Forschungs- & Entwicklungsinformationsdienst der Gemeinschaft - CORDIS

FP7

KBBPPS Berichtzusammenfassung

Project ID: 312060
Gefördert unter: FP7-KBBE
Land: Netherlands

Final Report Summary - KBBPPS (Knowledge Based Bio-based Products' Pre-Standardization)

Executive Summary:
The research project "Knowledge Based Bio-based Products' Pre-Standardization" (KBBPPS), is a project of seven research institutes and organizations involved in the bio-based economy. Besides those, six (beyond EU) organizations or individuals acted as official advisory partners.
The project aims at increasing the uptake speed of standards and certification systems for bio-based products. The project took three years until July 2015. KBBPPS covers research and demonstration on bio-based carbon content determination, biomass content methods not solely dependent on 14C-analysis and biodegradability and eco-toxicity test schemes. Next, identification and resolution of functionality related bottlenecks with the view to developing, harmonising and validating test methodologies have been undertaken. The possibilities for improving sample preparation, fractionation and thermal treatments have been studied in order to cover bio-based carbon and other bio-based elements determination. A comparison on what the optimum definition and determination of "bio-based" is has been concluded. Next, practical solutions for stakeholders, lab and field tests on biodegradation or biological derived elements will be investigated.

The project has a total of 33 deliverables of different nature. No peer reviewed articles have been published within the project period, but some are under development. No patents, trademarks, registered designs, etc. have come forward. The goal was that the project results can be copied one-to-one into European standards. This has been effective as two CEN Standards (CEN/TS 16640 and CEN/TR 16721) have been published based on KBBPPS data. Four standards under development on bio-degradability and bio-based content have been initiated by the project (partners). Several activities contributed to also reaching stakeholders beyond Europe, intending to have some standardization impact on a global level.

The project has exchanged information with ASTM and ISO and with organizations in the USA and Australasia; either directly or via one of its advisory partners. ASTM is discussing changes in its standard and a more formal exchange with CEN to coordinate research work on both sides of the Atlantic. Proposals for generic biodegradation standards to be developed under ISO have been developed by KBBPPS as CEN Members felt these tests involve not only bio-based products and are thus of a more generic nature and worldwide importance. By doing pre- and co-normative research for them, KBBPPS has allowed the European stakeholders to progress with well-defined, sound test methods correlated to actual field behaviour and applicability in the lab.
Project Context and Objectives:
The research project "Knowledge Based Bio-based Products' Pre-Standardization", is a project of seven research institutes and organizations involved in the bio-based economy:
1. NEN, the Netherlands Standardization Institute (NL),
2. ECN, the Stichting Energy research Centre Netherlands (NL),
3. UoY, the Green Chemistry Centre of Excellence at the University of York (UK),
4. nova, the nova-Institut für politische und ökologische Innovation GmbH (DE),
5. OWS, Organic Waste Systems NV (BE),
6. DLO-FBR, the Stichting Dienst Landbouwkundig Onderzoek, Institute Food & Bio-based Research at Wageningen University (NL), and
7. AUA, the Agricultural University of Athens (GR).

Besides the seven, six organizations or individuals acted as official advisory partners:
• Beta-Analytic (USA) a carbon dating lab,
• Europabio, the association for the European biotechnology industry,
• Scion from New Zealand a government owned non-food based bioproduct manufacturing and development institute,
• Prof R. Narayan from Michigan State University as an authority in ASTM and ISO on determination techniques for bio-carbon and biomass content,
• European Bioplastics representing over 100 bio-plastic producers, and
• The French plant-based chemistry association ACDV.

The project aims at increasing the uptake speed of standards and certification systems for bio-based products. The application of standards and certification systems in the European bio-based product industry has positive long-term effects on the overall development of bio-based product markets. Trade barriers are reduced and the development of a pan-European market for bio-based products is promoted. Finally, public acceptance of bio-based products is increased through ensuring and verifying the sustainable sourcing of raw materials, the effective bio-content and clear indication of their (comparative) functionality in relation to the regular products. The KBBPPS project aims at increasing the uptake speed of standards and certification systems for bio-based products.

This project covers research and demonstration on bio-based carbon content determination, biomass content methods not solely dependent on 14C-analysis and biodegradability and eco-toxicity test schemes. Next, identification and resolution of functionality related bottlenecks with the view to developing, harmonising and validating test methodologies have been undertaken. The possibilities for improving sample preparation, fractionation and thermal treatments have been be studied in order to cover bio-based carbon and other bio-based elements determination. A comparison on what the optimum definition and determination of "bio-based" is, has been concluded. Next, practical solutions for stakeholders, lab and field tests on biodegradation or biological derived elements will be investigated. The goal in the end is that the results can be copied one-to-one into European standards.

Following Mandates by the European Commission (EC), the European Standardization Committee (CEN) initiated a Technical Committee, CEN/TC 411. on "Bio-based products". The KBBPPS has participated in and reported to many of the groups developing standards under this committee. The project has exchanged information ASTM and ISO and with organizations in the USA and Australasia; either directly or via one of its advisory partners. By doing pre- and co-normative research for them, KBBPPS has allowed the European stakeholders to progress with well-defined, sound test methods correlated to actual field behaviour and applicability in the lab.

For the determination of the bio-based carbon content, tests methods focus on the application to specific products. Within this project a new horizontal standard for the determination of the bio-based carbon content for all bio-based products needed to be developed The standard includes all steps necessary to obtain reliable results, i.e. the sampling, the pre-treatment and the C14 determination. The work on bio-based carbon content was complemented by research addressing pre-treatments, direct bio-based content determination, and indirect biomass content assessments. Both the fractionation of formulations and new thermal treatments are examined as pre-treatments to enhance the clarity and accuracy of results from bio-based content analysis (Task 4.1). Additionally, reports on the direct determination of total bio-based content (Task 4.2), and the indirect calculation of total bio-based content (Task 4.3) have also been prepared. The objective of a standard test method and testing scheme for the determination of total bio-based content, that is not solely dependent on 14C analysis, has been supplied in the form of a series of recommendations on how best to implement the provisional European standards FprEN 16785-1 and prEN 16785-2. This is applicable to different bio-based products, especially lubricants, plastics, surfactants, and solvents which formed the focus of Work Package 4.

The last objective of this project was the development and the validation of biodegradation test methodologies in freshwater and soil for bio-based lubricants and bio-based solvents. The developed test methodologies are based on the current existing test methodologies for other product groups (chemicals, polymers, etc.) and consequently this work package comprises an extensive literature review of worldwide existing biodegradation test methodologies in different environments (freshwater, marine environment, anaerobic environment, compost and soil). The results of the validation of the methodologies were used as input by CEN.
Project Results:
Work packages 1 and 2 considered project management and dissemination respectively and their activiteis are reported in deliverables D1.3 and for instance D2.5, D2.6 and D2.8. Here we report only about the actual RTD work.

Work package 3: Bio-based carbon content
Work Package 3 was aiming at obtaining a complete horizontal standard for the determination of the bio-based carbon content for all bio-based products. In the field already some information is available on certain products. To harmonize all already available data (especially present in standards on a global level) an overview was made for all current relevant sampling and bio-genic carbon standards (D 3.1).

All relevant standards on a global level are reviewed with respect to the biogenic carbon con-tent determination. In general it is an overview of all standards that can be used when deter-mining the biogenic carbon content and will give directions when no relevant standards are available. The review is focused on all standards concerning sampling, pre-treatment and 14C determination of all product types, which includes solids, liquids, gasses and mixtures of these. Due to the fact that all three steps in the process of biogenic carbon determination are equally important, all the three steps are covered.

Generally, independently of solid, liquid or gaseous state of a material or product to sample, attention should be paid to representativeness of a sample. This is described in a large number of standards and is essentially not different for bio-based carbon determination as it is for all kinds of different chemical analyses. To release all carbon, material needs to be completely combusted, irrespectively of solid, liquid, or gaseous state of material. After the combustion procedure, all available carbon is collected as CO2 in a suitable absorber. After sampling, the collected CO2 is prepared for 14C analysis. The 14C determination method can be performed by three techniques, which are considered to be equivalent:
1) AMS - accelerated mass spectrometry
2) LSC - liquid scintillation counting
3) BI - beta-ionization technique

This was the starting point for the standardization process within TC411 (bio-based products)/WG 3 (chemical test methods). Within KBBPPS CEN/TS 16640 "Bio-based products — Determination of the bio based carbon content of products using the radiocarbon method” (D 3.2), was prepared and submitted to TC 411/WG 3. The Technical Specification CEN/TS 16640 was accepted by the work group. The Technical Specification incorporated the three steps for the complete process of the biogenic carbon determination, as observed in the literature review.

The first step is the sampling and within the Technical Specification all available sampling standards are cited. It was decided only to list all useful standards and not incorporate all possible sampling steps in the Technical Specification. The next step in the Technical Specification is the pre-treatment, which incorporates the complete transformation of all carbon present in the material into carbon-dioxide. This is the essential part of the Technical Specification, because it describes that for the biogenic carbon content, the bio-genic carbon content must be related to the total carbon content. For that step all carbon in the material need to be used for the biogenic carbon determination. Finally the C14 determination was described, including the two available methods that are widely used: Accelerated Mass Spectroscopy (AMS) and Liquid Scintillation Counting (LSC). In order to finalize a standard from this technical specification, a number of verification steps have to be followed. All steps were discussed within TC 411/WG 3, because the experts within WG 3 must be completely connected with the complete process, so clarity of the pro-cess is maintained.

The first step was a ruggedness test. At ECN a large number of different samples was tested and the results of these tests were presented in KBBPPS and also to TC 411/WG 3 (D 3.3 and D 3.4). The samples were provided through several (advisory) partners. The known 14C determination techniques are already standardized and exhibit a very high accuracy. Therefore it was decided that only a verification is needed for the total carbon recovery method which is based on complete combustion of a sample. Extraction of available carbon can be evaluated via determining the combustion recovery. For most tested materials, the CO2 conversion results indicate a very high carbon recovery rate (in the range 90 % -100 %) and thus prove the reliability of total carbon determination by the combustion and titration method. All performed measurements indicate a good agreement with data provided by sample suppliers (when available). Based on this, 95% of recovery is recommended in order to have a satisfactory result on the total bio-based carbon content.

Special attention shall be paid to those materials or products which contain volatile components since omitting the carbon from the volatile part can lead to incorrect value for the total bio-based carbon content. Also special attention should be paid when difficult combustible samples are involved. When combustion of the sample is not possible, a special combustion enhancer should be used to ignite the sample. For the correct bio-based carbon determination in the sample it is of importance to know the carbon content and the bio-based carbon content that is added to the system from the enhancer. Finally, attention should be given to Inhomogeneity, as it was illustrated by one of the analyzed materials. Large inhomogeneity can lead to several percent difference in the bio-based carbon content. In case a material is suspected to be inhomogeneous and a preparation of a representative sample is therefore of difficulty, it is better to analyze such material as a whole (when possible), or if possible, to analyze each component of it separately. All findings of the ruggedness test were incorporated in CEN/TS 16640 "Bio-based products — Determination of the bio based carbon content of products using the radiocarbon method”.

After the ruggedness test the next step for verification of the method is an interlaboratory test (D 3.4). The test was performed on a product for which it was assume difficult to determine the total carbon and eventually bio-based carbon content using CEN/TS 16640. A water-based paint containing volatile components and a low amount of carbon was chosen as difficult product. The results of both the total carbon content and the biogenic carbon content are satisfactory for all involved laboratories. Even though the pre-treatment that was performed by the different laboratories was different (especially the use of different combustion enhancers), the variation in the results could not be related to any pre-treatment.

The relative standard deviation for the total carbon content measured among the 5 different laboratories is 15% (11.77 ± 1.81, % of total C). For the biogenic carbon content measured among the 5 different laboratories, the relative standard deviations is 17% (11.0 ± 1.9, % of 14C). As stated before the use of different pre-treatment methods did not influence the final results. Care should be taken in case complete recovery after combustion is not obtained. This can become important when there is a distinct difference in biogenic carbon content between different components in the sample.

Concluding it was agreed in TC 411/WG 3 that with a difficult product analyzed with the present CEN/TS 16640 all laboratories obtained similar results and the next step in the verification process could be taken. Current tests will continue with a complete round robin in order to obtain the performance characteristics of CEN/TS 16640. For finalizing the standard a complete round robin will be performed within the Open-Bio project. The bio-lubricants (CEN/TC 19/WG 33) and bio-solvents (CEN/TC 411/WG 2) groups will wait for this standard in order to refrain from requiring ASTM D6866 in their documents.

Work package 4: Biomass content
The deliverables of Task 4.1 consisted of three reports, finalized in month 18 of the project. These correspond to D4.1 (Thermal treatment study: Assessment study report on novel thermal treatments for biogenic measurement), D4.2 (Assessment study report on fractionation of formulations pre-biogenic measurement), and D4.3 (Sample preparation techniques for total biomass content determination).
The results of the first study led to the recommendation that in instances where bio-based content analysis has produced a result of dubious accuracy, the combustion stage of sample preparation may be scrutinised to a greater degree with thermogravimetric analysis (TG). Some chemical functional groups are more susceptible to thermal decomposition than others, and so the carbon dioxide collected during combustion for subsequent bio-based carbon content analysis may not be representative of the entire sample. The example of a plastic material given below shows that mass loss under an oxygen rich atmosphere occurs in more than four stages as the temperature is increased (Figure 1). The depth of understanding obtained with TG and its hyphenation with infra-red (IR) spectroscopy is greatly improved over the typical thermal treatment methods, in which little is known other than the fact that combustion gases are evolved.

The fractionation methods demonstrated in D4.2 can be used in the verification of the total bio-based content of formulations. For example, the following formulation was successfully fractionated into its component ingredients (Figure2). The resulting fractions were analysed by a number of techniques, including nuclear magnetic resonance (NMR) and gas chromatography. In this instance separation was effective at producing the individual ingredients in quantitative amounts.

We found that simple preparative techniques such as freeze drying can assist conversion to carbon dioxide before radiocarbon analysis, and should be considered if combustion is not successful at first. Disadvantageously, chromatographic techniques either separated single ingredients into different substances, such as the triglycerides in vegetable oils, or could not identify and isolate the minor components of a formulation. Fractionation can also cause issues over the confidentiality of formulations, and agreements that formulators may enter into forbidding the analysis and separation of pre-formulated ingredients. Therefore fractionation can only be recommended if an independently determined total bio-based content of a formulation or composite is disputed by the supplier. Then the burden of proof should be with the formulator to provide the individual components of their bio-based product for separate bio-based content testing. With access to the ingredients, it is unlikely that fractionation of a finished article will actually be required.

Broader aspects of sample preparation are reviewed. The final conclusion being that there are sufficient spectroscopic, drying, and particle size reducing procedures already established for the needs of total bio-based content determination. These preparative methods were associated to the inventory of techniques relevant to the measurement of total bio-based content for elements other than carbon (primarily stable isotopes and elemental analysis) within D4.3.

The single deliverable of Task 4.2 concerns the direct analysis of total bio-based content. The direct determination of total bio-based content through analytical means (D4.4) can take the form of several approaches. It has been shown that the promising technique of stable isotope analysis is actually not suitable as a means of determining total bio-based content, at least not as a horizontal method. This is despite the technique featuring in CEN/TR 16721 (Bio-based products - Overview of methods to determine the bio-based content). Less well understood approaches (bio-markers, such as traces of DNA in a substance; spore elements, traces of nutrients indicative of plant origin; chirality) could not be developed into a comprehensive, unambiguous methodology.

The most robust approach to the direct determination of bio-based content is that of radiocarbon analysis combined with elemental analysis. To convert elemental composition data into a value of bio-based content the technique of atom connectivity must be applied (see later discussion on Task 4.3). Strictly speaking this is not a direct method because the origin of elements other than carbon is not measured, only inferred by their chemical bonding onto carbon atoms. Nevertheless the method is useful for communication of total bio-based content and is broadly applicable, as demonstrated by its development into the provisional European standard FprEN 16785-1.

To summarise, the main conclusions of D4.4 are as follows:
(1) measuring stable isotope ratios is, in general, not yet suitable to determine the bio-based content of products. The known variation in isotopic values due to source, type and geographical origin of the biomass used, applied processing technologies etc., is too large (see Figure 3).
(2) FprEN 16785-1 in its current form is considered being a validation method for bio-based content and is not applicable for direct measurement of the bio-based content of products.
(3) In spite of all efforts, the attempts to develop a direct measuring method to determine the bio-based content of products proved unsuccessful, implying that at this time there are no suitable direct methods for bio-based content determination available.

Task 4.3 produced a report on the indirect calculation of total bio-based content (D4.5). It was found that different calculations can give different results of total bio-based content. This is unadvisable, and a single approach was sought that gave the same result as other analyses to avoid an inherent bias depending on the approach used. A screening of existing calculation methods and novel approaches developed specifically for this work was applied across a large number of model products. The limitations and advantages of indirect calculations of total bio-based content were then considered. The most representative, robust and unambiguous technique was the carbon material balance. This is featured as an annex in prEN 16785-2 but is not the primary method. The bio-based carbon content of the final product can then be upgraded into total bio-based content by an atom connectivity calculation (Figure 4). The basis of the atom connectivity approach is that “if oxygen (O) and/or hydrogen (H) and/or nitrogen (N) element(s) is(are) bound to a carbon structure derived from biomass, its(their) fraction is(are) considered to be part(s) of the bio-based content” (source: FprEN 16785-1). Results for the total bio-based content obtained in this manner are the most intuitive and reproducible of the indirect techniques, and also match the results expected from the method described in FprEN 16785-1.

The format of the method presented in D4.5 was subsequently revised after discussion with CEN/TC 411/WG 3. An updated protocol has been provided to the aforementioned working group for reference. For example, the original test method in D4.5 produced a value for the average total bio-based content. This was proven to be the most suitable means of communicating the utilisation of biomass in the production chain in terms of the total bio-based content. The revised test method now calculates an analytically verifiable minimum total bio-based content, reflecting the requirements in the B2B reporting template of provisional European standard prEN 16848.

The work contained in D4.5 differs from the current developments in bio-based content standardisation, and for this reason KBBPPS deliverable report D4.6, which acts as a final series of recommendations regarding total bio-based content, is more harmonious with the provisional European standards FprEN 16785-1 and prEN 16785-2. In D4.6 a satisfactory framework for utilising prEN 16785-2 with validation made possible by FprEN 16785-1 has been constructed. Records of the bio-based content of intermediates along the production chain and final products should maintained with prEN 16785-2, and be verifiable by FprEN 16785-1 as and when required. Reporting for B2B communication can be done using prEN 16848. The key recommendations are listed here:
1. A material balance (prEN 16785-2) should be constructed from a full understanding of the process and the contribution of the biomass feedstock(s).
2. A minimum bio-based content (total and carbon) must be reported in a way that can be validated by 14C radiocarbon analysis (according to CEN/TS 16640 or equivalent) and elemental analysis (according to FprEN 16785-1).
3. Communication of the total bio-based content (and the bio-based carbon content) should exist between consecutive production chains and throughout the supply chain according to the reporting template contained within prEN 16848 (or equivalent). Business to consumer communication of total bio-based content shall take the form dictated by CEN/TC 411/WG 5 in a future standard.
4. Validation of bio-based content should be applicable to any intermediate product. Where bio-based content is unknown, or validation fails, the total bio-based content must be assumed to be zero and downstream calculations revised accordingly.

A representative schematic of a production chain is given as Figure 5. The transfer of documents (preferably as the datasheet contained in prEN 16848) stating the minimum bio-based content is required for each intermediate and ultimately the final product. If for any reason the claimed minimum bio-based content according to prEN 16785-2 cannot be validated using FprEN 16785-1 then its bio-based content must be assumed as zero. In such a circumstance, if intermediate ‘D’ of Figure 5 failed a validation for example, the (minimum) total bio-based content that can be reported for product ‘E’ would fall from 55% to 25%.

Work package 5: Bottlenecks and impacts on functionally tests
In the first half of the project, a list of 26 bio-based products was chosen as a basis for the research work (D5.2), after a stakeholder workshop was successfully held for validation of the list and its objectives (D5.1). The analysis of existing barriers hampering market entry for bio-based products (BBP) led to the Deliverable D5.3 “Market entry barriers”. The main focus of this research was on technical bottlenecks for BBP stemming from regulations, codes, norms and standards, but another aspect of the analysis were also barriers in the process chain such as access to raw materials, unsuitable political framework, lack of information, inappropriate communication and labelling as well as finance.Three categories of barriers stemming from norms and standards were identified:
1. Commonly used product specifications are not addressing favourable bio-based properties
2. Commonly used product specifications cover properties that are not really necessary for or related to product functionality, but these are not fulfilled by bio-based products
3. Bio-applicability is missing due to “old thinking” in terms of conventional products

During the synthesis of the results and discussions with partners – also from the Open-Bio project – seven products (groups) were selected for further study, based on the factors: existence of relevant barriers in terms of technical product properties, relevant market shares and existing testing facilities within the project consortia. The selected products were
• Packaging films,
• Disposable cups,
• WPC decking,
• Natural fibre insulation,
• NPK fertilizer,
• Bio-based mulch films and adhesives and binders.

In the second step of the bottleneck research, we conducted further expert interviews with the objective to confirm the identified barriers and to come up with solutions related to standardisation and testing. The results were presented in D5.4. Overall, not a lot of confirmed barriers stemming from norms and standards or test methods were identified. While it is still not unusual that bio-based products struggle to fulfil certain functionality requirements, this is mostly not due to discrimination or unjust determination of test methods or standards.

It needs to be stressed though that this results should be interpreted with some caution, since the requirements are very peculiar to each product group and also to the application. This is the reason that a lot more work was put into expert interviews than was originally envisaged. But even when talking to experts it is noticeable that the route of enquiry is unfamiliar for most of them, since they are much more focused on technically improving product properties and do not reflect on unfair treatment in standards or norms. Very few industry experts are the exception to this. Another caveat is that the research focused only on a selection of bio-based products, which is representative but not comprehensive. Also, the focus was very much on directly product / material related regulations, not on all the regulations for every conceivable application field. This would not have been possible within the framework of this project.

For some products, however, some very concrete problems were found in standards and test methods. The confirmed results are summarized in Table 1.

The analysis of a variety of green labels with a view on including bio-based content as a criterion yielded an overview report (D5.5) of the most popular ecolabels in Europe, investigated four of them in more detail and provides a very useful basis for the further analysis of the EU Ecolabel carried out in Open-Bio. The report concluded that for the four most popular European Type I multi-criteria ecolabels it is technically possible to add a bio-based share of products as a criterion to existing or newly developed criteria catalogues. Especially the EU Ecolabel, the Nordic Swan and the Blue Angel offer good framework conditions for such a development. The EU Ecolabel already requires lubricants to be made of a certain share of renewable raw materials, while the Nordic Swan covers bio-based shares (renewable raw materials or wood should be used as a raw material) for durable wood alternatives to impregnated wood, disposables for food and floor coverings. Both the Nordic Swan and the Blue Angel follow a policy that aims to support the use of renewable resources, which is stated in the general documents. The Blue Angel and the EU Ecolabel already offer facilities for a special sign on the label that could also advertise the use of renewable raw materials as a specific environmental advantage. All three cover samples of bio-based products in some products categories without them being specifically declared as bio-based.

Worldwide, there is much more potential to find other labels that could also integrate a bio-based share of the raw materials basis as a criterion for green products. However, within the scope of this task, it was not possible to go into detailed analysis of all these labels. Further research is needed, if concrete findings and recommendations were to be developed for the multitude of ecolabels.

Work package 6: Biodegradability
The work in this work package was initiated by an extensive literature study reviewing existing biodegradation and toxicity test methodologies in different environments on a worldwide basis (CEN, ASTM, ISO, etc.). Moreover existing labelling systems, certification schemes and standard specifications in which biodegradability is included were discussed (deliverable report D6.1, Report on current relevant biodegradation and ecotoxicity standards; publicly available on KBBPPS website). This deliverable is a detailed and technical review of the topic containing information on inter-national (e.g. ISO, US, Australian, EU, etc.) standards in addition to the review of toxicity standards and a discussion on specifications of the (national) European labels.

Subsequently, questionnaires were sent to lubricant and solvent industry in order to investigate needs and problems related to biodegradability, environmental safety and labelling. The contact persons were mainly participants from CEN/TC 19/WG 33 “Bio-lubricants” and CEN/TC 411/WG 2 “Bio-solvents” (deliverable report D6.2, Draft biodegradability standard). For lubricants, it could be concluded from the answers to questionnaires that the existing OECD methods are well established and there is no need to write completely new biodegradation testing methods or ecotoxicity testing methods. Focus should be on improvement of biodegradation testing methods (addition methods for poorly water-soluble test items, reproducibility, variation in the inoculum, etc.). For solvents, the responses showed that no further work on biodegradation and toxicity seemed necessary. This was confirmed in a meeting with CEN/TC 411/WG 2.

In a next step some preliminary tests with respect to sample addition, reference material and inoculum were executed by OWS (freshwater and soil) and AUA (soil) in order to create some background information for the development of the test methodologies. Simultaneously with the first preliminary tests executed in freshwater and soil, biodegradation test methodologies in freshwater and in soil were developed for bio-lubricants (deliverable report D6.2, Draft biodegradability standard). Following freshwater biodegradation methodologies were developed in CEN/TC 19/WG 33 TF Biodegradation: (1) Method A (carbon conversion method): Liquid petroleum products - Bio-lubricants - Determination of aerobic bio-logical degradation of fully formulated lubricants in an aqueous solution - Test method using detection of CO2 production and (2) Method B (manometric respirometric method): Liquid petroleum products - Bio-lubricants - Determination of aerobic biological degradation of fully formulated lubricants in an aqueous solution - Test method based on O2 consumption. Project partner OWS participated to the meetings and reviewed the methodologies. The above mentioned methodologies are based on ISO 9439 Water quality – Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium – Carbon dioxide evolution test (1999) and ISO 9408 Water quality – Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium by determination of oxygen demand in a closed respirometer (1999), respectively. Improvements related to reference material, addition method and inoculum were included in order to increase the reproducibility of the methods. The test methodology in soil was developed within the project partners and was based on ISO 17556 Plastics – Determination of the ultimate aerobic biodegradability of plastic materials in soil by measuring the oxygen demand in a respirometer or the amount of carbon dioxide evolved (2012). Improvements related to reference material and sample addition were included.
In the final phase of the project the reproducibility of the developed test methodologies was evaluated by means of two interlaboratory tests (deliverable report D6.4, Biodegradability method validation and deliverable report D6.5, Biodegradability standards assessment report).

The objective of the first part of the interlaboratory test in freshwater was the comparison between two different addition methods: (1) direct addition of sample on a stirrer and (2) solution of sample in a solvent (on request of CEN/TC 19/WG 33). The standard deviation in the series with the stirrer was higher when compared to the addition method in the solvent (= hexane) (Figure 6). The results of the first part of the interlaboratory test were presented by OWS during the meeting of CEN/TC 19/WG 33 “TF Biodegradation” in Mannheim (August 2014). The results confirmed the expectations of the other participating laboratories (addition method in a solvent is the most optimal).

In the description of work it was mentioned that WP6 would focus on bio-based lubricants and bio-based solvents. After the discussions with CEN/TC 411/WG 2 “Bio-based solvents” and based on the results of the questionnaires, it was decided to focus only on bio-based lubricants as pre-standardisation work related to biodegradation and toxicity of bio-based solvents was deemed not necessary by the stakeholders.

The objective of the second part of the interlaboratory test in freshwater was the evaluation of the reproducibility between the laboratories (as requested by CEN/TC 19/WG 33). The test was executed on three samples (low, medium and high biodegradability) provided by CEN/TC 19/WG 33. The test was executed by 3 laboratories of CEN/TC 19/WG 33, AUA, DLO-FBR, OWS and advisory partner Scion from New Zealand. The results of the freshwater biodegradation test after 28 days were characterised by a maximum standard deviation around 10%. Such standard deviations are comparable to the standard deviations reported in RR# D02-1584 (Inter-laboratory study to establish precision statements for ASTM D5864, Standard test method for determining aerobic aquatic biodegradation of lubricants or their components (13 December 2005)). The difference between the samples with high, medium and low biodegradation was clearly observed (Figure 7). The biodegradation results (freshwater) were forwarded to CEN/TC 19/WG 33 “TF Biodegradation” in order to determine the reproducibility of the developed freshwater methodologies. The results of the biodegradation tests in freshwater were presented by OWS during the meeting of CEN/TC 19/WG 33 “TF Biodegradation” in Berlin (May 2015).

The samples received from CEN/TC 19/WG 33 for the interlaboratory testing in freshwater were also used for the interlaboratory testing in soil, which was performed by AUA, OWS and advisory partner Scion from New Zealand. The results of the soil biodegradation test were characterised by standard deviations < 7%. Such standard deviations are comparable/lower than standard deviations reported in the Round Robin test that was executed in ISO 17556:2012 on microcrystalline cellulose reference material and starch/poly(butylene adipate-co-butylene terephthalate) blend test material. The difference between the samples with high, medium and low biodegradation was clearly observed (Figure 8).

Finally, the validation of the laboratory tests by a field test was executed by AUA. Biodegradability in soil under laboratory conditions was determined by measuring the CO2 production, while in the field the evolution of the organic carbon content in the soil was determined to estimate qualitatively the fate of the lubricant. Although the field test took place under uncontrolled conditions, namely varying temperature and water content of the soil, biological factors and occasional presence of natural rain water, it can be concluded that the biodegradation of the samples roughly followed the same pattern as observed in the laboratory tests (Figure 9).

Potential Impact:
An overview was made for all current relevant sampling and biogenic carbon standards (D 3.1). This was the starting point for the standardization process within CEN/TC 411/WG 3, to obtain a horizontal standard for the determination of the bio-based carbon content for all bio-based products and to harmonize the new standard with the already available ASTM D6866 standard (which contain some points regarding the determination process of the biogenic carbon content which are debateable). This process resulted in CEN/TS 16640 "Bio-based products — Determination of the bio based carbon content of products using the radiocarbon method (D 3.2). CEN/TS 16640 was accepted by TC 411/WG 3. In order to get a complete standard from this technical specification, a number of verification steps have to be followed. Within this project the steps of verification of the method (D 3.3, D 3.4 and M6) and the interlaboratory test (D 3.5 and M7) were performed. The results of these steps were discussed within TC 411/WG 3 and improvements were incorporated in CEN/TS 16640. For finalizing the standard a complete round robin will be performed within the Open-Bio project.

Discussions on the harmonization of CEN/TS 16640 with ASTM D 6866 have been supported by the project results and partners and possible solutions are currently under review. The main difference is that ASTM determines the bio-based content on the basis of the total organic carbon. The KBBPPS project has defined additional sample preparation steps for products containing inorganic carbon as well as internal verification criteria to determine whether these have been successful. That allows the test laboratory to determine the total biogenic carbon content. Harmonising CEN and ASTM would be preferable, but difficult given the current status and embedding of the ASTM standard in the US. Question is how this can be solved. Especially the advisory partners Beta-Analytics and Prof. Narayan had assisted the partners in resolving this. The optimal possibility now put forward to CEN, is to introduce clear remarks in the forewords of both standards about the differences in wording and terminology, another solution is to change carbon content into biogenic carbon con-tent. This will have further complications in other standards and therefore will have to be discussed within CEN/TC 411.

For standard being developed for the bio-based content , the standard regard-ing the bio-based carbon content is an essential part for pr EN 16785: “Determination of the bio-based content using the radiocarbon analysis and elemental analysis”. The work on bio-based content can be summarised as a process of eliminating unsuitable approaches to the determination of total bio-based content, and refining a set of acceptable methods from what initially consisted of many possibilities (Figure 10). The recommended techniques for the determination of total bio-based content have been demonstrated to work together in a complementary way. Those methods that were not harmonious were discounted (e.g. stable isotope analysis, mass balance). How to apply the acceptable methods in such a manner to produce equivalent results was presented to CEN as D4.6.

The research into barriers stemming from standards, norms or test methods yielded less results than expected. It is still not completely clear whether this is simply due to a lack of discrimination against bio-based products in these frameworks, or whether there is a lack of awareness among the interviewed industry experts about these issues. The scope of the project was not sufficient to investigate all standards and norms related to applications of bio-based products (i.e. construction etc.) which might constitute unjust barriers.

The development of direct and indirect approaches to the determination of total bio-based content has been conducted with the continued input of CEN/TC 411/WG 3. An update to D4.5 was made after consultation with the aforementioned working group. The results of Task 4.2 and Task 4.3 are now of relevance to continued co-normative research in the Open-Bio project, and for the successful implementation of provisional European standards FprEN 16785-1 and prEN 16785-2.

The first objective of the functionality work was to identify the most important bio-based intermediates and materials from a market and functionality point of view. For this, list of 26 products (D5.2, see Table 2) was compiled during the first reporting period including a wide range of products, covering many different application sectors, markets, materials etc. This list of materials is the basis not only for the functionality aspects covered in this work package, but also for the testing in all other work packages.

Another objective was identifying the functionality related issues that hinder bio-based products from entering the market and then make to suggestions for adjusting, developing, expanding, harmonising and validating test methodologies for functionality testing. In order to reach this objective, extensive desk research and an industry survey served to investigated the most important barriers and bottlenecks impeding the market uptake of the selection of bio-based products shown above (deliverable D5.3). Possible solutions were also developed and a resolution action plan was conceptualized (D5.4).

Lastly, the work package also comprised a review of existing ecolabels for the selected group of products to discuss the possible conflicts of harmonization with the bio-carbon or biomass content. This analysis has been used as input to Open-Bio in order to support the further development of an ecolabelling scheme considering bio-based content in the criteria catalogues.

Next, it was mentioned in the description of work that research with regard to toxicity would be executed. However, that work during the project was rather limited as the results of the questionnaires demonstrated that no needs existed in the industry and amongst the CEN experts with regard to toxicity. Moreover, the performed literature study revealed that the current approach used by the labelling schemes (aquatic toxicity tests on different trophic levels) is very detailed and takes into account the current European legislation in order to avoid that toxic compounds enter the environment. Notwithstanding this, CEN/TC 19/WG 33 developed an idea on a work item for ecotoxicity that was balloted and accepted at the end of the project.

An extensive literature review on biodegradation and toxicity test methodologies in freshwater, marine environment, anaerobic conditions, soil and composting was published (publicly available on the KBBPPS website). This document was used as reference work in a French standard for home compostable products (NF T 51-800 Spécifications pour les plastiques aptes au compostage domestique), with the assistance of advisory partners ACDV and Scion.

Biodegradation test methodologies in freshwater and soil for bio-based lubricants have been developed within the project. The freshwater biodegradation methodologies were developed in cooperation with CEN/TC 19/WG 33 TF Biodegradation (with input of KBBPPS partners), while the test methodology in soil was developed by the project partners. The test methodologies were validated within the project partners (AUA, DLO-FBR and OWS). Moreover, advisory partner Scion from New-Zealand participated to the interlaboratory testing. The results were used by CEN/TC 19/WG 33 in order to evaluate the reproducibility of the biodegradation test methodology in freshwater. This input may have a positive impact on further development and uptake speed of this standard. Especially because two proposals for new work under CEN based on the KBBPPS data have recently been accepted for development into European Standards.

Besides the development and validation of biodegradation testing methods, following acceptance criteria are considered to be suitable according to the KBBPPS partners:

Freshwater:
The interpretation of the results of the biodegradation test in freshwater varies in function of the composition of a test material.
Option 1: Test material is a pure substance
At least 60 % absolute biodegradation needs to be reached within 28 days in order to call the test material ready biodegradable (in line with requirement as prescribed by OECD 301).
Option 2: Test material is a blend of different substances
At least 90 % biodegradation (absolute or relative when compared to a suitable reference material) needs to be reached for the test material within 56 days in order to call the material biodegradable in a freshwater environment (in line with the requirement of EN 14987). Moreover, constituents present in a concentration between 1 % and 10 % need to be evaluated separately on biodegradation.

Soil:
At least 90 % biodegradation (absolute or relative when compared to a suitable reference material) needs to be reached for the test material within 2 years in order to call the material biodegradable in a soil environment. Moreover, constituents present in a concentration between 1 % and 10 % need to be evaluated separately on biodegradation.

In the final advisory workshop the relation and maybe necessary distinction between bio-beginning and bio-end-of-life was debated. Participants didn’t think there is a relation that needs to be addressed via standards or further research, although in communication of products it can be helpful to be clear on end-of-life. Toxicity and composting were also discussed. Toxic intermediates can be present in organic compost, but after a while it may mature and loose its toxicity. This would however be very difficult to measure. Conclusions of the discussion were;
• There is a non-link between bio-begin-of-life and bio-end-of-life
• There is a need for horizontal standards, structure is to be elaborated further
• Environmental safety; is still an open domain, potential toxicity of metabolites.

The idea of the horizontal biodegradation standards was introduced to the CEN/TC 411 meeting of 25 June 2015. In this meeting, it was decided that CEN/TC 411 was not the suitable group in order to start work on horizontal biodegradation standards (as otherwise people could get confused by making a link between the terms “biodegradable” and “bio-based”). With assistance of ECOS (European Environmental Citizens' Organisation for Standardisation) and other CEN/TC 411 experts agreed to assist in developing such idea in a new group on environmental claims/characterization. This would be part of the Open-BIO project.

During the final advisory workshop five reasons were established why bio-based content should be preferred over bio-based carbon content:
1. One claim on the market would be preferred. As supporting the bio-based market is the main aim of the KBBPPS project, bio-based content makes the most sense as the bio-based content method gives a complete analysis.
2. Only bio-based content is preferred, because carbon content can give the wrong impression. In the US only carbon is taken in account (also because of carbon footprint), but if you’re looking into LCA you see that’s not the most relevant and can lead to wrong implications.
3. Strictness; CEN/TC 411 and the bio-based sector are so strict. No other sector is so exactly working. For example, such strictness is not observed in biofuels; not measured. Why can we release strict bio-based content limits and not just work with ranges? We’re maybe too ambitious.
4. Bio-based content concept; easy to integrate products that are 100% bio-based who don’t have bio-based carbon content.
5. An example of a bio-based product is the so-called ‘fossil-tomato’; using fossil carbon gasses for production of tomatoes in green house. The tomato is absolutely bio-based, but in the measurement it will be derived as not bio-based carbon.
The follow-up EU-funded Open-Bio project will look further into these issues. Additionally, it will be very difficult to measure carbon content in mixtures, so it isn’t only a problem for bio-based content measurements. This discussion also has an impact on the talks between the USA and the EU as the diverging views on what sufficiently defines bio-based content are the basis of policies to promote bio-based products on both sides of the Atlantic.

List of Websites:
project-website: www.kbbpps.eu
project manager:
O.M. Costenoble, M.Sc.
Netherlands Standardization Institute
NEN Energy Resources
Vlinderweg 6, 2623 AX Delft, the Netherlands
Tel.: +31 (15) 2690 326
Fax: +31 (15) 2690 207
E-mail: energy@nen.nl

Verwandte Informationen

Dokumente und Veröffentlichungen

Kontakt

Annetta van Wijk, (Financial Coordinator)
Tel.: +31152690211
E-Mail-Adresse

Fachgebiete

Scientific Research
Datensatznummer: 184230 / Zuletzt geändert am: 2016-06-02
Informationsquelle: SESAM