoda wire made of copper has to be contaminated with the plastics to be investigated. Now thecontaminated wire has to be given into a high temperature flame. When the flame gets green veryplainly it is almost sure that the sample is made from PVC. The green colour shows the contentsof chlorine in the sample and PVC is the plastics with the highest chlorine contents.

17 Further analysis of the recovered PVC-samples were carried out to get information about thecontents of plasticiser and stabiliser after long time storage in landfill. The methods are describedin the section Chemical analysis in this annex.

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18 Due to time constraints PVC-materials could not be inserted in a landfill. Short term impact of alandfill to PVC would not be detectable and processes would not be describable and comparableto the other experiments carried out in this study. Therefore it was necessary to find a method tosimulate landfill processes in a very short time. A biological waste treatment plant during thephase of intense decomposition seemed to be suitable as alternative to a landfill. That means anacceleration of landfill degradation processes with the same final result as achieved in a landfill[SPILLMANN 1999].

19 The biological waste treatment plant at the landfill Parkentin (Mecklenburg-Vorpommern,Germany) was chosen. There the Herhof-method is used. During treatment organic waste is putfor about two weeks into 35 m³-containers for intensive decomposition. During this phase thewaste is ventilated with fresh air from the bottom of the container. At the same time the contentsof water could be regulated by irrigation of the waste. Temperatures up to 70°C are reachable.Samples were stored in very strong nets made of fibre-reinforced plastic with 10 mm meshes. Inthis way the same conditions outsides and insides the net were guaranteed.

20 The organic municipal waste contains small amounts of normal municipal waste so that thecontents of material is comparable to a landfill, but the degradation processes are much moreintensive and aggressive. Further the organic waste not contaminated with PVC was chosen toexclude interactions as far as possible and to obtain distinct results.

21 To guarantee the development of a microbial population comparable to landfills the PVC sampleswere contaminated and blended with municipal waste before storing them in the containersdesignated for treatment of organic waste.

2 These investigations are described in JOURDAN et.al. 1982 and FISCHER et.al. 1998

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22 After completion of the investigations the inserted PVC-materials were taken out of the plant andanalysed with the same methods as described in section 1 of this annex.

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23 For the lysimeter tests a well established bioreactor was used, this reactor was previouslyemploid to investigate decomposition processes of various kind of organic and municipal waste.The following illustration visualises the lysimeter set up.

figure 1: lysimeter set up for simulation of landfill processes

24 The reactors consist of a QVF - glass column with 10 cm diameter of about 8 litres total volumeequipped with a head and a bottom seal with tube connectors. The system is closed and allowsanaerobic as well as aerobic experiments. To make absolutely sure that the atmosphere is totallyanaerobic the lysimeters are put under pressure by leading argon into them. In this way gaseousemissions can be detected.

25 Gas supply for aerobic and aerobic-anaerobic experiments is guaranteed by compressed air at aconstant air flow rate. For regulation and measurement of gas flow 3.1005.01-flowmeters fromReglerwerk Dresden were used. To analyse exhaust fumes it has to be dried first. Thereforegases were condensed at 6°C with a Proficool WKT 300-1-cooler from National Lab Inc�

gas analysis

temperature controlto compensate lossof energy

leachate recirculationwith pump

gas sampling

heating

PVC samplesin municipal waste

temperature sensor

closed glass reactor

grating

gas supply

flowmeter

gas sample

gas supply

HH22 OO

gas condenser

HH22OO

gas moistening

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Condensates were collected in a glass vessel. Glass pipes filled with charcoal were connecteddirectly to the gas condensers in regular intervals.

26 On the basis of continuos measurements of oxygen and carbon dioxide with Pewatron gasmonitors (EGC 030, EGC 100) oxygen demand as well as carbon dioxide production wasinvestigated. Temporary monitoring of methane production was performed with ProRae gasmonitor.

27 In the lysimeters the waste represents an original section of a landfill and is nearly identical bycomposition to a landfill (see para 30). The lysimeter fulfils the stipulated parameter such as heatbalance, water balance and gaseous balance of the given environment for simulation.

28 The essential problem consists of the accurate simulation of heat balance in conjunction with thebalance of substance within the hyper-thermophilic sphere. The system regulates itself accordingto measurements of its inherent dynamism. The heat-exchange over the surface must be nearlyreduced to zero because of the restricted sample mass and low internal heat production. Adefined heat removal avoids any overheating process which would stop microbiological activity.For this purpose a controllable heating surface, self regulated by internal energy production, isintegrated in the lysimeter.

29 Temperature measurement was realised by using PT100 temperature sensors. Regulation baseson comparison of heating and waste temperature. Energy supply is controlled by a programmablemicroprocessor (Conrad electronics). The datalogger BMC 3010 connected to a personalcomputer was used to record continuously temperature and gas values.

30 To characterise the conditions in the lysimeter the municipal waste used during lysimeter tests willbe described as follows. The waste from which samples were taken, comes from residential areasof the town of Rostock (Mecklenburg-Vorpommern, Germany, approx. 230.000 inhabitants). Thewaste used for the investigations was taken from the surface from the landfill Parkentin nearRostock. The sample area was the area where the fresh municipal waste was landfilled. Thatguarantees that the waste is not older than one week. Sampling at seven different places withinthis surface followed by intensive mixing lead to a representative waste-sample for the lysimetertests. The waste was sieved, the fraction smaller but 50 mm was used after mixing andhomogenising it thoroughly for the lysimeter studies. Well visible pieces of plastics and parts withdisruptive influence (for example batteries) were sorted out. Residues consist mainly of organicwaste. The fillings of the lysimeters were carried out as equally as possible.

31 There was no mechanical deformation such as shredding or grinding carried out to preserve theoriginal structure. On this basis it is possible to compare degradation processes in landfill,biological waste treatment plant and lysimeter.

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32 To examine gaseous emissions from PVC the condensate from lysimeter gas and the gas,enriched on charcoal, from the lysimeters were analysed to characterise its composition. Allanalyses of gas and condensate from the lysimeters was performed as gaschromatographicalfingerprint. The aim of the examination was not to identify substances but to recognise differencesbetween gases.

33 Analysis of the condensate from the lysimeter gas was carried out with the same method as usedfor plasticiser analysis of leachate as described below. For analysis of gaseous emissions from

6

the lysimeter the gas stream was lead through a tube filled with 100 mg charcoal. Most volatileorganic substances adsorb to the coal and enrich by the time. That tube was taken out after 10days of enrichment in the gas stream�and all substances from the charcoal were extracted with 2ml CCl. 1 µl of the extract was injected into the gas chromatograph. The used equipment was atfirst a Hewlett Packard Gas chromatograph but at the end of the study a gas chromatographPerkin Elmer 8500 was used because of new acquisition.

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34 To evaluate emissions caused by the PVC polymer or additives excluding stabilisers the leachatefrom the lysimeters was analysed by gas chromatography. The samples were prepared with liquidextraction. 5 ml of liquid sample were shaken with 5 ml dichloromethane and 2 g waterfree NaSO4

for 30 minutes. The solution was centrifuged and the organic phase was separated. The organicphase was analysed using a gas chromatograph and connected mass spectrometer. Identificationof substances was carried out using the data bank NIST98.

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35 The contents of heavy metals was analysed by the company Nordtest according to the followingstandardised methods: for lead DIN 38406-E6-1, for zinc DIN 38408-E8-1 and for cadmium DINEN ISO 5961 – E19.

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36 For the leaching tests the surface/ volume relation of the different PVC materials I to VII are to beminimised and standardised. The single materials to be analysed were dissolved in a solvent.Afterwards a defined amount was put into a glass cylinder with a diameter of 40 mm. Amongst thepossibility to dissolve PVC – products and to transform them to foils, this method offers a furtheradvantage. Pure PVC – powder and pure PVC – powder combined with additives can betransformed to foils with a defined composition. After vaporisation of the solvent a foil develops,which contains the quantity of the original substances. The foil can be pealed off the groundwithout any deformation and so it can be used for different tests. This method was developed atUniversity of Rostock.

37 To process the foils a 5.1 g sample of pure PVC as well as of PVC with additives was dissolved ina 250 g ml bottle within 100 ml of the pure solvent tetrahydrofurane (THF). The completedissolution to reach a clear fluid of the sample took about 24 hours. Frequent shaking wasnecessary. The premise for a smooth homogeneous surface was the vaporisation of the solvent,slowed down in time. To realise that, a hard filter paper with a pore diameter of 1µm was put onthe abraded rim of the 40 mm glass cylinder. The pouring happened on a levelled glass slice of200 mm x 200 mm. This slice was cleaned with ethanol before each experiment. Before use, thePVC-foils were stored more than 10 hour in a store with a temperature of 60°C.

38 The chosen approach can be transferred to bigger sample sizes without any problem. Theamount of 2 ml in 960 mm² pure PVC lead to a membrane of 20 µm thickness and PVC-sampleswith plasticisers to 25 µm. A modification is possible by an addition of different additives [Körtel1999].

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39 The microbiological investigations were carried out using bacteria cultures from the landfill forhousehold/municipal waste in Stendal (Saxony-Anhalt, Germany). The waste samples from whichthe bacteria populations were extracted in August 1998 contained a considerable amount ofplastics, i.e. a PVC window frame. Thus a very wide range of cultures including species havingfavourably acclimatised to this kind of material is obtained. Bacteria cultures were taken directlyfrom the surface of plastics found in waste samples. The original incubation was carried out with10 g of this waste and 90 ml mineral medium. Additionally, 1 g pure PVC – powder VINOFLEX –S 6115 was added to reach an acclimatisation of the micro organisms. That mineral medium wasnecessary to meet the micro-organisms demand of minerals (Körtel, 1999).

40 Micro-organisms from the suspension were given into the different culture media mineral medium,half concentrated mineral medium and tripton-dextrose suspension (see tables 2 and 3 on thefollowing pages). The half concentrated mineral medium showed the highest growth of thepopulation and was further used to enrich the cultures.

41 The next step of the investigations was to compare the growth and the development of theisolated strains on PVC of different compositions. Therefore these cultures were brought incontact with the different PVC products without any further source of carbon� These incubationtest series were carried out in glass vials. After counting the bacteria cells two cultures wereidentified to show the highest growth. These cultures were used during all following experiments.

&KDUDFWHULVDWLRQ�RI�WKH�EDFWHULD�FXOWXUHV

42 For the purpose of characterisation of the bacteria cultures the optimum growth temperature andthe population's development at this temperature were analysed. The temperature optimum wasdetermined through incubation of the bacteria cultures inoculated with mineral medium andglucose at different temperatures and observation of the number of cells in the used vials. Analuminium block, where a constant temperature gradient prevails (50° to 80°)�was used to performall bacterial tests at the same time with exactly the same inoculum. This guarantees comparabilityof the results. The following table illustrates the results of the test.

Table 1: Growth of the bacteria cultures isolated from municipal waste landfill under differenttemperatures

WHPSHUDWXUH�>�&@ ��

number of cells of culture 10[107 cells/ml]

0,08 2,26 0,5 0,26 0,4 0,5 1,23

number of cells of culture 17[107 cells/ml]

0,1 1,0 0,73 0,46 11,5 0,93 0,93

43 From these results it can be concluded that the optimum temperature for the bacteria culture'sgrowth is in the area around 62°C and therefore all microbiological investigations of thepopulation's behaviour were carried out at 60°C. To characterise the population's growth thepopulation density was measured with the steady optical deterioration of the transparency of theinoculum and recorded with a personal computer under ideal conditions. The development of thetwo cultures in trypton-dextrose-medium is visualised in the following figure.

8

FXOWXUH��

FXOWXUH��continuous growth of the micro-organisms population

cultures: 10, 17medium: trypton-dextrose 10mlinoculum: 0,25 mlincubation time: 24 htemperature: 60°C

WLPH

GHQVLW\�RI

SRSXODWLRQ

figure 2: Development of the bacteria cultures isolated from municipal waste landfill under idealconditions

44 Both cultures show slight differences in growth speed and adaptation phase time. Generally thebehaviour of the cultures is comparable to bacteria species which are usually involved inbiological degradation processes. The differences show that the cultures contain different bacteriaspecies. Both cultures were mixed together for all investigations of microbial attack on PVC. Thusall species from the landfill sample which are adapted to PVC were included in the study.

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45 For the investigations during the microbiological experiments the same foils were produced asdescribed in chapter 6 of this annex. The foils were made 40 µm in thickness because increasedstability was necessary and the foils were produced in unplasticised PVC-cylinders. The PVCcylinders were made from a PVC-wastewater-pipe which was 35 mm in diameter. To avoidinfluences of the additives in this tube the cylinders were covered with self produced pure PVC. Atthe end of this preparation method the foil (which had to be investigated) and the cylinder werejoined together to a watertight vessel.

7HVW�VHULHV�IRU�WKH�LQYHVWLJDWLRQ�RI�PLFURELDO�DWWDFN�RQ�39&

46 To investigate the attack on PVC three different parallel test series were carried out at 60°C. Inevery series the PVC vessel with the foil at its bottom was filled with 10 ml medium and storedunder defined conditions (60°C in closed glass containers). A loss of liquid from the vesselsduring the test caused by evaporation was refilled with distilled water.

9

47 Series A: Series A was carried out as blank control. The PVC-vessels were filled with 10 ml puremineral medium. Its composition is to be found in table 2. No glucose and no micro-organisms were added. This series included all investigated materials twice, the firstones were incubated 23 days and the second ones 43 days.

Table 2: Composition of the mineral medium in accordance with DIN EN ISO 846

substance amount

NaNO3

KH2PO4

K2HPO4

KCl

MgSO4 * 7 H2O

FeSO4 * 7 H2O

H2Odest

pH

2,00 g/l

0,70 g/l

0,30 g/l

0,50 g/l

0,50 g/l

0,01 g/l

2000 ml*

7,2 ± 0,2*according to positive results from pre-tests for the purposes of this study only half concentrated mineral medium was

used, generally 1000 ml distilled water have to be used

48 Series B: In Series B the PVC-vessels were filled with 10 ml pure mineral medium. Itscomposition is to be found in table 2. No glucose was added but the micro-organismcultures were inoculated. The cell concentration at the start of the test was 6,2 * 106

cells/ml suspension. This series included all investigated materials three times. Thefirst ones were incubated 23 days and the second ones 43 days, both withoutdisturbance. From the third vessel of each material samples were taken regularly tocount the cell density and to investigate the population behaviour (see below).

49 Series C: In Series C the PVC-vessels were filled with 10 ml pure mineral medium enriched with0,5 % glucose. The composition of the mineral medium is to be found in table 2.Additionally the micro-organism cultures were inoculated. The cell concentration at thestart of the test was 6,2 * 106 cells/ml suspension. This series included all investigatedmaterials three times exactly as described for series B.

,QYHVWLJDWLRQ�RI�PLFURELDO�JURZWK�RQ�39&

50 To investigate the microbial growth in the PVC vessels samples from the suspensions of theseries B and C were taken. Results were controlled by analysis of the presence of micro-organisms in the vessels of series A. The sample amount was 300 µl. This loss of liquid from thevessels was refilled with 300 µl pure mineral medium. The sample suspension was mixed with100 µl 2 % formaldehyde to decrease the mobility of the cells and then put into the cell countingdevice according to THOMA (depth 10 µm). The counting was carried out with a light-microscopeenlarged 1000fold using additionally immersion oil. Based on the counting results the populationdensity in the PVC vessel was calculated.

,GHQWLILFDWLRQ�RI�WKH�PLFUR�RUJDQLVPV�UHVSRQVLEOH�IRU�WKH�DWWDFN�RQ�39&

51 For purposes of collecting data about the micro-organisms which seem to be responsible for theindicated attack on PVC the species contained in the bacteria cultures used during theinvestigations were examined. For identification first single strains were isolated from the bacteriacultures. The suspensions containing the micro-organism cultures were diluted and spread onsolid culture media with a spatula. The composition of the media is to be found in table 3. Fromthe bacteria colonies growing on the media's surface samples were taken and transmitted on

10

sterile new media. After some repetitions of this procedure the single strains were isolated. A longtime growth on the media (about one week) showed if there would be any contamination of thestrains with other bacteria.

Table 3: Composition of the culture media for isolation of the single micro-organism strains

VXEVWDQFH DPRXQW

FXOWXUH�PHGLXP�1b+5$*$5�,,�DFFRUGLQJ�WR�6LILQ�*PE+�%HUOLQ

pancreatic peptone

caseine

yeast extract

NaCl

agar

H2Odest

pH

6,75 g/l

1,75 g/l

1,50 g/l

5,00 g/l

15,00 g/l

1000 ml

7,2 ± 0,2

half-concentrated NÄHRAGAR II

pancreatic peptone

caseine

yeast extract

NaCl

Agar

H2Odest

pH – Wert

6,75 g/l

1,75 g/l

1,50 g/l

5,00 g/l

30,00 g/l

2000 ml

7,2 ± 0,2

TRYPTON – DEXTROSE – AGAR according to DIFCO Laboratories Detroit, USA

trypton

dextrose

agar

H2Odest

pH

10,00 g/l

5,00 g/l

15,00 g/l

1000 ml

6,7 ± 0,2 at 25 °C

52 Now the single strains were characterised by their growing behaviour on the media, by theappearance of the cells under the microscopy and by the properties of the cell walls using Gram´smethod. In the following strains which appeared to be different to one another but representativefor the cultures were identified using the test systems API 20 E and API 50 CH from the companyBIO MERIEUX Deutschland GmbH.

53 These test systems consist of a variety of different micro-tubes containing substrates whichindicate cell properties by changing colours. A suspension containing the single strains has to begiven into these tubes and the reaction has to be noted down. The results were checked andcompared with values from the data bank of BIO MERIEUX Deutschland GmbH. As result we gotthe names of the strains and the degree of probability of the identification. If that is higher than75 % a certain identification can be considered according to the test specifications.

11

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54 In co-operation with Prof. Schiffmann from the Institute of Animal Physiology,Cytopathophysiology Unit at University of Rostock the toxicological effects of PVC-degradationproducts in liquid phase were investigated. The intended method called “Syrian hamster embryo(SHE) micronucleus test in vitro” is described following in brief.

55 This test assesses the incidence of micronuclei (small chromatin bodies) in cells. SHE-cells havebeen shown to produce a dose dependent increase in the number of micronuclei in response tocarcinogens. The result of the test is the number of cells containing micronuclei. According toknown data from previous studies, where about 75 of well established carcinogens and mutagenswere tested, these results are assessed and comparable. This in vitro test is preferred to otherinvestigations because quantities of an in vivo test do not correspond to concentrations of thechemical in the SHE culture medium. In earlier studies DEHP was already tested andcarcinogenic activity was evident.

56 The SHE-cells are taken from embryos of hamsters in the 13th week and were stored in liquidnitrogen. During the test the SHE-cells (1.5 x 105 cells per well) are incubated in IBR-modifiedDMEM-medium and different concentrations of the test substance at 37°C for 24 hours.Afterwards the standard test substances α- and β-trenbolone (α-TBOH, β-TBOH) as positivecontrols, testosterone and di-hydrotestosterone as negative controls were administered aftersolving them in DMSO. After an incubation of five hours the substances are eliminated bychanging the medium. During an incubation of 2 - 72 hours the specimens are fixed with absolutemethanol (10 min) and coloured with Hoechst 33258 (1 µg/ml, 4 min). The counting of themicronuclei is carried out using fluorescence microscopy (enlarged 400fold).

57 A more detailed report is published in: Mutation Research, 319 (1993) 47-53: SCHIFFMANN,FRITZENSCHAF, KOHLPOTH, AND RUSCHE: “Testing of known carcinogens andnoncarcinogens in the Syrian hamster embryo (SHE) micronucleus test in vitro; correlation’s within vivo micronucleus formation and cell transformation“.

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Detailed descriptions to accompany text Chapter 6

CONTENTS

1 Conditions during lysimeter studies2 Visible changes in PVC-materials taken from the lysimeters3 Changes of the surfaces of the PVC-materials examined by

scanning electron microscopy4 Mechanical properties of the PVC materials5 Report on molecular weight distribution6 Analysis of gaseous emissions from lysimeters

1

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10

20

30

40

50

60

70

80

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temperature

carbon dioxide

Course of temperature and carbon dioxide production in lysimeter 1 (aerobic, without added PVC)during the lysimeter investigation

0

10

20

30

40

50

60

70

80

0,0 15,0 30,0 45,0 60,0 75,0 90,0 105,0 120,0

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0

0,2

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temperature

carbon dioxide production

Course of temperature and carbon dioxide production in lysimeter 2 (aerobic, with added PVC)during the lysimeter investigation

2

0

10

20

30

40

50

60

70

80

0,0 15,0 30,0 45,0 60,0 75,0 90,0 105,0

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0,2

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Course of temperature and carbon dioxide production in lysimeter 3 (alternating aerobic-anaerobic, without added PVC) during the lysimeter investigation; varying courses of temperatureand carbon dioxide production depend on alternating aeration

0

10

20

30

40

50

60

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Course of temperature and carbon dioxide production in lysimeter 4 (alternating aerobic-anaerobic, with added PVC) during the lysimeter investigation; varying courses of temperatureand carbon dioxide production depend on alternating aeration

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The table summarises the visible changes in PVC-materials after taking them from the lysimeters,below photographs of the materials are shown.

3

Material Changes in the aerobiclysimeter 2

Changes in the anaerobic-aerobic lysimeter 4

Changes in the anaerobiclysimeter 6

PVC I polyurethane foam is degraded

completely; strong increased

brittleness

polyurethane foam is degraded

partial; colour has changed from

grey to light red partially;

increased brittleness

polyurethane foam is degraded

completely; increased brittleness

PVC II colour has changed from light

beige to light red/brown; very

strong increased brittleness

colour has changed from light

beige to light brown; strong


colour has changed from light

beige to light red; slightly


PVC III discolouration from green to milky

white/light yellow; strong

deformation; strong increased

brittleness

discolouration from green to

transparency; slight deformation;

slight increased brittleness

discolouration from green to

transparency; slight deformation;

slight increased brittleness

PVC IV colour has changed from brown to

dark brown, strong increased

brittleness; strong deformation;

blisters up to 5 mm diameter were

formed

colour has changed from brown to

dark brown, increased brittleness;

some deformation

colour has changed from brown

to nearly black, increased

brittleness; slight deformation

PVC V colour has changed from white to

light orange; strong deformation

colour has changed from white to

beige; deformation

colour has changed from white

to light beige; slight deformation

PVC VI colour has changed from

transparency to dark orange,

partial to light orange; very strong

deformation; very strong increased

brittleness

colour has changed from

transparency to milky white, partial

to light orange and light yellow;

strong deformation; strong


colour has changed from

transparency to slight milky

white; deformation; increased

brittleness

PVC VII colour has changed from dirty

white to light yellow

colour has changed from dirty

white to yellow

colour has changed from dirty

white to yellow

Changes in PVC-material I, the new car interior trim, caused by the different kinds of treatment;from left to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

4

Changes in PVC-material II, the used car interior trim, caused by the different kinds of treatment;from left to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

Changes in PVC-material III, the new flooring, caused by the different kinds of treatment; from leftto right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

Changes in PVC-material IV, the used flooring, caused by the different kinds of treatment; fromleft to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

5

Changes in PVC-material V, the new window frame, caused by the different kinds of treatment;from left to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

Changes in PVC-material VI, the new packaging foil, caused by the different kinds of treatment;from left to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

6

Changes in PVC-material VII, the old window frame, caused by the different kinds of treatment;from left to right: 1. raw material, 2. PVC VI from lysimeter 2 (aerobic), 3. PVC VI from lysimeter 4(aerobic-anaerobic), 4. PVC VI from lysimeter 6 (anaerobic), 5. PVC VI from biological wastetreatment plant

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The table summarises the changes of the surfaces of the PVC-materials after taking them fromthe lysimeters in comparison to the raw materials, on the following pages photographs of thescanning electron microscopy are shown if effects were recognised.

Material raw material Lysimeter 2

aerobic

Lysimeter 4

aerobic - anaerobic

Lysimeter 6

anaerobic

PVC I PVC I is a very porous

material with a lot of

small and big holes at

the surface

Any interpretation of the photographs is not possible because of the very porous

raw material. Differences are not recognisable.

PVC II Because of the long term

use (seven years)

corrosion effects are

visible. The surface is not

homogenous.

A densely microbial

population is investigated

at the surface. The

micro-organisms must

not use the PVC as

source of carbon. Further

corrosion effects are not

visible.

No significant changes in

the surface are visible.



PVC III PVC III shows a

homogenous surface

with a lot of inclusions.

The visible black points

are holes. The bigger

light spots are very

probably beginning

migration effects (bulges)

of plasticisers. The holes

can be burst bulges.

No investigation was

carried out.



PVC IV PVC VI shows clear

signs of use –

mechanical erosions as

scratches and holes.

The plainly visible

blisters, holes and burst

blisters show a certain

migration of additives,

very probable

plasticisers.



The effects as described

for lysimeter 2 are less

visible but recognisable.

PVC V PVC V shows clear signs No significant changes in No investigation was A densely microbial

7

of the production process

- mechanical erosions as

scratches.

the surface are visible. carried out. population is investigated

at the surface. The

micro-organisms must

not use the PVC as

source of carbon. Further

corrosion effects are not

visible.

PVC VI PVC V has a very

homogenous surface.

The light spots are dust

particles settled down

during microscopy.

First significant signs of

an attack to the PVC are

visible as craters with

about 80 – 100 µm

depth. At the surface a

densely microbial

population is

investigated.


the surface are visible

because of the

insufficient quality of the

picture.



8

Photograph from scanning electron microscopy of the raw material PVC I, new car interior trim;due to the very porous surface no effects were detectable during investigation of the samplestaken from the lysimeters and the biological waste treatment plant, therefore no furtherphotographs are shown

9

Photograph from scanning electron microscopy of the raw material PVC II, used car interior trim;due to the long term use (seven years) corrosion effects are already visible

Photograph from scanning electron microscopy of the material PVC II, used car interior trim,taken from lysimeter 2 (aerobic); a densely microbial population is investigated at the surface,corrosion effects are not visible; no effects on this PVC product was visible at samples taken fromthe other lysimeters and the biological waste plant

10

Photograph from scanning electron microscopy of the raw material PVC III, new flooring; thematerial shows a very homogenous surface

Photograph from scanning electron microscopy of the material PVC III, new flooring, taken fromlysimeter 2 (aerobic); visible dark points are holes, bigger light spots are very probably beginningmigration effects (bulges) of plasticisers, the holes can be burst bulges; under the other treatmentconditions no effects were observed

11

Photograph from scanning electron microscopy of the raw material PVC IV, used flooring; due tothe long term use corrosion effects probably caused by mechanical stress are visible

Photograph from scanning electron microscopy of the material PVC IV, used flooring, taken fromlysimeter 2 (aerobic); plainly visible blisters, holes and burst blisters show a certain migration ofadditives, very probable plasticisers

12

Photograph from scanning electron microscopy of the material PVC IV, used flooring, taken fromlysimeter 6 (anaerobic); the rough surface shows plainly corrosion effects but less than underaerobic conditions

13

Photograph from scanning electron microscopy of the raw material PVC V, new window frame;scratches caused by the production process are visible at the surface

Photograph from scanning electron microscopy of the material PVC V, new window frame, takenfrom lysimeter 6 (anearobic conditions); densely microbial population is investigated at thesurface but no corrosions has occurred

14

Photograph from scanning electron microscopy of the raw material PVC VI, new packaging foil; avery homogenous surface is visible, the light spots are dust particles settled down duringmicroscopy

Photograph from scanning electron microscopy of the material PVC VI, new packaging foil, takenfrom lysimeter 2 (aerobic conditions); significant signs of an attack to the PVC are visible ascraters with about 80 – 100 µm depth, at the surface a densely microbial population isinvestigated

15

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In the following the behaviour of the PVC products during the tensibility tests is shown tocharacterise changes in the PVC materials during investigations in the lysimeters and thebiological waste treatment plant. The names in the diagrams are German and mean tension(“Spannung”) and strain (“Dehnung”). The different courses in each diagram represent thetensibility tests of the single tension test specimen. Several tests have to be performed with onematerial to get representative results.

Courses of the tensibility test of the raw material ofPVC I, new car interior trim, typical behaviour of aplasticised PVC is visible

Courses of the tensibility test of PVC I, new carinterior trim, taken from lysimeter 2 (aerobic); thesteep gradient at the beginning of the testcharacterises certainly a rise of brittleness, thetensile strain limit decreased clear

Courses of the tensibility test of PVC I, new carinterior trim, taken from lysimeter 4 (aerobic-anaerobic); the gradient at the beginning of the testraises in comparison to the raw material but lessthan during aerobic investigation, a decrease of thetensile strain limit had occurred

Courses of the tensibility test of PVC I, new carinterior trim, taken from lysimeter 6 (anaerobic); aslight decrease of the tensile strain limit hadoccurred

Courses of the tensibility test of PVC I, new carinterior trim, taken from the biological wastetreatment plant; a slight decrease of the tensilestrain limit had occurred

16

Courses of the tensibility test of the raw material ofPVC II, old car interior trim, typical behaviour of aplasticised PVC is visible

Courses of the tensibility test of PVC II, old carinterior trim, taken from lysimeter 2 (aerobic); thesteep gradient at the beginning of the testcharacterises certainly a rise of brittleness, thetensile strain limit decreased clear

Courses of the tensibility test of PVC II, old carinterior trim, taken from lysimeter 6 (anaerobic); thegradient at the beginning of the test raises incomparison to the raw material but less than duringaerobic investigation, a slight decrease of thetensile strain limit had occurred

Courses of the tensibility test of PVC II, old carinterior trim, taken from the biological wastetreatment plant; the gradient at the beginning of thetest raises in comparison to the raw material butless than during aerobic investigation, a slightdecrease of the tensile strain limit had occurred

17

Courses of the tensibility test of the raw material ofPVC III, new flooring, the behaviour shows that thematerial is laminated

Courses of the tensibility test of PVC III, newflooring, taken from lysimeter 2 (aerobic); tensilestrenght as well as tensile strain limit decreasedclear, interpretation of effects is difficult due to thelamination of the material

Courses of the tensibility test of the raw material ofPVC IV, old flooring, the behaviour shows that thematerial is laminated

Courses of the tensibility test of PVC IV, oldflooring, taken from lysimeter 2 (aerobic); thegradient at the beginning of the test raises incomparison to the raw material

18

Courses of the tensibility test of the raw material ofPVC V, new window frame, typical behaviour of anunplasticised PVC is visible

Courses of the tensibility test of PVC V, newwindow frame, taken from lysimeter 2 (aerobic);tensile strength decreased slightly, the tensilestrain limit decreased clear

Courses of the tensibility test of PVC V, newwindow frame, taken from lysimeter 6 (anaerobic);no clear difference to the behaviour of the rawmaterial was observed

Courses of the tensibility test of PVC V, newwindow frame, taken from the biological wastetreatment plant; no clear difference to thebehaviour of the raw material was observed

19

Courses of the tensibility test of the raw material ofPVC VI, new packaging foil, typical behaviour of aPVC with low content of plasticiser is visible

Courses of the tensibility test of PVC VI, newpackaging foil, taken from lysimeter 2 (aerobic); thesteep gradient at the beginning of the testcharacterises certainly a rise of brittleness, thetensile strain limit decreased; almost typicalbehaviour of anplasticised material is visible

Courses of the tensibility test of VI, new packagingfoil, taken from lysimeter 4 (aerobic-anaerobic); thegradient at the beginning of the test raises incomparison to the raw material but less than duringaerobic investigation

Courses of the tensibility test of VI, new packagingfoil, taken from lysimeter 6 (anaerobic); the gradientat the beginning of the test raises in comparison tothe raw material but less than during aerobicinvestigation

Courses of the tensibility test of PVC IV, newpackaging foil, taken from the biological wastetreatment plant; no clear effects are visible

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For reason of certainty the analysis report on determination and interpretation of molecular weightdistribution is shown as copy in this section.

23

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24

4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00

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1000000

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Abundance

TIC: 99091603.D

4.96

5.22

5.44

5.67

5.72

5.98

6.55

7.14 8.59

11.75

5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00

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Table to accompany text Chapter 5

1

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Initially, information about existing and/or ongoing research analysis as regards the behaviour of PVCwaste in landfills was acquired from private and public organisations, and from libraries. Since thereare rather few studies about this subject and evidence prevails that adverse effects on theenvironment must be expected from additives in PVC products the literature survey was extended.

A comprehensive online search of protected databases via STN International (Scientific and TechnicalInformation Network) covering the data bases American Chemical Society, Medline and ULIDAT wascarried out including not only the search for studies on PVC waste in landfills but also on the behaviourof relevant plasticisers and stabilisers in landfills, under landfill conditions and to a certain extent inenvironmental media such as soil, sediment, water and atmosphere. Keyword combination for theonline-search is given below.

Search PVC + (waste-soil-landfill-groundwater-sediment) +

code No. results Keyword combination Relevant resultsL29 48 microbiol-bacteria-yeast-fungus-protozoan-bioaccum-biodegrad 7L30 38 Degrad-decomp 5L31 8 Anaerobic-aerobic-digestL32 21 Toxic-ecotoxic-fungitox-carcinogen-mutagen-teratogenL33 2 toxicologyL34 2 Gas-methanL35 26 corrosionL36 14 microbiol-bacteria-yeast-fungus-protozoan-bioaccum-biodegrad/�� 19 Degrad-decomp 2L38 2 Anaerobic-aerobic-digestL39 5 Toxic-ecotoxic-fungitox-carcinogen-mutagen-teratogenL40 1 toxicologyL41 5 Gas-methanL42 9 corrosionL43 55 Sewage-sludge-compost+microbio-toxic-corrosionL44 1 Sewage-sludge-compost+toxicology

Search Phthalates-(waste-soil-landfill-groundwater-sediment) +

code No. results Keyword combination Relevant resultsL45 30 microbiol-bacteria-yeast-fungus-protozoan-bioaccum-biodegrad 11L46 11 Degrad-decomp 3L47 2 Anaerobic-aerobic-digestL48 16 Toxic-ecotoxic-fungitox-carcinogen-mutagen-teratogenL49 12 toxicology 1L50 0 Gas-methanL51 62 microbiol-bacteria-yeast-fungus-protozoan-bioaccum-biodegrad 6L52 30 Degrad-decomp 1L53 5 Anaerobic-aerobic-digestL54 40 Toxic-ecotoxic-fungitox-carcinogen-mutagen-teratogenL55 2 toxicologyL56 1 Gas-methanL57 71 Sewage-sludge-compost+microbio-toxic-corrosion 3L58 0 Sewage-sludge-compost+toxicology

The search profile for the search in other databases is slightly amended and includes now alsoBisphenol A. The information content of studies and articles as shown below vary on account of theirsource origin. Certain information content, particularly with regard to detail of abstracts, was taken intoconsideration as supplied by databases. The results of the literature survey are structured as follows:

• Degradation of plasticisers• Stabilisers, heavy metals• Release of plasticisers• Estrogenic effects

2

Degradation of plasticisers

Author Adams, William J.; Renaudette, Wilfred J.; Doi, John D.; Stepro, Mitch G.; Tucker,Michael W.; Kimerle, Richard A.; Franklin, Brenda B.; Nabholz, J. Vincent

Title Experimental freshwater microcosm biodegradability study of butyl benzyl phthalate

Year 1988

Language English

Institute Environ. Sci. Cent., Monsanto Co., St. Louis, MO, 63167, USA

published in ASTM Spec. Tech. Publ. (1988), 1007(Aquat. Toxicol. Environ. Fate: 11th Vol.), 19-40

Code, ISSN ASTTA8; ISSN: 0066-0558

Document Journal

Abstract A 30-day freshwater microcosm study was conducted to measure the biodegradabilityof Bu benzyl phthalate (I) in water and sediment. The microcosms were designed tosimulate the flow rate, water to sediment surface ratio, and environmental conditionsof the Illinois River, Illinois. Water and undisturbed sediment cores were brought intothe lab. from the Illinois River and placed in 53-L all-glass microcosms. The degrdn.of I was tested in the microcosms at concn. levels of 10 and 100 .mu.g/L and in asterilized control microcosm at a level of 100 .mu.g/L, with each concn. beingreplicated 5 times. I was added to each microcosm 3 times/wk at 1/2 the initial dose. Iuniformly ring-labeled with 14C was used as the test material, and analyses wereperformed for parent I as well as for 14C intermediates. The microcosms were sealedto trap 14C-CO2 for purposes of assessing mineralization and obtaining a massbalance on each microcosm. The results indicated that I was readily degraded inwater and sediment. The estd. half-life in water for primary degrdn. was typically.ltoreq.2 days. Mineralization of I did occur, with an av. of 10.4% of the total I dosed ineach microcosm trapped as 14CO2. Concns. of I in the sediments were lower thanpredicted from sediment partition coeffs. (200-600 .mu.g/kg) and ranged from 7 to 23.mu.g/kg. The sediment and water analyses showed that the majority of the 14Cactivity detected was not I. The transient appearance of primary metabolites wasobsd.; however, the preponderance of 14C remaining in soln. was not I. A massbalance of each component (water, sediment, CO2, etc.) in each microcosm indicatedthat 78.2% of the total amt. of 14C-labeled I added to the microcosms could beaccounted for. About 50% of the mass remained as 14C metabolites in the water, andonly 1.8 and <0.1% were found as 14C and parent I, resp., in the sediment. Theremainder of the 14C-labeled I was on the glass, in silicone joints, in stoppers, or inevolved CO2 or was removed by water sampling. The collective data indicate that Ishould not be a persistent chem. in freshwater environments.

3

Author Albrechtsen, H.

Title Investigations at Vejen Landfill. The microbiology of the groundwater zone

Year 1989

Language Danish

Institute Copenhagen University, DTU (Technical University of Denmark)

published in Danish Environmental Protection Agency, Lossepladsprojektet P6-2 (The LandfillProject)

Code, ISSN -

Document Report

Abstract To gain a more detailed knowledge of microbial activity in the groundwater zonepolluted or not polluted. Samples from 19 drillings at Vejen Landfill are investigated.Potential of aerobic degradation of phenol, dichlorphenole, DEHP and m-xylen wasinvestigated.

Author Anna Ledin

Title Natural attenuation as remediation of landfill leachate plumes.

Year 1998-2000

Language Danish

Institute Department of Environmental Science and Engineering, Centre of Groundwater,Technical University of Denmark

published in Not published, ongoing investigations 1998-2000

Code, ISSN -

Document -

Abstract Samples of leachate from 10-12 danish landfills, both new and old landfills, will beinvestigated including chemical analysis and biotests on samples. The objective of thestudy is to verify that degradation of organic compounds (ie dimethylphthalate,diethylphthalate, di-n-propylphthalate, di-n-butylphthalate, di-isobutylphthalate, di-pentylephthalate, di-(2-etylhexyl) phthalate, butylbenzylphthalate, di-cyklohexylphthalate, mono- and di-esters of phthalic-acid) from pollution takes place inthe landfill and in the groundwater below by monitoring the existence of specificproducts of degradation. It includes a survey of the existence of polar and ionicorganic compounds in landfills and in the groundwater downstream of the landfill.

4

Author Anon

Title Degradation of dibutyl phthalate and bis(2-ethylhexyl)phthalate by Rhodococcuserythropolis

Year 1994

Language Russian

Institute Belarus

published in Dokl. Akad. Nauk Belarusi (1994), 38(6), 64-6

Code, ISSN DABSEU

Document Journal

Abstract A Rhodococcus erythropolis strain isolated from soil was capable to utilize 0.1-2%vol./vol. di-Bu phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) as a solecarbon source. DBP and DEHP metab. is carried out by Rhodococcus erythropolis viathe following steps: diester.fwdarw.phthalate.fwdarw.benzoate. fw darw.p -hydroxybenzoate. fwdarw.protocatechuate. fwdarw.3-ketoadipinate. Such capabilityof the Rhodococcus erythropolis stain to mineralize these compds. make it suitable forbiol. treatment of natural waters and soils polluted by wastewater discharges fromplasticizer manuf.

5

Author Bauer, Martin J.

Title Verhalten von Phthalsäureestern in anaeroben Hausmüllsickerwaessern ausBioreaktoren und Deponien

Year 1997

Institute University of Bayreuth

Code, ISSN ISBN 3-8265-2912-X

Document Dissertation

Language German

Abstract The objective of this thesis was to investigate the fate and behaviour of phthalic acidesters during anaerobic conditions in municipal solid waste landfills. The methodsrequired to analyse PAE were specifically developed and optimized. Laboratory scalebioreactors containing exactly defined municipsal waste saturated with continuouslycirculated water were used to stimulate the processes and variable conditions ofanaerobic digestion. In order to verify the results obtained in the laboratory, landfillleachates of different origin were also examined. In the bioreactor experiments theleachate was able to extract at least 0.6 mg of DEHP and 0.2 mg of DBP per kg ofmoist refuse mass during the stabilisation of waste. The elution was more effective,when the respective PAE was more water soluble, and when there was higher amountof PAE available in the waste material. DMP, being very water soluble, could bebiologically transformed during the anaerobic degradation sequence of the municipalwaste regardless of the time of spiking. A primary degradation of DEHP during thehydrolytic and acidogenic phases of anaerobic digestion could not be precluded.However, there was no evidence of a transformation of DBP and BBP. Duringmethanogenesis all the phthalic acid esters but DMP turned out to be persistent.DEHP could not even be decomposed abiotically at pH 9. So, the majority of phthalicacid esters was available for transport by leachate. In the course of the municipalwaste digestion sequence DEHP accumulated at suspended solids. As a result,merely about a quarter of the overall loud with DEHP could be found in solution. In thebioreactors’ leachates there was more phthalic acid ester in the solution with higherwater solubility of the respective PAE. The presence of dissolved organic substancesin the leachate resulted in a solubility enhancement of the PAE. Increasedconcentrations of DEP, DBP and BBP could be observed during the acidogenicphase. Nevertheless, volatile fatty acids could be ruled out as the cause for thisphenomenon. Fractionation experiments using ultrafiltration techniques showed thatDBP could be transported via macromolecular substances (>3000 Da) in the leachate.In most cases, the DEHP concentration in the leachate increased not before thetransition phase to methanogenesis was reached. Substances with a molecular weight> 50000 Da were the reason for this enhancement of the PAE’s water solubility. Itcould be concluded that these macromolecules changed their shape with decreasingconcentration of dissolved organic carbon (DOC), thereby increasing the molecularsurface required for the adsorptive binding of DEHP. In experiments with landfillleachates an effect neither of pH nor of conductivity of the solution on the DEHPconcentration was observed. The results of the investigation of several leachates frommunicipal solid landfills indicate that humic and fulvic acids were acting as thesolubilizing macromolucular agents. Thus, the concentration of DEHP in solution wassignificantly dependent on the amount of humic substances. About 10 % of DOC inlandfill leachates consisted of dissolved humic substances. Therefore, a correlationwas also found between the sum of PAE and radioactively labelled DEHP,respectively, and the concentration of DOC. Even in diluted landfill leachates DOCwas able to solubilize 14C-DEHP. The influence of the macromolecular humicsubstances resulted in the decrease of particle bound transport of hydrophobic PAE in

6

landfill leachates. Therefore, a mean of 85 % of the overall PAE load was carried bythe solution. Hence, phthalic acid esters leaking from municipal solid waste landfillswill continue to be a threat especially to the ground water.

Author Bauer, M. J.; Herrmann, R.; Martin, A.; Zellmann, H.

Title Chemodynamics, transport behavior and treatment of phthalic acid esters in municipallandfill leachates

Year 1998

Language English

Institute Chair of Hydrology, University of Bayreuth, Bayreuth, 95440, Germany

published in Water Sci. Technol. (1998), 38(2), 185-192 Elsevier Science Ltd.

Code, ISSN WSTED4; ISSN: 0273-1223

Document Journal

Abstract Large amounts of phthalic acid esters (PAEs) are leached from plastics dumped atmunicipal landfills. This leachate transports PAEs either adsorbed on particulatematter or in dissolved phase. Dissolved organic macromolecules, mainly humic-likesubstances, enhance the solubility of PAEs. In the biochemical environments ofmunicipal landfills short chain PAEs can be degraded by base-catalyzed hydrolysis orby microorganisms which enzymically split the side chains. However, there is nocleavage of the aromatic ring. Long chain PAEs like di-(2-ethylhexyl) phthalate areneither degraded abiotically nor by microorganisms. Hence, these PAEs can beleached and washed out of leaky landfills into the groundwater and thus continue to bea threat to the aquatic environment. Only a combined UV radiation/ozonizationtreatment is capable of fully destroying PAEs.

7

Author Cadogan, D.F., Papez, M., Poppe, A.C., Pugh, D.M. and Schuebel, J.

Title An assessment of the release, occurrence and possible effects of plasticisers in theenvironment

Year 1993

Language English

Institute -

published in PVC 93: The Future. The Institute of Materials, p260-274

Code, ISSN -

Document Conference

Abstract Accurate statistical information together with a careful and practical analysis of lossmechanisms and routes have been used to make reliable estimates of plasticiseremissions to the environment. The emissions sources examined include theproduction, use and final disposal of a wide range of flexible PVC articles as well asplasticiser production and distribution. The existing information on the environmentalbehaviour of phthalates is critically reviewed and areas requiring further studyidentified. Levels of phthalates in sediments are relatively high and little is known ofthe effects of such concentrations on the organisms living in that compartment. It isrecommended that further studies are carried out in this area. It is concluded that eventhough the total quantity of phthalates in existence continues to increase annually, theenvironmental burden is static or possibly decreasing.

Author Chen, Yingxu; Shen, Dongsheng; Hu, Zhiqiang; Liu, Xiaoling; Wu, Donglei; Zhao,Desheng; Zhang, Jianying

Title Degradation of phthalic acid esters (PAEs) in soils

Year 1997

Language Chinese

Institute Dep. Environmental Scis., Zhejiang Agricultural Univ., Hangzhou, 310029, Peop. Rep.China

published in Huanjing Kexue Xuebao (1997), 17(3), 340-345

Code, ISSN HKXUDL; ISSN: 0253-2468

Document Journal

Abstract The degrdn. of DBP (di-Bu phthalate) and DEHP (di(2-ethylhexyl) phthalate) wasstudied in several soils. The results showed that the degrdn. rates of DEHP and DBPcould be described by first-order kinetics equation. The degrdn. of PAEs in three soilswere different. DBP in soils was more readily degraded than DEHP. The degrdn.rates of DEHP in sterilized soils was obviously slow. In soil with degrading DEHPbacteria added, the rate was increased. Temp. and water content of the soil affectdegrdn. rates of DBP and DEHP. Nine bacteria and eleven fungi strains capable ofdegrading and using DEHP were isolated from the PAEs polluted soil.

8

Author Cheng, Guisun; Liu, Xiaoyang

Title Microbiological degradation of dibutyl phthalate, a plasticizer

Year 1986

Language Chinese

Institute Inst. Soil Fertilizer, Chinese Acad. Agric. Sci., Peop. Rep. China

published in Huanjing Kexue (1986), 7(6), 25-7

Code, ISSN HCKHDV; ISSN: 0250-3301

Document Journal

Abstract Di-Bu phthalate in soil was degraded by microorganisms. In soils contg. 0.10 mg di-Bu phthalate/g, 14.1% of the plasticizer was degraded in 50 days. Pseudomonasfluorescens and Xanthomonas campestris were among the degradingmicroorganisms.

Author Doerfler, U.; Adrian, P.; Scheunert, I.

Title Pruefung der biologischen Abbaukapazitaet von Boeden in Abhaengigkeit vonjahreszeitlichen Bedingungen. Biological Degradation Capacity of Soils as Influencedby Seasonal Conditions.

Year 1990

Institute Forschungszentrum fuer Umwelt und Gesundheit, Institut fuer Bodenoekologie,Oberschleissheim)

Code, ISSN UBA-FB 92-011

Document Report

Language Deutsch

Abstract The influence of seasonal conditions on the biomineralization of organic xenobiotics to14CO2 was investigated in three soils, using two 14C-labeled environmentalchemicals - n-dodecylbenzenesulfonate (LAS) and di(2-ethylhexyl)phthalate (DEHP) -as examples. Biomineralization was determined by daily measurement of 14CO2formed during defined time periods (one to four weeks) and by establishing the half-lives of nonmineralized 14C. In addition, the variable parameters soil temperature, soilmoisture, pH-value and ATP content were determined. In the first part of the project,degradation experiments were carried out at room temperature, whereas in thesecond part they were carried out under thermostatized conditions at constant soilhumidity. For LAS, in the three soils a negative correlation between half-lives and soilhumidity was found; in the soil ’Baierbrunn‘ , half-lives were correlated negatively alsowith pH, and in the soil ‘Ebersberger Forst‘ , with the ATP content. In all three soils,biomineralization of both test compounds was strongly dependent on soil temperature.Degradation of LAS was negligible at temperatures below 3 degrees C, that of DEHPat temperatures below 10 degrees C.

9

Author Ejlertsson, Jörgen

Title Fate of Phthalic Acid Esters during Digestion of Municipal Solid Waste under LandfillConditions.

Year 1997

Language English

Institute Institute of Tema Research. Department of Water and Environmental Studies,Linköping University, Sweden

published in -

Code, ISSN ISBN 91-7871-958-5 ISSN 0282-9800

Document -

Abstract The objective of this thesis has been to investigate whether anaerobic microorganismsdeveloping in acidogenic and methanogenic landfill environments have the potential todegrade phthalic acid esters (PAEs) and what kinds of intermediates may be formed,assuming PAE degradation. PAEs form a group of compounds widely used in hugeamounts worldwide, mainly as plasticiser in PVC-plastics. PAEs are presently enteringSwedish landfills, mostly via PVC-plastics deposited as refuse, but also via otherproducts. At landfills they are subjected to an anaerobic environment and may bestored for several decades and centuries under such conditions. Diluted andhomogenised municipal solid waste (MSW) samples from different landfillenvironments were used as inocula in an assay developed for the purpose todetermine the potential of microbial PAE degradation. The results showed that themicroorganisms present in the MSW-samples were able to transform almost all PAEsinvestigated. However, the degradation of PAEs may give rise to compounds whichare more chemically inert than the parental compounds. As an example bis(2-ethylhexyl) phthalate (DEHP) was observed to be degraded to mono(2-ethylhexyl)phthalate during 300 days of incubation. Monoesters of PAEs were observed inleachate from methanogenic landfill lysimeters in concentrations up to 12 mg per litreduring MSW degradation. Ten fold amounts of PVC-plastic were also added to landfilllysimeters to investigate whether PAEs or degradation intermediates could bedetected in the lysimeter leachate above the indigenous concentrations of PAEs. Thiswas shown not to be the case for methanogenic conditions. However, the PVC-plastics subjected to methanogenic conditions were shown to be leached of PAEs,which did not occur for samples under acidogenic conditions. The results imply thatmicrobial degradation enhanced the loss of PAEs from the PVC-plastics incubatedunder methanogenic conditions.

10

Author Ejlertsson, J.; Johansson, E.; Karlsson, A.; Meyerson, U.; Svensson, B.H.

Title Anaerobic degradation of xenobiotics by organisms from municipal solid waste underlandfilling conditions

Year 1996

Language English

Institute Department of Water and Environmental Studies, Linkoeping University, Linkoeping,S-581 83, Swed.

published in Antonie van Leeuwenhoek (1996), 69(1), 67-74

Code, ISSN ALJMAO; ISSN: 0003-6072

Document Journal

Abstract The potential for biol. transformation of 23 xenobiotic compds. by microorganisms inmunicipal solid waste (MSW) samples from a lab. scale landfill reactor was studied.The influence of these xenobiotic compds. on methanogenesis was investigated. AllR11, 1,1-dichloroethylene, 2,4,6-trichlorophenol, di-Me phthalate, phenol, benzoateand phthalic acid added were completely transformed during the period of incubation(>100 days). Parts of the initially added perchloroethylene, trichloroethylene, R12,R114, di-Et phthalate, di-Bu phthalate and benzylbutyl phthalate were transformed.Methanogenesis from acetate was completely inhibited in the presence of 2,5-dichlorophenol, whereas 2,4,6-trichlorophenol and R11 showed an initial inhibition,whenafter methane formation recovered. No transformation or effect on the anaerobicmicroflora occurred for R13, R22, R114, 3-chlorobenzoate, 2,4,6-trichlorobenzoate,bis(2-ethyl)hexyl phthalate, diisodecyl phthalate and dinonyl phthalate. The resultsindicate a limited potential for degrdn., of the compds. tested, by microorganismsdeveloping in a methanogenic landfill environment as compared with other anaerobichabitats such as sewage digester sludge and sediments .

11

Author Ejlertsson, J.; Meyerson, U.; Svensson, B.H.

Title Anaerobic degradation of phthalic acid esters during digestion of municipal solid wasteunder landfilling conditions

Year 1996

Language English

Institute Department of Water and Environmental Studies, Linkoping University, Linkoping, S-581 83, Swed.

published in Biodegradation (1996), 7(4), 345-352

Code, ISSN BIODEG; ISSN: 0923-9820

Document Journal

Abstract Anaerobic microorganisms in municipal solid waste samples from lab.-scale landfillreactors and a pilot-plant biogas digester were investigated with the aim of assessingtheir ability to transform four com. used phthalic acid esters (PAEs) and phthalic acid(PA). The PAEs studied were di-Et phthalate (DEP), Bu benzyl phthalate (BBP), di-Buphthalate (DBP), and bis(2-ethylhexyl) phthalate (DEHP). No biol. transformation ofDEHP could be detected in any of the expts. Together with waste samples from thesimulated landfilling conditions, the PAEs (except DEHP) were hydrolyticallytransformed to their corresponding monoesters. These accumulated as end products,and in most cases they were not further degraded. During incubation with waste fromthe biogas digester, the PAEs (except DEHP) were completely degraded to methaneand carbon dioxide. The influence of the landfill development phase on thetransformations was investigated utilizing PA and DEP as model substances. Wefound that during both the intense and stable methanogenic (but not the acidogenic)phases, the microorganisms in the samples had the potential to transform PA. Ashorter lag phase was obsd. for the PA transformation in the samples from the stablemethanogenic phase as compared with earlier phases. This indicates an increasedcapacity to degrade PA during the aging phases of the municipal solid waste inlandfills. No enhancement of the DEP transformation could be obsd. as conditions inthe methanogenic landfill model changed over a year’s time. The results indicate thatmicroorganisms developing in a methanogenic landfill environment have asubstantially lower potential to degrade PAEs than those developing in a biogasreactor.

12

Author Gledhill, William E.; Kaley, Robert G.; Adams, William J.; Hicks, Orville; Michael, PaulR.; Saeger, Victor W.; LeBlanc, Gerald A.

Title An environmental safety assessment of butyl benzyl phthalate

Year 1980

Language English

Institute Monsanto Co., St. Louis, MO, 63166, USA

published in Environ. Sci. Technol. (1980), 14(3), 301-5

Code, ISSN ESTHAG; ISSN: 0013-936X

Document Journal

Abstract The current environmental safety assessment concluded that, under presentuse/disposal patterns, Bu benzyl phthalate (BBP) [85-68-7] does not constitute ahazard to the aquatic environment. BBP is relatively insol. in water and tends topartition to soil, sediment, and biota in the aq. environment. Biodegrdn., the controllingrate process for environmental degrdn. of BBP, is rapid and extensive in natural waterand sewage systems. Environmental levels of BBP averaged <1 .mu.g/L in water and<100 ng/g in sediment. BBP is acutely toxic to a variety of algae, invertebrates, andfish in the 0.5-5 mg/L range and chronically toxic to Daphnia and fathead minnows inthe 0.1-0.8 mg/L range. A bioconcn. study indicated that BBP was not anaccumulative or persistent chem. in fish. Comparison of mean environmental waterconcns. of BBP to lab. chronic toxicity values for Daphnia and fathead minnowsshowed an av. safety margin of approx. 3 orders of magnitude.

Author Henriksen, Kaj

Title Degradation and transport of organic compounds injurious to the environment insoil/sludge systems

Year 1998-1999

Language Danish

Institute Aalborg University, Denmark, Institute for water, soil and environmental technics.Centre for sustainable usage of areas and management of compounds injurious tothe environment, carbon and nitrogen.

published in Not published, ongoing project

Code, ISSN -

Document -

Abstract To investigate the physical, chemical and biological fate of compounds injurious to theenvironment and to create a model in order to simulate the degradation andtransportation of the compounds in the soil. Soil samples from agricultural areas willbe examined to investigate the degradation and destiny of compounds (DEHP etc.) inwastewater sludge put on agricultural areas.

13

Author Inman, John C.; Strachan, Stephen D.; Sommers, Lee E.; Nelson, Darrell W.

Title The decomposition of phthalate esters in soil

Year 1984

Language English

Institute Dep. Agron., Purdue Univ., West Lafayette, IN, 47907, USA

published in J. Environ. Sci. Health, Part B (1984), B19(2), 245-57

Code, ISSN JPFCD2; ISSN: 0360-1234

Document Journal

Abstract Factors affecting the decomposition of carboxyl-labeled (14C) phthalic acid (PA) [88-99-3], monobutyl phthalate (MBP) [131-70-4], and di-Bu phthalate (DBP) [84-74-2]were studied in soil incubation expts. conducted under lab. conditions. A lag phase of10-20 days occurred before soil microbes initiated metab. of MBP and DBP, whereasPA was rapidly decomposition. Approx. 90% of DBP added to soils at 0.1-0.4% wasdecomposition within 80 days under both aerobic and anaerobic conditions.decomposition of DBP was enhanced in soils by increasing soil pH from 5.2 to 7.0, byadding org. matter, and by elevating the temp. from 23.degree. to 30.degree.. Varyingsoil characteristics and the simultaneous addn. of ammonium, CaCO3, or sewagesludge had little effect on the rate or extent of DBP degrdn. The addn. of DBP insewage sludge or other waste materials to soils should not pose a long-termpersistence problem.

Author Jacobsen H.J.

Title Compounds injurious to the environment at sludge composting

Year 1998

Language Danish

Institute Odense Vandselskab as and Odense Renovationsselskab A/S

published in Stads- og Havneingenioren no. 6/7, p. 14-15

Code, ISSN –

Document Journal

Abstract The municipality of Odense produces every year approx. 38,000 tonne dewateredwastewater sludge. The degradation of DEHP by composting is investigated.

14

Author Johnson, B. Thomas; Heitkamp, Michael A.; Jones, John R.

Title Environmental and chemical factors influencing the biodegradation of phthalic acidesters in freshwater sediments

Year 1984

Language English

Institute Columbia Natl. Fish. Res. Lab., US Dep. Inter., Columbia, MO, 65201, USA

published in Environ. Pollut., Ser. B (1984), 8(2), 101-18

Code, ISSN EPSPDH; ISSN: 0143-148X

Document Journal

Abstract A wide range of environmental and chemical factors influenced the biodegradation ofsimple and complex phthalic acid esters in an aquatic environment. The length andconfiguration of the alkyl phthalate diester significantly affected the primarybiodegradation of di-n-butyl (DBP) [84-74-2], di-2-ethylhexyl (DEHP) [117-81-7],diisooctyl (DIOP) [27554-26-3], and diisononyl phthalate (DNIP)(I) [28553-12-0]. After14-days incubation in aerobic sediments at 22.degree, <2% of the branched-chainalkyl phthalates-DEHP, DIOP, and DINP (at µg concentration) were biodegraded,compared with 85% of the linear alkyl DBP. Primary biodegradation of DEHP, DIOP,and DINP was significantly greater at high concentration (>µg/L) and hightemperatures (>22.degree.) in freshwater sediments. Preexposure of the sediments toDBP, DEHP, DIOP, and DINP did not influence their biodegradation. The addition oforganic nutrients significantly affected the primary biodegradation of DBP with variedresults, depending on the nutrient, its concentration, and the time of addition. Neitherinorganic N nor P alone or in combination influenced the degradation of DBP. DEHPin sediments biodegraded under anaerobic conditions; even though the process wasslow, both primary and ultimate degradation did occur.

Author Karegoudar, T. B.; Pujar, B. G.

Title Biodegradation of phthalates and phthalate esters

Year 1984

Language English

Institute Dep. Chem., Karnatak Univ., Dharwad, 580 003, India

published in Proc. - Indian Acad. Sci., Chem. Sci. (1984), 93(7), 1155-8

Code, ISSN PIAADM; ISSN: 0253-4134

Document Journal

Abstract Several microorganisms utilizing terephthalate and diethyl phthalate (I) were isolatedfrom garden soil. Protocatechuic acid was one of the intermediates in the degrdn. ofterephthalic acid and I. Accumulation of protocatechuate during the growth of thesestrains was described.

15

Author Karegoudar, Timmanagouda B.; Pujar, Basayya G.

Title Metabolism of diethyl phthalate by a soil bacterium

Year 1984

Language English

Institute Dep. Chem., Karnatak Univ., Dharwad, India

published in Curr. Microbiol. (1984), 11(6), 321-4

Code, ISSN CUMIDD; ISSN: 0343-8651

Document Journal

Abstract A microorganism capable of degrading diethylphthalate as a sole C source wasisolated from garden soil and tentatively identified as Micrococcus sp.Monoethylphthalate and phthalic acid were shown to be the intermediates by TLC andspectrophotometric and mass spectral anal. The strain degraded diethylphthalatemainly through monoethylphthalate and phthalic acid as was evidenced by O uptakeand enzymic studies. Ethanol also supported the growth of this organism. Itappeared that the entire mol. was metabolized by Micrococcus sp.

Author Mersiowsky, I., Stegmann, R., Ejlertsson, J., Svensson, B.

Title Long-term behaviour of PVC products under soil-buried and landfill conditions

Year 1999

Institute Technical University of Hamburg-Harburg, Dept. of Waste Management, Germany;Linköping University, Dept. of Water and Environmental Studies, Sweden

Document Research Report

Language English

Abstract The long-term behaviour of various PVC products was investigated in laboratory scalelandfill simulation assays. Leachate and gas were monitored and PVC samples wereanalysed in order to assess whether a degradation of the PVC polymer or a loss ofplasticisers (phthalic acid esters) or stabilisers occurred. Degradation of the PVCpolymer was not observed. Some of the plasticised PVC products showerd a partialloss of additives. Furthermore, leachate samples from full-scale landfill sites wereanalysed for phthalates and organotin compounds. A preliminary assessment of theenvironmental impact indicates that the investigated PVC products do not significantlycontribute to the concentrations of heavy metals in landfills. The concentrations ofphthalates and organotin compounds found in leachate are not assessed to constitutea risk to the environment.

16

Author Miranda Romero; Luis A.; Gutierrez Castrejon, Teodoro

Title Biodegradation of plasticized poly(vinyl chloride) by Rhodotorula sp

Year 1985

Language Spanish

Institute Inst. Politec., Esc. Nac. Cienc. Biol., Mex.

published in Rev. Latinoam. Microbiol. (1985), 27(3), 231-6

Code, ISSN RLMIAA; ISSN: 0034-9771

Document Journal

Abstract The degrdn. of dioctylphthalate (I) and of PVC plasticized with I, using a Rhodotorulaspecies, was studied. Degradation of I was max. at pH 6.5 and 22.5.degree., at anaeration rate of 200 vols./min. Degradation of PVC film was >2% when the ratio ofPVC to I was 1.0 and <1% when the ratio was 0.4. When the PVC films were in sterilesoil inoculated with Rhodotorula and held for 28 days, the wt. loss was >3% and <2%,resp., for PVC/I ratios of 1.0 and 0.4.

Author Mogil’nitskii, G. M.; Sagatelyan, R. T.; Kutishcheva, T. N.; Zhukova, S. V.; Kerimov, S.I.; Parfenova, T. B.

Title Deterioration of the protective properties of poly(vinyl chloride) coating bymicroorganisms

Year 1987

Language Russian

Institute USSR

published in Zashch. Met. (1987), 23(1), 173-5

Code, ISSN ZAMEA9; ISSN: 0044-1856

Document Journal

Abstract Aerobic soil bacteria and fungi are involved in the deterioration of PVC [9002-86-2]tape coatings by reducing their adhesion, esp. around the holes. No egradation ofPVC tapes bonded to a metal pipe with a Bu rubber adhesive was observed whenexposed to the cultures of Pseudomonas fluorescens and Aspergillus niger.

17

Author Nielsen, S.

Title Investigation into the degradation of compounds injurious to the environment in sludge

Year 1998

Language Danish

Institute Hedeselskabet, Genanvendelsesrådet

published in Not published, ongoing investigations

Code, ISSN –

Document –

Abstract Investigation of the degradation of compounds injurious to the environment in sludgeby treatment in a demineralisation sludge basin and by simple storage of 9-12 months.The results will be compared with Danish limits of the compounds in sludge foragricultural use. It will also be evaluated if it is possible to decrease the content of thecompounds. The investigations will be carried out during 1½ year.

18

Author O’Connor, Owen A.; Rivera, M. D.; Young, L. Y.

Title Toxicity and biodegradation of phthalic acid esters under methanogenic conditions

Year 1989

Language English

Institute Inst. Environ. Med., New York Univ., New York, NY, 10016, USA

published in Environ. Toxicol. Chem. (1989), 8(7), 569-76

Code, ISSN ETOCDK; ISSN: 0730-7268

Document Journal

Abstract Phthalate, di-Me phthalate, di-Et phthalate, di-Bu phthalate, and di(2-ethylhexyl)phthalate were evaluated for their anaerobic biodegradability and toxicity tomethanogenesis. Two anaerobic bioassays (the biochemical methane potential andthe anaerobic toxicity assay) were used to monitor the stoichiometric conversion ofadded substrate to carbon dioxide and methane. Each phthalic acid ester was theonly added carbon source (20 to 200 mg/L) prepared in prereduced defined mediumusing a 10% inoculum of municipal digester sludge. Over an extended incubationperiod (50 to 100 d), all concentrations. of phthalate and di-Bu phthalate and lowconcentrations (20 mg/L) of di-Me phthalate and di-Et phthalate achieved 75 to 100%of their theor. methane potentials. Higher concentrations. (100 to 200 mg/L) of di-Mephthalate and di-Et phthalate achieved 25 to 50% of their theoretical methanepotentials. Di(2-ethylhexyl) phthalate showed little mineralization at anyconcentrations, although biotransformation of this substrate was indicated.Acclimation for most of the compounds took several days to weeks before degradationcommenced. In the anaerobic toxicity assay, only concentrations. greater than 20mg/L di-Et phthalate produced any significant suppression of methanogenesis overtime. All other substrates produced little inhibition of methanogenesis during the initialperiod of incubation. Generally, increased incubation led to increased levels ofmethane production above active control levels. Thus, many of these compoundswere metabolized completely under methanogenic conditions and were obsd. toproduce little inhibition of methane production Their fate, therefore, may besignificantly influenced by their concentrations. and residence time in methanogenichabitats.

19

Author Osipoff, Robert J.; Hutzler, Neil J.; Crittenden, John C.

Title Interaction of specific toxic organic chemicals percolating through a soil

Year 1981

Language English

Institute Williams Works, Inc., Grand Rapids, MI, 49501, USA

published in Proc. Ind. Waste Conf. (1981), Volume Date 1980, 35, 17-23

Code, ISSN PIWCAX; ISSN: 0073-7682

Document Journal

Abstract Batch rate studies done under high mixing conditions showed that di-Me phthalate (I)[131-11-3] and o-chlorophenol (II) [95-57-8] (both chems. are on the EPA list ofpriority pollutants) were both rapidly adsorbed onto the exterior surface of soilparticles. It appears that the liq.-phase mass transfer rate would control theadsorption rate. The adsorption capacity of the soil for each chem. could be describedby a nearly linear isotherm, with the relative adsorption capacity for II about equal tothat for I. Biodegradation studies using unacclimated soil cultures indicated that I wasreadily biodegradable, while II was not at concentrations equiv. to 10 mg C/L. A math.model which assumed instantaneous equil. was developed to predict the velocity ofthe chem. front based on the adsorption isotherm and to predict the service life of aland disposal site.

20

Author Pantke, Michael

Title Gravimetrisch, elektronenoptisch und chemisch erfaßbare Veränderungen an PVC-Folien nach Erd-Eingrabeversuchen

Year 1970

Language German

Institute Bundesanstalt für Materialprüfung

published in Material und Organismen (1970), No. 5, p. 197-215

Code, ISSN –

Document Journal

Abstract Microbiological attack of plastified polyvinyl chloride was gravimetrically, electronoptically and chemicaly investigated. 7 different PVC formulations were used for thetests. Relatively resistant phthalic acid esters with chain lengths of C8 and C9 wereadded to the basic polymer substance as primary plasticisers. Three test seriescontained an additional secondary plasticiser, i.e. a fatty acid ester which is known tobe susceptible to deterioration. After soil buried tests of 2, 4, 8, 12, 18, 24 and 48weeks the weight losses of the specimens measured in per cent were determined.During the first eight weeks deterioration proceeded rather rapidly, but the rate ofattack decreased later. Deterioration had not come to a standstill one year later.Weight losses amounted to 7% with secondary plasticisers and to 5% with primaryplasticisers only. The surface quality of small specimens of all tests series wasexamined by means of stereoscan. There was a good agreement between the relativeweight losses of the specimens and the degree of a progressive surface destruction.After a test period of 48 weeks a chromatographic investigation of the individualmixtures revealed that the original amounts of primary and secondary plasticiserswere reduced to 70-75% and 20-40%, respectively.

Author Peciulyte, D.

Title Utilization of phthalate esters by microorganisms

Year 1997

Language English

Institute Institute of Botany, Vilnius, 2021, Lithuania

published in Biologija (1997), (2), 33-37

Code, ISSN BOLOE8; ISSN: 1392-0146

Document Journal

Abstract The ability of microorganisms to use dioctylphthalate (DOP) and dibutylphthalate(DBP) as a source of nutrient carbon was investigated. During long-term studies onbiodegrdn. of plastics compounded with plasticizers we invented 16 fungal, 3 bacterialand 2 yeast strains able to use phthalate esters as the sole carbon and energy source.The selection of active biodegradants of the most common plasticizer,dioctylphthalate, was carried out. Strains of Rhodotorula rubra (Demme) Lodder J-96-1 and Aspergillus puniceus Kwon et Fenn. J-86-2 showed the best stability andadaptability in the process of phthalate ester degradation.

21

Author Plate, Dorothea

Title Schadstoff-Freisetzung aus Kunststoffen unter Deponie-Milieu-Bedingungen

Year 1997

Language German

Institute Forschungsinstitut für Leder- und Kunstledertechnologie

published in Abfallwirtschaftsjournal (1997), No. 10

Code, ISSN –

Document Journal

Abstract For the investigation of the behaviour of flexible PVC and the release of harmfulsubstances from PVC under soil-buried and landfill conditions test proceduresaccording to DIN 53 739 were modified. Degradation of the PVC polymer was notobserved. Although a loss of additives (plasticisers and stabilisers) were detected, dueto leaching and biodegradation processes, no accumulation of this components wasobserved in the soil.

Author Rossi, E., Ettala, M.

Title Environmental impact of packaging plastics disposal in sanitary landfills

Year 1988

Language English

Institute –

published in Third International Conference on Environmental Contamination. Venice, Italy 26-29.9.1988

Code, ISSN –

Document Conference

Abstract A review of the available technical information was carried out to elucidate themechanisms and products of plastics degradation in the environment. In addition,studies were made at several landfills of the condition of landfill refuse, quality ofgaseous emissions, leachate discharge and leachate in the refuse. From the synthesisof these studies it was concluded that packaging plastics undergo very slowdegradation in sanitary landfills. Important factors slowing down the degradationprocess are absence of UV light and low temperatures. The most importantdegradation processes are stress cracking and leaching out of additives. Stresscracking mainly produces inert macromolecules, which do not contaminate theleachate water or landfill gases. Nevertheless, stress cracking may make polymersmore liable to chemical or biological decomposition. PVC plastics contain a largeproportion of plasticisers, which are leached out fairly easily. Some plasticisers aretoxic and may contribute to contamination of leachate water.

22

Author Sakai, S.; Urano,S.; Takatsuki, H.

Title Leaching behaviour of persistent organic pollutants (POPs) in shredder residues

Year 1998

Language English

Institute Kyoto University, Kyoto City, Japan

published in Chemosphere v 37 n 9-12, Oct-Nov 1998 p. 2047-2054

Code, ISSN –

Document Journal

Abstract It is well known that some kinds of waste contain persistent organic pollutants (POPs)such as PCDD/DFs and PCBs. Leaching behaviours of these chemicals, however,have not been focused so much because of their low leachability. On the other hand,shredder residues originated from automobiles and electric appliances consist mainlyof plastics, such as PVC, which contain additives including DEHP. In this study,contents analyses and leaching tests with and without surfactant-like substances forshredder residues were conducted. As a result, shredder residues from automobileand electric appliance contained PCBs in ppm level and a quantity of PCDD/DFs.Surfactant-like substances increase the leaching concentration of POPs. DEHP alsoleached out considerably even though using distilled water.

Author Shanker, Rishi; Ramakrishna, C.; Seth, Prahlad K.

Title Degradation of some phthalic acid esters in soil

Year 1985

Language English

Institute Ind. Toxicol. Res. Cent., Lucknow, 226 001, India

published in Environ. Pollut., Ser. A (1985), 39(1), 1-7

Code, ISSN EPEBD7; ISSN: 0143-1471

Document Journal

Abstract The biodegradation of 3 phthalic acid esters (PAE's), di-Me phthalate (DMP) [ 131-11-3 ], di-Bu phthalate (DBP) [ 84-74-2 ] and bis(2-ethylhexyl) phthalate (DEHP)[117-81-7] was studied in a garden soil. The degradation rates of DMP and DBP weregreater than that of DEHP under aerobic conditions. Anaerobiosis created by floodinggreatly retarded the degradation of the three PAE's. The results suggest thatmicroflora, esp. bacteria, are actively involved in the degradation of the 3 phthalateesters.

23

Author Wams, T.J.

Title Diethylhexyl phthalate as an environmental contaminant - a review.

Year 1987

Language English

Institute –

published in Sci. Tot. Environ. (1987), 66: 1-16

Code, ISSN –

Document Journal

Abstract Di(2-ethylhexyl)phthalate (DEHP) is a priority pollutant in several countries; annualproduction amounts to 3-4 million tonnes. Approximately 95% is used as a plasticizerin polyvinylchloride (PVC). DEHP is emitted to the environment during the productionof plastics and plastic products, during their use and after disposal. In theenvironment, physico-chemical degradation of DEHP is practically non-existent.Biodegradation occurs readily under aerobic conditions (t1/2 = 2-4 weeks), but notunder anaerobic conditions. The acute toxicity of DEHP to mammals is low. Manysubchronic and chronic effects have, however, been identified. The most important ofthese are: influence on the liver and energy metabolism, teratogenicity, adverseeffects on male reproductive organs, carcinogenicity and influence on the immunesystem. On the basis of figures concerning human exposure, most of these effects arenot likely to occur. With respect to carcinogenicity the situation is uncertain, especiallyfor some risk groups. The ecotoxicology of DEHP is especially relevant for aquaticcommunities where data are contradictory: several authors have found adverse effectson Daphnia and fish species after exposure to the present environmentalconcentrations; others, however, produced less alarming results. Emissions of DEHPcan be reduced by the biological treatment of wastewater and waste gas, the use ofalternative plasticizers in PVC or the substitution of other plastics for PVC.

24

Author Wang, Jianlong; Liu, Ping; Shi, Hanchang; Yi, Qian

Title Biodegradation of phthalic acid ester in soil by indigenous and introducedmicroorganisms

Year 1997

Language English

Institute Environment Simulation and Pollution Control State Key Joint Laboratory, Departmentof Environmental Engineering, Tsinghua University, Beijing, 100084, Peop. Rep.China

published in Chemosphere (1997), 35(8), 1747-1754

Code, ISSN CMSHAF; ISSN: 0045-6535

Document Journal

Abstract The biodegradation of di-Bu phthalate (DBP) in soil microcosms by indigenousmicrobial population and a DBP degrading inoculum as well as DBP adsorption by soilwas investigated. The adsorption of DBP by soil conformed to Freundlich equation.The indigenous bacteria were capable of degrading phthalate in soil. The inoculationof the soil with DBP degrader enhanced the DBP degradation rate. The enumerationof microorganisms indicated a good correlation between phthalate degradation andmicrobial counts.

Author Wolfe, N. L.; Burns, L. A.; Steen, W. C.

Title Use of linear free energy relationships and an evaluative model to assess the fate andtransport of phthalate esters in the aquatic

Year 1980

Language English

Institute Environ. Res. Lab., EPA, Athens, GA, 30613, USA

published in Chemosphere (1980), 9(7-8), 393-402

Code, ISSN CMSHAF; ISSN: 0045-6535

Document Journal

Abstract The hydrolysis, photolysis, biolysis and volatilization of di-Me phthalate (I) [131-11-3],di-Et phthalate (II) [84-66-2], di-Bu phthalate (III) [84-74-2], dioctyl phthalate (IV)[117-84-0] and bis(2-ethylhexyl) phthalate (V) [117-81-7] in a river, a pond, aeutrophic lake, and in an oligotrophic lake were detd. I showed little tendency to becaptured by bottom sediments, was rapidly degraded and removed from contaminatedsystems. On the contrary, V accumulated significantly and was removed slowly fromthe aquatic systems. Volatilization accounted for 20% of IV loadings but only 2% of Vloadings. Apparently, hydrolysis, biolysis, photolysis, volatilization, and export can allbe competing processes depending on the properties of the phthalate esters and theecosystem. In general, the higher mol. wt. esters will not undergo significanttransformation.

25

Author Wolkober, Z.; Gyarmati, I.; Farkas, M.

Title Microbiological stability of soft PVC during ground storage

Year 1981

Language German

Institute Mikrobiol. Inst., Semmelweis Univ. Med., Budapest, Hung.

published in Kunstst. Fortschrittsber. (1981), Volume Date 1980, 7, 265-80

Code, ISSN KUFODG

Document Journal

Abstract The microbiological stability of PVC to soil bacteria and molds is discussed. Theplasticisers are subject to microbiological degradation. No known biocides can giveadequate protection to plasticisers against microorganisms at 30.degree and 100%relative humidity. Therefore, under such conditions, one should use plastics whichhave a sufficient inherent microbiological stability.

Author Yabannavar, A.; Bartha, R.

Title Biodegradability of some food-packaging materials in soil

Year 1993

Language English

Institute Rutgers Univ.; Njaes, Dept. biochem. & microbiol., Newbruswick, NJ08903

published in Soil Biology & Biochemistry, 1993, V25, N11 (nov), p.1469-1475

Code, ISSN –

Document Journal

Abstract The imminent shift of urban solid waste disposal from landfilling to recycling-composting programs directs attention to the biodegradability of certain foodpackaging items that are not suitable for recycling. Novel plastic wrap formulationsclaiming to be more degradable than their predecessors are now being marketed.Because biodegradability claims often appear in poorly documented promotionalliterature only, a comparative biodegradability survey of some novel highly plasticisedpolyvinyl chloride (PVC), traditional polyethylene (PE) and polypropylene (PP) wrapsas well as coated or impregnated paper products was made. All materials wereexposed in soil under conditions generally favourable for biodegradation. Themeasurement of CO2 evolution in Biometer flasks, decline in tensile strengths, incombination with newly developed residual weight determinations, and other residueanalysis techniques were utilized in assessing biodegradation. During 3 months ofexposure, traditional PE and PP films did not undergo measurable deterioration, but agroup of newly formulated and heavily plasticised PVC films underwent extensivebiodeterioration and up to 27.3% of their carbon was converted to CO2. However, gaschromatography, residual weight determination, chloride release and viscositymeasurements indicated that only the plasticiser but not the PVC resin wasmineralized. The wax-impregnated paper products were rapidly and completelymineralized. The PE-coating did not prevent the rapid mineralization of the cardboard,even when the material was left unshredded.

26

Author Yabannavar, Asha V.; Bartha, Richard

Title Methods for assessment of biodegradability of plastic films in soil

Year 1994

Language English

Institute Dep. Biochem. Microbiology, Rutgers Univ., New Brunswick, NJ, 08903-0231, USA

published in Appl. Environ. Microbiol. (), 60(10), 3608-14

Code, ISSN AEMIDF; ISSN: 0099-2240

Document Journal

Abstract Traditional and novel techniques were tested and compared for their usefulness inevaluating biodegradability claims made for newly formulated degradable plastic filmproducts. Photosensitized polyethylene (PE), starch-PE, extensively plasticized PVC,and polypropylene (PP) films were incorporated into aerobic soil. Biodegradation wasmeasured for 3 mo under generally favorable conditions. Carbon dioxide evolution,residual wt. recovery, and loss of tensile strength measurements were supplemented,for some films, by gas chromatog. measurements of plasticiser loss and gelpermeation chromatog. (GPC) measurement of polymer mol. size distribution. Six-and 12-wk sunlight exposures of photosensitized PE films resulted in extensivephotochem. damage that failed to promote subsequent mineralization in soil. An 8%starch-PE film and the plasticised PVC film evolved significant amts. of CO2 inbiodegradation tests and lost residual wt. and tensile strength, but GPCmeasurements demonstrated that all these changes were confined to the additivesand the PE and PVC polymers were not degraded. Carbon dioxide evolution wasfound to be a useful screening tool for plastic film biodegradation, but for films withadditives, polymer biodegradation needs to be confirmed by GPC. Photochem.crosslinking of polymer strands reduces soly. and may interfere with GPCmeasurements of polymer degradation.

27

Author Yano, Hiroshi

Title Studies on health effects of chemical products through environmental pollution levels.I. studies on health effects of phthalate esters

Year 1979

Language Japanese

Institute Fac. Med., Kobe Univ., Kobe, Japan

published in Nippon Eiseigaku Zasshi (1979), 34(2), 429-36

Code, ISSN NEZAAQ; ISSN: 0021-5082

Document Journal

Abstract Di-Bu phthalate (I) [84-74-2] and bis(2-ethylhexyl) phthalate (II) [117-81-7] were detd.by gas chromatog.-mass spectrometry. I and II were detected in many environmentalmaterials (e.g. human blood, mother’s milk, fish,, processed foods, fruits, leaves, riverwater, and sediments). Tree leaves contained high I (0.8-1.0 ppm) and II (0.7-0.8ppm), suggesting that they occurred naturally in plants. The gastrointestinalabsorption of I and II in mice was very low. Only 1.8% of I administered i.p. wasdetected in the body after 24 h, and II was decreased by half in .apprx.12 days. II wasnot absorbed within 49 days when administered orally to mice. Phthalic acid [88-99-3]was found in the urine as a I metabolite after i.v. administration. Dispersed livertissues of mice metabolized I to mono-Bu phthalate [131-70-4], mono-Et phthalate[2306-33-4], and phthalic acid. Neither I nor II was absorbed into goldfish after stayingin water (contg. 1 ppm I and II) for 2 wk and they were easily decomposted by bacteriaThus, the human health could hardly be affected by environmental contamination ofphthalate esters.

Author Ziogou, K.; Kirk, P. W. W.; Lester, J. N.

Title Behavior of phthalic acid esters during batch anaerobic digestion of sludge

Year 1989

Language English

Institute Civ. Eng. Dep., Imp. Coll. Sci. Technol., London, SW7 2BU, UK

published in Water Res. (1989), 23(6), 743-8

Code, ISSN WATRAG; ISSN: 0043-1354

Document Journal

Abstract In expts. with batch anaerobic digestion of sewage sludge spiked with di-Me, di-Et, di-Bu, butyl-benzyl, di-(2-ethyl-hexyl) and di-n-octyl phthalic acid esters, at a concn. of0.5-10 mg/L, the 1st 4 esters were degraded rapidly with degrdn. rates following 1storder reaction kinetics, whereas di-(2-ethylhexyl) and di-n-octyl phthalates appearedto be persistent under the same experimental conditions.

28

6WDELOLVHUV��KHDY\�PHWDOV

Author DEPA (Danish Environmental Protection Agency)

Title Leachate from construction waste (Udvaskning af byggeaffald)

Year 1992

Language Danish

Institute DTI Kemiteknik, COWI

published in DEPA (Danish Environmental Protection Agency), Work report no. 3

Code, ISSN –

Document Report

Abstract The primary objective of the investigations has been to provide a better foundation forestimating the problems of recycling and depositing of building and constructionwaste. Based on studies on literature on chemical components in building productsand collection of information in Denmark and abroad about leaching methods, anumber of clean sorted types of building waste was exposed to leaching tests andsubsequent determination of the concentration of selected chemical components. TheAmerican Toxicity Characteristic Leaching Procedure (TCLP) test has been used. Thismethod was developed for application on all types of waste. The experiments in thelaboratory showed that the method is practical applicable for examination of buildingwaste. The results indicate that problems might arise with uncontrolled depositing ofimpregnated wood, roofing felts and PVC where the concentration of a few chemicalcomponents exceed a number of national and international threshold limit values. Itwill be necessary to carry out a series of additional full scale lysimeter tests in order todocument the practical utility of the test method.

29

Author Hjertberg, Thomas; Gevert, Thomas

Title Evaluation of possible degradation of pipes and cable insulation of PVC-Resultsobtained with samples collected after about 25 years use

Year 1995

Language English

Institute Department of Polymer Technology, Chalmers Technical University of Gothenburg,Sweden

published in

Code, ISSN –

Document report

Abstract Degradation of soil buried PVC pipes and cable coverings used for about 25 yearshave been evaluated. Samples were analysed with respect to content of plasticiserand lead stabiliser, and possible degradation of the polymer. Furthermore, thesurrounding soil was analysed with respect to lead and phthalates. The PVC polymerin both samples did not show any signs that degradation had occurred during theapplication time. The content of plasticiser in the cable insulation had dropped toabout 20% from an expected value of 26-28%. The distribution of lead across the pipewall showed no indication of migration of lead from the material. The level of lead inthe soil samples collected close to the cable is most probably related to pollution fromthe traffic.

Author Länge, Reinhard

Title Environmental Risk Assessment of Organotin Stabilizers.

Year 1998

Language English

Institute –

published in not published

Code, ISSN –

Document internal document

Abstract The exposure and effects of mono- and diorganotin stabilizers were assessed. Mono-and diorgantotin stabilizers do not persist in the aquatic environment, however,degradation mainly by microorganisms is relatively slow. Half-life estimates for butyltincompounds range from a few days to three months under environmental conditions. Inwaste water treatment plants the butyl- and octyltin stabilizers are effectivelyeliminated. Adsorption to sewage sludge was observed for butyl- and octyltincompounds. Methyltin compounds were not found. Measured environmentalconcentrations are in the order of a few ng/l for methyl- and butyltin stabilizers, octyltinstabilizers were not detected in the environment. Leachates from landfills containedorganotin stabilizers at concentrations which were much below the predicted no-effectconcentration. This was confirmed by preliminary results of laboratory lysimeter study.The determined effect concentrations for mono- and dialkyltin stabilizers were so highin comparison with the estimated environmental concentrations that no risk for theaquatic environment was identified.

30

Author Yamamoto, T., Yasuhara, A.,

Title Quantities of bisphenol A leached from plastic waste samples

Year 1999

Language English

Institute -

published in Chemosphere (1999), 38: 2569-2576

Code, ISSN –

Document Journal

Abstract To quantify the leaching of bisphenol A into water, various samples of plastic wastewere cut into small pieces, soaked in water for two weeks at room temperature in thedark, and the concentration of bisphenol A in the water determined. The amount ofbisphenol A leached from the plastic wastes ranged from undetectable to 139 ug/g.The detection limit was 2 ng/g when 100 g of plastic waste was used. Polyvinylchloride products yielded the highest concentrations because bisphenol A is used inits manufacture as a stabilizer. As mentioned above, waste plastics belonging to thegroup with high leaching rates, such as polyvinyl chloride may be one of the mostimportant source of bisphenol A found in landfill leachate samples. Moreover, sincethe production and use of polyvinyl chloride products are far larger than ones ofpolycarbonate or epoxy-resin products, more attention should be paid to the use ofbisphenol A as stabilizer for polyvinyl chloride and the possible environmentalconsequences of this use.

31

5HOHDVH�RI�SODVWLFLVHU

Author Borisov, B. I.

Title Effect of aging on structure change in poly(vinyl chloride) coatings in the ground

Year 1980

Language Russian

Institute Vses. Nauchno-Issled. Inst. Moigistral’nykh Truboprovodov, Moscow, USSR

published in Korroz. Zashch. Neftegazov. Prom-sti. (1980), (6), 11-14

Code, ISSN KZNPAN

Document Journal

Abstract The thermal aging of poly(vinyl chloride) (I) insulating coatings on underground pipesat 286-9 K causes cracking, and eventually complete breakdown. Deterioration of Icoatings is also caused by plasticizer migration, which is even more significant causeof cracking than thermal aging. The most rapid aging of I coatings occurred in theKara Kum desert, where the av. soil temp. is 289.15 K, and soil porosity is 55%.

Author Greenpeace, Sweden

Title What is running out of our landfills (Vad rinner ut ur våra tippar)

Year 1999

Language Swedish

Institute Greenpeace, Sweden, SGAB/Analytica AB

published in www.greenpeace.se then press “Mediacenter”

Code, ISSN -

Document Internet-publication

Abstract During autumn 1998 Greenpeace investigated leachate from 28 landfills in Sweden.Samples of leachate from these landfills were analysed to determine compoundsinjurious to the environment. All together approx. 65 compounds are analysed for eachlandfill. Among these compounds are approx. 10 phthalates.

32

Author Kjoelholt, Thomsen, Hansen

Title Cadmium and DEHP in compost and in material from biogas production

Year 1998

Language Danish

Institute COWI

published in DEPA (Danish Environmental Protection Agency), Environmental Project No. 385

Code, ISSN –

Document Report

Abstract The objective of the study has been to investigate whether Danish compost andresiduals from biogas production based completely or partially on organic domesticwaste, comply with the existing and future threshold values for heavy metals andorganic micropollutants. Compost samples from nine composting facilities and onebiogas plant were analysed with regard to the content of cadmium and DEHP andsources of pollution are evaluated. The lowest amount of cadmium (0.25-0.30 mg/kgdw) was found in plants with the highest amount of organic domestic waste, while insamples from plants processing significant amounts of green waste, from urban areasin particular, the cadmium level typically increases to about 0.4-0.5 mg/kg dw.Regarding the DEHP levels found, the compost obtained from organic domestic wastemainly contains the highest concentrations of DEHP with a range of 20 –139 mg/kgdw. Sources for cadmium found in compost might be batteries, which still, byoccasional mistakes, can end up in the organic fraction of the domestic waste. Othersources must be sought among certain old plastic or metal products with longdurability or contaminated soil, though these materials ought not to occur in the waste.The pollution of DEHP is likely to come from a lot of small sources as PVC-products,certain glues and prints, colour printings from magazines, plastic bags etc. Aninvestigation of DEHP content in 17 categories of materials frequently observed asimpurities in organic waste from households revealed that no category can be singledout as the main responsible of the observed contamination level.

33

Author Randall Curlee, T., Sujit Das

Title Plastic wastes: Management, Control, Recycling and Disposal

Year 1991

Language English

Institute Oak Ridge National Laboratory, U.S. EPA

published in –

Code, ISSN –

Document –

Abstract The report was developed in response to the Plastic Pollution Research and ControlAct (1987) which directs EPA to investigate and to report on various issues concerningplastic waste in the environment, including: articles of concern in the marineenvironment, impacts of plastic waste on solid waste management, methods forreducing impacts of plastics on the environment and solid waste management. Thefocus of the report is plastic wastes in the municipal waste stream: the amount of suchwaste; its impact on human health, the environment, and management of the MSWstream and option for reducing these impacts. Section 4 examines managementissues and environmental concerns associated with disposing plastics (as part of theMSW) by the two primary means used in the United States: landfilling andincineration. Results regarding disposal of plastic wastes in landfills are summarisedas follows: Plastic polymers do not represent a hazard to toxic leachate formationwhen disposed in landfills, data are too limited to determine whether additives inplastics add significantly to the toxicity of MWS landfill leachate, one laboratory studyindicates that plastic wastes containing cadmium based pigments do not release toxicmetals in sufficient quantities to pose an environmental hazard. Analysis of leachatefrom monitoring of MSW landfills has detected organic chemicals such as are used asplasticisers; one widely used plasticiser, di(2-ethylhexyl)phthalate, has been detectedin a number of leachate analyses at a range.

34

Author Svetov, A. Ya.; Gutsalyuk, V. G.

Title Aging of plasticized poly(vinyl chloride) used as an insulating coating for undergroundpipelines

Year 1982

Language Russian

Institute USSR

published in Tr. Inst. Khim. Nauk, Akad. Nauk Kaz. SSR (1982), 57, 134-49

Code, ISSN TIKNAG; ISSN: 0568-5087

Document Journal

Abstract Elongation at break of PVC [9002-86-2] tape coatings contg. tricresyl phosphate[1330-78-5] as a plasticizer increased from 145 to 220% during 25 yr service on anunderground petroleum pipeline. Similar coatings contg. dibutyl phthalate [84-74-2]and dibutyl adipate [105-99-7] showed during the same period a decrease in theelongation at break due to deplasticization. The deplasticization theory was confirmedby the fact that the mech. loss peak of the 1st coating occurred at a lower temp. thanthat of the other coatings. The aging of coatings applied over a bitumen mastic waslower than in the case of a poly(tetrachloroethylene) [25135-99-3] adhesive.

35

(VWURJHQLF�HIIHFWV

Author Feldman, D.; Krishnan, A.

Title Estrogens in Unexpected Places: Possible Implications for Researchers andConsumers

Year 1995

Language English

Institute University Stanford, Stanford, , Ca/USA

published in EHP (Environmental Health Perspectives) Supplements (1995) Bd 103(7) S. 129-133

Code, ISSN

Document Journal

Abstract Estrogenic activity originating in unexpected places was encountered on threeoccasions during an investigation of whether Saccharomyces cerevisiae synthesizedestrogens. In each instance, estradiol found in the conditioned yeast-culture mediumoriginated from an exogenous source and was not synthesized by the yeast. In thefirst instance, yeast grown in the laboratory showed a time-dependent increase inestradiol in the conditioned medium. However, the culture medium supplement Bacto-peptone was found to contain large amounts of estrone. When added to yeast culturesin the form of YPD medium (yeast extract, Bacto-peptone, and dextrose), S.cerevisiae converted the estrone to estradiol leading to the accumulation of estradiolover time. In the second instance, commercially purchased S. cerevisiae grown in amolasses medium exhibited substantial amounts of estradiol. However, corn and beetmolasses contained sufficient estrone and estradiol to account for the findings. As inthe first instance, the yeast converted the estrone into estradiol. In the third instance,autoclaving culture medium in polycarbonate plastic flasks was found to cause anestrogenic substance to be added to the medium, whether yeast were present or not.It was determined that the autoclaving process leached bisphenol-A (BPA) out of thepolycarbonate plastic. BPA was shown to bind to estrogen receptors and to induceestrogenic activity, including stimulation of MCF-7 breast cancer-cell proliferation andinduction of the expression of progesterone receptors. The three instances highlightpotential problems for investigators who might inadvertently add estrogens toexperimental systems confounding their results. The BPA findings raise concernsabout the possible addition of this estrogenic molecule to the food supply sincepolycarbonate plastic is used in myriad applications in the packaging of food andbeverages. Although we are unaware of the substantial contamination of foodproducts with BPA, we believe this possibility should be carefully investigated.

36

Author Jobling, S., Reynolds, T., White, R., Parker, M. D., Sumpter, J. P.

Title A variety of environmentally persistent chemicals, including some phthalateplasticisers, are weakly estrogenic

Year 1995

Language English

Institute –

published in Environmental Health Perspectives (1995), 103:582-587

Code, ISSN –

Document Journal

Abstract Sewage, a complex mixture of organic and inorganic chemicals, is considered to be amajor source of environmental pollution. A random screen of 20 organic man-madechemicals present in liquid effluents revealed that half appeared able to interact withthe estradiol receptor. This was demonstrated by their ability to inhibit binding of 17ß-estradiol to the fish estrogen receptor. Further studies, using mammalian estrogenscreens in vitro, revealed that the two phthalate esters butylbenzyl phthalate (BBP)and di-n-butylphthalate (DBP) and a food antioxidant, butylated hydroxyanisole (BHA)were estrogenic; however, they were all less estrogenic than the environmentalestrogen octylphenol. Phthalate esters, used in the production of various plastics(including PVC), are among the most common industrial chemicals. Their ubiquity inthe environment and tendency to bioconcentrate in animal fate are well known.Neither BBP nor DBP were able to act as antagonists, indicating that, in the presenceof endogenous estrogens, their overall effect would be cumulative. Recently, it hasbeen suggested, that environmental estrogens may be etiological agents in severalhuman diseases, including disorders of the male reproductive tract and breast andtesticular cancers. The current finding that some phthalate compounds and some foodadditives are weakly estrogenic in vitro, needs to be supported by further studies ontheir effects in vivo before any conclusions can be made regarding their possible rolein the development of these conditions.

37

Author Harris, Catherine A.; Henttu, Pirkko; Malcolm, G. Parker; Sumpter, John P.

Title The estrogenic activity of phthalate esters LQ�YLWUR

Year 1997

Language English

Institute Department of Biology and Biochemistry, Brunel University, Uxbridge, Middlesex, UK;Molecular Endrocrinology Laboratory, Imperial Cancer Research Found, London, UK

published in Environmental Health Perspectives, Vol. 105, No. 8, August 1997

Code, ISSN

Document Journal

Abstract A large number of phthalate esters were screened for estrogenic activity using arecombinant yeast screen. A selection of these was also tested for mitogenic effect onestrogen-responsive human breast cancer cells. A small number of the commerciallyavailavle phthalates tested showed extremely weak estrogenic activity. The relativepotencies of these descended in the order butyl benzyl phthalate (BBP)>dibutylphthalate (DBP>diisobutyl phthalate (DIDP)>diethyl phthalate (DEP)Ydiisononylphthalate (DINP). Potencies ranged from approximately 1 x 106 to 5 x 107 times lessthan 17 -estradiol. The phthalates that were estrogenic in the yeast screen were alsomitogenic on the human breast cancer cells. Di(2-ethylhexyl) phthalate (DEHP)showed no estrogenic activity in these LQ�YLWUR assays. A number of metabolites weretested, including mono-butyl phthalate, mono-benzyl phthalate, mono-ethylhexylphthalate, mono-Q-octyl phthalate; all were found to be inactive. One of the phthalates,ditridecyl phthalate (DTDP), produced inconsistent results; one sample was weaklyestrogenic, whereas another, obtained from a different source, was inactive. Analysisby gel chromatography-mass spectrometry showed that the preparation exhibitingestrogenic activity contained 0.5% of RUWKR-isomer of bisphenol A. it is likely that thepresence of this antioxidant in the phthalte standard was responsible for thegeneration of a dose-response curve – which was not observed with an alternativesample that had not been supplemented with R�S¶-bisphenol A – in the yeast screen;hence, DTDP is probably not weakly estrogenic. The activities of simple mixtures ofBBP, DBP, and 17 -estradiol were assessed in the yeast screen. No synergism wasobserved, although the activities of the mixtures were approximately additive. Insummary, a small number of phthalates are weakly estrogenic in vitro. No data has yetbeen published on whether these are also estrogenic in vivo; this will require testsusing different classes of vertebrates and different routes of exposure.

38

Author Nordic Council of Ministers, Koebenhavn, /DK

Title Chemicals with Estrogen-like Effects

Year 1996

Language English

Institute

published in Koebenhavn/DK: Nordisk Ministerrad, TemaNord. Bd 580

Code, ISSN ISBN: 92-9120-918-X

Document

Abstract A variety of different chemicals used by industry and contained in everyday productshave proven to possess weakly estrogenic properties when tested in vitro and/or invivo. This status report collocates information on the Nordic use, consumption,discharge, environmental fate and ecotoxic effects of selected chemicals whichpossess such properties, i.e. bisphenol A, butylbenzyl phthalate (BBP), di-n-butylphthalate (DBP), nonylphenol ethoxylate (NPnEO) and octylphenol ethoxylate(OPnEO). The chemicals examined are all consumed in large annual volumes withinthe Nordic countries and throughout the world, which makes their presence andeffects in the environment likely. Based on data from the Nordic Products Registers,the total annual consumption of SIGMANPnEO and OPnEO, bisphenol A, BBP andDBP within the four countries Sweden, Denmark, Norway and Finland amounted to5330 t, 257 t, 2004 t and 2468 t, respectively, in 1994/1995. These consumptionfigures have a degree of uncertainty due to differences among the registers inprocedures used for the declaration and registration of products. This includesproducts containing chemicals with estrogen-like effects. The Nordic consumption ofNPEO declined significantly (41 percent) during the period from 1988/89 (8,500 t) to1994/1995 (5,020 t). This figure must, however, be viewed only as an indication of atrend because several uncertainty factors are associated with its calculation. In someNordic countries, the substitution of DBP with other plasticisers in product types suchas joint materials, flexo-dyes and photogravure dyes has begun in recent years.NPnEO and OPnEO are predominately used as emulsifying agents and surfactants incleaning and washing products. The phthalates BBP and DBP are mainly contained inproduct types such as paints, lacquers, joint materials, glues, printing inks, etc.Bisphenol A is mainly used as an intermediate in the production of epoxy andpolycarbonate resins, as a stabiliser for plasticisers in PVC and as an antioxidant inrubber and plastics.

39

Others

Author Liu, Xiaoyang; Cheng, Guisun

Title Effect of dibutyl phthalate on crops and microorganisms

Year 1992

Language Chinese

Institute Inst. Soils Fertil., Chin. Acad. Agric. Sci., Beijing, 100081, Peop. Rep. China

published in Zhongguo Huanjing Kexue (1992), 12(2), 158-60

Code, ISSN ZHKEEI; ISSN: 1000-6923

Document Journal

Abstract In green house pot expts., 7 species of plants were cultivated in soil which contained1000 ppm di-Bu phthalate (DNBP). At harvest, carrot roots, Chinese cabbage leaves,and tomato fruits contained 14.4, 6.1, and 3.3 ppm DNBP, resp. The dry powder ofsoybean seeds, sunhemp stems, mung bean seeds, and rice contained 20.0, 8.0, 6.5,and 5.0 ppm DNBP, resp. The height of mung bean seedlings is influenced when thesoil contained 200 ppm DNBP. Height and survival are both influenced with 400 ppm.When DNBP contents in soil are 0, 100, 200, 400, and 1000 ppm, the nos. of DNBP-degraded microbes are 1.57, 10.9, 19.1, 101.5, and 167.0.times. 106/g dry soil, resp.

40

Author Mueller, J.; Koerdel, W.

Title Occurrence and fate of phthalates in soil and plants

Year 1993

Language English

Institute Fraunhofer-Inst. Umweltchem. Oekotoxikol., Schmallenberg-Grafschaft, D-5948,Germany

published in Sci. Total Environ. (1993), (Suppl., Pt. 1), 431-7

Code, ISSN STENDL; ISSN: 0048-9697

Document Journal

Abstract Phthalate concentrations (di-(2-ethylhexyl)phthalate, dibutylphthalate andbutylbenzylphthalate) were measured in the neighborhood of phthalate-emitting plantsand in unpolluted areas in soil and maize. Special emphasis was given to differentiatebetween deposition and contamination via the soil -root pathway. Therefore, theenvironmental anal. program was extended by model experiments. Plots werefertilized with phthalate-containing sewage sludge prior to the cultivation of maize,oats and potatoes. In another experiment, plants were exposed to phthalate-treateddust. Degradation and uptake by plants of the three phthalates were studied. Theresults show that phthalates are general air contaminants and can be found inunpolluted areas, too. The concentrations ranged from background levels to peakvalues of 490 mg/kg for DEHP and 560 mg/kg for DBP in soil and 20 ppm DBP inplants. The model experiments suggest that surface accumulation of phthalates inplants and transport of the substances into other parts of the plants was notdetectable. Uptake of phthalates via the soil path was not detected, either. Theresults confirm that the accumulation of airborne phthalates in plant cuticles may bean important path, whereas the bioavailability of phthalates in soil and from leaves canbe ignored.

41

Author Ohtake, Yoshito; Kobayashi, Tomoko; Itoh, Shigeki; Yamamoto, Yuka; Yabuki, Masuo;Asabe, Hitoshi; Ono, Katsumichi

Title Study of biodegradability of LDPE, PS, PVC and UF concealed in soil for over 32years

Year 1993

Language Japanese

Institute Chem. Inspect. Test. Inst., Tokyo, 131, Japan

published in Nippon Gomu Kyokaishi (1993), 66(4), 266-75

Code, ISSN NGOKAF; ISSN: 0029-022X

Document Journal

Abstract Effects of microbes on LDPE, polystyrene (I), PVC, and urea-formaldehydecopolymers (II) buried in relatively highly microbial active soil for 32-37 yr were examd.by SEM, DSC, and FTIR spectroscopy. I and II were not affected as confirmed bytheir good transparency. plasticisers near the surface of PVC decreased, and PVCwas degraded by oxidn., but no change was detectable on its appearance. LDPE wasdegraded, giving whitening on both sides of its films, and there were no antioxidantsleft. When LDPE films were piled up, the parts not in contact with soil maintainedtransparency and gloss, but those parts in contact with the ground where aerobicbacteria were active decompd. to give C=O. The FTIR spectra of whitened andtransparent parts of LDPE and exts. in Et2O showed peaks of C=O, OH, OOH, andCO2R. The amt. of C=O was small wherever the degrdn. became severe in LDPE,being equal to that in the parts not in contact with soil. The amt. of Et2O ext. wastwice as large in the whitened parts as in transparent parts, indicating that in theformer depolymn. was in progress due to microbes.This study indicated that LDPEwas strongly affected by microbes in 32 yr.

Author Otha, Masaharu; Kubo, Tsugio; Matsumoto, Tadashi

Title Deterioration of plastic films in fungus resistance test and soil burial test

Year 1989

Language Japanese

Institute Air Cond. Res. Lab., Matsushita Electr. Ind. Co., Ltd., Japan

published in Bokin Bobai (1989), 17(10), 465-71

Code, ISSN BOBODP; ISSN: 0385-5201

Document Journal

Abstract To investigate microbial deterioration of plastic materials, fungus resistance (.ltoreq.5mo) and soil burial (.ltoreq.8 mo) tests were carried out, and the alteration of tensilestrength and elongation was inspected, using film-form test pieces. Polyesterpolyurethane films showed considerable strength degradation by microorganisms, anddegradation of the material by only the culture medium was also large. PVC,polyether polyurethane, polyamide, and polystyrene films were more or less affectedby microorganisms. Polyethylene film showed little degradation For the investigationof degradation of mech. properties in the fungus resistance test, it was important tosep. the effects caused only by the culture medium from those caused bymicroorganisms.

42

Author Safronova, R. F.; Strods, J.; Antipenko, L. D.; Khmelevskaya, I. O.; Sprintsyn, G. I.;Zicans, J.

Title Aging of poly(vinyl chloride) films in some corrosive media

Year 1981

Language Russian

Institute USSR

published in Sozdanie Primen. Polim. Izdelii Stroit. Melior. Sist. (1981), 82-90. Editor(s): Metra, A.Ya. Publisher: Vses. Nauchno-Proizvod. Ob’edin. Primen. Polim. Mater. Melior. Vodn.Khoz., Elgava, USSR.

Code, ISSN 46ZQAV

Document Conference

Abstract Plasticized PVC [9002-86-2] films contg. 10-20 parts/100 parts resin of VPN 1[69864-96-6] oligoester have increased resistance to aggressive media. The PVCfilms, 200-250 .mu.m thick, were prepd. by 15 min mixing at 160-165.degree. and 5min press forming at 160.degree. and 5 MPa pressure. The resistance of the films inaggressive media was examd. in distd. H2O, 10% HCl, and NaOH and 25% solns. ofCaCl2, MgSO4, and FeCl3, which are usually present in soils. The diffusion coeff. ofthe solns., tensile strength, and relative elongation coeffs. were used as agingparameters. The highest resistance to aggressive media was obsd. for PVC contg. noVPN 1, compared to the lowest wt. loss of samples modified with VPN 1. Thechanges in diffusion coeff. of modified PVC were related to the polymer-oligoesterinteraction leading to crosslinking and changes in structural ordering of the compn.PVC compns. contg. 10-20 parts VPN 1 had the lowest change in strength anddeformation properties independent of the chem. nature of the media.

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Author Thuren, A.

Title Determination of phthalates in aquatic environments

Year 1986

Language English

Institute Lab. Ecol. Chem., Univ. Lund, Lund, Swed.

published in Bull. Environ. Contam. Toxicol. (1986), 36(1), 33-40

Code, ISSN BECTA6; ISSN: 0007-4861

Document Journal

Abstract A method was developed for detg. phthalates in water, sediment, and organismssampled from 2 rivers in southern Sweden, near phthalate-consuming industries. AVarian model 3700 gas chromatograph with a 63Ni electron-capture detector,equipped with a 15 m .times. 0.25 mm (inner diam.) fused silica column, was used forthe sepn. and quantification of di-Me phthalate (DMP) [ 131-11-3 ], di-Bu phthalate(DBP) [ 84-74-2 ], benzyl butyl phthalate (BBP) [ 85-68-7 ], and di(2-ethylhexyl)phthalate (DEHP)(I) [117-81-7]. The phthalates eluted from the gas chromatog.column in the order DMP, DBP, BBP, and DEHP, and the response of the detectorincreased in the order DBP, DMP, DEHP, and BBP. The detector response was linearbetween 0.5-100 ng. The detection limit was 0.1 ng for DMP, DBP, and DEHP and0.05 ng for BBP. The recovery ranged from 25 to 30% for DMP, 60-70% for DBP, 60-130% for BBP, and 80-90% for DEHP.

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