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Im DIN-Normenausschuß NMP 412 wurden in der Vergangenheit verschiedene Verfahren zur Holzschutzmittelanalytik genormt, die vorrangig einige der klassischen Holzschutzmittelkomponenten betreffen. Für die zunehmend auf den Markt drängenden neuen Wirkstoffe fehlen genormte Analysenverfahren. Der Bericht enthält einen Überblick zu gegenwärtig verfügbaren und angewandten Analyseverfahren.
Emissions OECD guidelines
(2004)
Standardized tests for wood preservatives are performed with defined fungal strains to ensure comparability between laboratories. However, changes of virulence and variation of results are well known events. Suitable and reliable measures to control the stability of the test organisms are necessary.Comparison of protein patterns produced by SDS-electrophoresis was already described by several authors as a possible way to identify and to characterize fungal species and strains, i.e. for Serpula, Coniophora and Poria. We compared protein patterns of several strains of Antrodia vaillantii, Poria placenta, Gloeophyllum trabeum, Lentinus lepideus, and Coniophora puteana. Isoelectric focussing and detection of esterase isoenzymes proved to be an alternative method. The investigations resulted in species-specific protein and enzyme patterns. By comparing the strains of single species it was possible to form groups with similar patterns. Possible misidentifications could be detected. The described methods will be further developed and used to follow possible changes in our test strains.
Methods for the determination of biocide emissions from treated materials into water and air were developed and tested in order to support a comparative ecological assessment of biocidal products. Leaching tests, experiments with simulated rain, extraction cleaning of carpets and emission chamber tests were performed with a series of treated materials. The experiments focused on the effect of changes in the procedure as well as characteristics of the specimens and demonstrate the suitability of the proposed methods for biocides of different product types.
It was demonstrated that emissions of biocides into water can be compared on the basis of leaching tests in which the emission kinetics of the active ingredients are recorded. However, the water volume per surface area and the timetable for water changes have to be defined in such tests. Functions of flux rates related to time can be well described for inorganic compounds, whereas modelling of the data is more complicated for organic substances.
Emission chamber tests using 20-litre and 23-litre glass exsiccators, originally developed to study volatile organic compounds, were successfully adapted for the investigation of the emission of biocides from treated materials which are usually semi volatile organic compounds. However, test parameters and the method of analysis have to be adapted to the substances to be determined.
Generally, it was found that the emission curves for the semi volatile organic compounds investigated differ from those of volatile organic compounds.
Vergleichsanalysen zur Bestimmung von Permethrin aus Holz ergaben, dass sich sowohl Extraktion mit Methanol im Ultraschallverfahren als auch Soxhlet-Extraktion mit Ethylacetat gut eignen, um Permethrin aus behandeltem Holz zu lösen. Verschiedene andere Extraktionsverfahren führen zu Minderbefunden. Zur quantitativen Bestimmung von Permethrin können sowohl Hochdruckflüssigchromatographie als auch Gaschromatographie eingesetzt werden.
Hintergrund, Ziel und Zweck Die Belastung von Flie?gewässern durch organische Mikroverunreinigungen wirft häufig die Frage der Quellenzuordnung auf. Baumaterialien als Quellen problematischer Spurenstoffe finden in der Gewässerbeurteilung bisher wenig Beachtung, obwohl bereits heute biozide Wirkstoffe aus Materialschutzanwendungen zu einer Belastung des Regenwasserabflusses führen. In der vorliegenden Untersuchung wurden (1) die ökotoxikologischen Kenngrößen für typische Biozide in Fassadenbeschichtungen ermittelt, (2) die Auswaschung von besonders problematischen Bioziden aus Fassaden quantifiziert und (3) das Belastungsrisiko für Gewässer mittels Stofftransportmodellierung abgeschätzt.
The content of chromium in different oxidation states in chromium-treated wood was studied with XANES (X-ray absorption near-edge structure) measurements at the Cr K absorption edge. It could be shown that wood samples treated with Cr(VI) (pine and beech) did still contain a measurable content of Cr(VI) after four weeks conditioning. If such wood samples were heat exposed for 2 h with 135 °C prior conditioning, Cr(VI) was no longer detected by XANES, indicating a complete reduction to chromium (III).
Fenoxycarb ist ein insektizider Wirkstoff,
der wegen seiner hormonähnlichen Wirkung in sehr
geringen Konzentrationen in Holzschutzmitteln eingesetzt
werden kann. Das hat zur Folge, dass aus Extrakten von
behandeltem Holz relativ geringe Fenoxycarb-Mengen vor
dem Hintergrund ebenfalls extrahierter Holzinhaltsstoffe
zu bestimmen sind. In Vergleichsanalysen verschiedener
Laboratorien wurde gezeigt, dass Fenoxycarb durch Methanol
mit hoher Ausbeute aus Holz extrahierbar ist und
in den Extrakten durch Hochdruckflüssigchromatographie
in Kopplung mit UV-Detektion bestimmt werden kann.
Fenoxycarb-Konzentrationen im unteren Bereich der
erforderlichen Einbringmengen können mit dem erprobten
Verfahren nur nach zusätzlicher Probenaufarbeitung
bestimmt werden. Bedingt durch schwer auswertbare
Chromatogramme sind die Abweichungen der Ergebnisse
zwischen verschiedenen Laboratorien relativ hoch.
Facades are attacked by algae and fungi during weathering, impairing the surfaces visually and leading to long-term damage. To prevent this, appropriate biocides are used in facade coatings.
These can be washed out during weathering, especially when it rains. A standardized laboratory procedure to determine the amount of biocides released under practical conditions has been developed and is accessible as European Standard FprEN 16105.
Treated wood is frequently used for construction. However, there is a need to ensure that biocides used for the treatment are not a threat for people or environment. The paper focused on Pinus sylvestris treated with copper–boron–azole (CBA), containing tebuconazole as organic biocide and monoethanolamine (Mea).
This study investigates chemical mechanisms of fixation and mobilisation involved in the leaching process of the used inorganic and organic biocides in CBA.
A pH dependent leaching test was performed, followed by a set of complementary analysis methods in order to identify and quantify the species released from wood. The main findings of this study are:
-Organic compounds are released from untreated and treated wood; the quantity of released total organic carbon, carboxylic and phenolic functions increasing with the pH.
-Nitrogen containing compounds, i.e. mainly Mea and its reaction products with extractives, are released in important quantities from CBA treated wood, especially at low pH.
-The release of copper is the result of competitive reactions: fixation via complexation reactions and complexation with extractives in the liquid phase. The specific pH dependency of Cu leaching is explained by the competition of ligands for protonation and complexation.
-Tebuconazole is released to a lesser extent relative to its initial content. Its fixation on solid wood structure seems to be influenced by pH, suggesting interactions with –OH groups on wood. Boron release appears to be pH independent and very high. This confirms its weak fixation on wood and also no or weak interaction with the extractives.
Säulenperkolationsversuche werden u.a. zur Ermittlung der Freisetzung von Schadstoffen aus Böden durchgeführt. Im Entwurf der novellierten Bundesboden-schutz- und Altlastenverordnung ist neben Schüttelverfahren (DIN 19527 und 19529) ein Säulenperkolationsverfahren (DIN 19528) zur Eluatgewinnung aus Böden festgeschrieben. Mit diesem Verfahren kann im Vergleich zu den Schüttelversuchen auch der zeitliche Verlauf der Schadstofffreisetzung erfasst und bewertet werden. Allerdings sind die Verfahren bisher nur für anorganische Stoffe und wenige prioritäre organische Schadstoffe validiert worden (PAK, MKW, PCB, Phenole).
Aber auch Schadstoffe wie perfluorierte Tenside (PFT), die z.B. für die Veredlung von Papier, Textilien und Haushaltsgeräten eingesetzt werden oder Biozide, mit denen Bauprodukte zum Schutz vor mikrobiellem Befall ausgerüstet werden (z.B. Fassadenbeschichtungen und Holz), geraten auf Grund ihrer gesundheits- und umwelt-schädlichen Eigenschaften immer stärker in die Diskussion.
Die Europäische Bauprodukteverordnung (EU) Nr. 305/2011 ermöglicht den Mitgliedstaaten Vorschriften zur Bewertung der Umweltauswirkungen ihrer Bauwerke zu erlassen. Ziel des Pro-jektes war es, Empfehlungen für eine Testbatterie zur ökotoxikologischen Bewertung der Um-weltverträglichkeit von Bauprodukten für die Außenanwendung zu erarbeiten, die zur Europä-ischen Harmonisierung von Prüfmethoden beitragen. Aus einer Auswahlliste von 39 Produkten wurden 20 Produkte in das ökotoxikologische Untersuchungsprogramm einbezogen. Monoli-thische und flächige Bauprodukte wurden in der horizontalen dynamischen Oberflächenaus-laugprüfung (DSL-Test) nach CEN/TS 16637-2, granulare Produkte im Schütteltest nach DIN EN 12457-1 eluiert. Die Eluate wurden in vier aquatischen Toxizitätstests (Algen, Daphnien, Leuchtbakterien, Fischeier), einem Gentoxizitätstest (umu-Test) und im Respirometertest (OECD 301 F) untersucht. Hierbei wurden niedrige bis sehr hohe Ökotoxizitäten (bis Verdün-nungsstufe 1536) bestimmt. Zudem wurde ein Europäischer Ringversuch mit 17 Teilnehmern und zwei Bauprodukten konzeptionell vorbereitet, durchgeführt und gemäß DIN ISO 5725 ausgewertet. Nach Ausschluss der nicht validen bzw. als Ausreißer identifizierten Biotests war die laborübergreifende Streuung des Gesamtverfahrens zur ökotoxikologischen Charakterisie-rung von Bauprodukten akzeptabel. Der Variationskoeffizient für die Konzentration, die einen 50%igen Effekt induziert (EC50) lag für die verschiedenen Tests und Bauprodukte zwischen 9 und 110% und beschreibt die Variabilität des gesamten, komplexen Verfahrensablaufs vom Elutionsprozess über Probenlagerung bis hin zur eigentlichen Biotestdurchführung. Es wurden Empfehlungen zur Planung und Durchführung von Ökotoxizitätstests zur Bewertung von Bau-produkten erarbeitet und bei der für die europäische Harmonisierung von Auslaugtests für Bauprodukte zuständigen CEN-Arbeitsgruppe eingereicht.
The European Construction Products Regulation allows Member States to adopt rules for evaluating the environmental impact of their buildings. The aim of the project was to develop recommendations for a test battery for the ecotoxicological assessment of the environmental impact of construction products for outdoor use and contribute to the European harmonization of test methods. From a shortlist of 39 products 20 products were included in the ecotoxicological testing program. Monolithic and plate-like construction products were eluted in the Dynamic Surface Leaching test (DSLT) in accordance with CEN/TS 16637-2, granular products were eluted in a one stage batch test in accordance with DIN EN 12457-1. The eluates were examined in four aquatic toxicity tests (algae, daphnia, luminescent bacteria, fish eggs), a genotoxicity test (umu test) and in the respirometer test (OECD 301 F). Here, low to very high ecotoxicity was observed (up to a dilution factor of 1536). Six out of 8 eluates, whose TOC exceeded 10 mg L⁻1 showed a good biodegradability above 75%. The intra-laboratory repeatability of the Lowest Ineffective Dilution (LID) usually was within ±1 dilution steps (ecotoxicity tests) and ±2 dilution steps (leaching and ecotoxicity tests). This is acceptable, when considering that the overall variability of sample preparation, leaching test, and bioassays add up. The conclusions lead to practical recommendations for a suitable combination of leaching and ecotoxicity tests.
Biocide leaching was investigated for acrylate and vinyl acetate based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
A European round robin test according to ISO 5725-2 was conceptually prepared, realised, and evaluated. The aim was to determine the inter-laboratory variability of the overall process for the ecotoxicological characterization of construction products in eluates and bioassays. To this end, two construction products BAM-G1 (granulate) and HSR-2 (roof sealing sheet), both made of EPDM polymers (rubber), were selected. The granular construction product was eluted in a one stage batch test, the planar product in the Dynamic Surface Leaching test (DSLT). A total of 17 laboratories from 5 countries participated in the round robin test: Germany (12), Austria (2), Belgium (1), Czech Republic (1) and France (1). A test battery of four standardised ecotoxicity tests with algae, daphnia, luminescent bacteria and zebrafish eggs was used. As toxicity measures, EC50 and LID values were calculated. All tests, except the fish egg test, were basically able to demonstrate toxic effects and the level of toxicity. The reproducibility of test results depended on the test specimens and the test organisms. Generally, the variability of the EC50 or LID values increased with the overall level of toxicity. For the very toxic BAM-G1 eluate a relative high variability of CV ¼ 73%e110% was observed for EC50 in all biotests, while for the less toxic HSR-2 eluate the reproducibility of EC50 varied with sensitivity: it was very good (CV ¼ 9.3%) for the daphnia test with the lowest sensitivity, followed by the algae test (CV ¼ 36.4%). The luminescent bacteria test, being the most sensitive bioassay for HSR-2 Eluate, showed the highest variability (CV ¼ 74.8%). When considering the complex overall process the reproducibility of bioassays with eluates from construction products was acceptable.
Im Vortrag werden Auswaschversuche mit Bauprodukten vorgestellt, die dazu dienen sollen, Bauprodukte mit geringer Auswaschung zu erkennen. Zu verschiedenen Bauprodukten (Lacke für Außenanwendungen, Wärmedämmverbundsystemen, Dachziegel und Dachfolien) werden ausgewählte Ergebnisse vorgestellt. Die Eignung der Auswaschverfahren und die Testergebnisse werden bewertet.
Auslaugung von Stoffen aus Bauteilen kann zu einer Belastung von Boden und Gewässern führen. Das Simulationsmodell COMLEAM (COnstruction Material LEAching Model) wurde eingesetzt, um die Stoffauswaschung besser zu verstehen und das damit verbundene Umweltrisiko besser einschätzen zu können. Emissionsfunktionen sind Bestandteil dieses Modells. Hier werden fünf verschiedenen Funktionen beschrieben, getestet und hinsichtlich ihrer Eignung für Prognosemodelle bewertet.
Construction products are in contact with water (e.g., rain, seepage water) during their service lifetime and may release potentially harmful compounds by leaching processes. Monitoring studies showed that compounds attributed to construction products are found in storm water and the receiving bodies of water and that the release of biocides in urban areas can be comparable to the input of pesticides from agricultural uses. Therefore, a prospective risk assessment of such products is necessary. Laboratory leaching tests have been developed by the Technical Committee CEN/TC 351 and are ready to use. One major task in the future will be the evaluation of the leaching test results, as concentrations found in laboratory experiments are not directly comparable to the field situations. Another Task will be the selection of compounds to be considered for construction products, which are often a complex mixture and contain additives, pigments, stabilization agents, etc. The formulations of the products may serve as a starting point, but total content is a poor predictor for leachability, and analysis of the eluates is necessary. In some cases, nontargeted approaches might be required to identify compounds in the eluates. In the identification process, plausibility checks referring to available information should be included. Ecotoxicological tests are a complementary method to test eluates, and the combined effects of all compounds—including Degradation products—are included. A bio test battery has been applied in a round robin test and was published in a guidance document. Published studies on the ecotoxicity of construction products show the tests’ suitability to distinguish between products with small and larger effects on the environment.
Leaching of biocides from construction products is currently a research topic receiving attention from the European regulation authorities (CEN/TC 351).
In this paper we have focused on the leaching behaviour of CBA (copper-borateazoles) treated Pinus sylvestris.
To better define the chemistry of the leaching phenomena, two leaching tests (a static equilibrium test and a dynamic surface leaching test) have been carried out on untreated and treated wood, which offered more information about how the leaching of biocides interferes with other substances released from the wood structure.
Eluates, in liquid and lyophilised form, were further analyzed by analytical methods.
Organic (tebuconazole) and inorganic (Cu, B) biocides were quantified and several organic compounds have been identified (e.g.
carboxylic acids, phenols, amines, etc.).
Also, the total amount of phenols and of carboxylic groups was determined.
Results on inorganic compounds are in accordance with previous studies made on treated wood.
Furthermore, organic carbon, tebuconazole and other organic compounds' behaviour was extensively investigated.
This study aims to complete existing leaching data and to help developing a chemical model for several biocides in wood, including Cu, B and tebuconazole.
The current European legislation requires that combined effects of the active substances and any substance of concern contained in biocidal products are taken into account in environmental risk assessment. The hypothesis whether the consideration of active substances together with all formulation additives that are labeled as presenting an environmental hazard is sufficient for a reliable environmental risk assessment was tested in the present study by investigating 3 wood preservative products. Relevant single substances in the products, some of their generic mixtures, the biocidal products themselves, and aqueous eluates prepared from the products (representing potential environmental mixtures) were tested for effects on algal growth and Daphnia acute immobilization as well as reproduction. Predictions for the products and the eluates were based on the concept of concentration addition and were mostly found to provide reliable or at least protective estimates for the observed acute and chronic toxicity of the mixtures. The mixture toxicity considerations also indicated that the toxicity of each product was dominated by just 1 of the components, and that assessments based only on the dominating substance would be similarly protective as a full-mixture risk assessment. Yet, there remained uncertainty in some cases that could be related to the toxicity of transformation products, the impact of unidentified formulation additives, or synergistic interaction between active substances and formulation additives.
Auslaugversuche wurden mit verschiedenen Bauprodukten durchgeführt, die unter Anwendungsbe-dingungen mit Niederschlägen in Kontakt kommen können. In das Testprogramm wurden Lacke für Außenanwendungen, Wärmedämmverbundsysteme, Dachziegel und polymere Dachfolien einbezogen.
Mit diesen Produkten wurden der von CEN TC 351 entwickelte dynamische Oberflächenauslaugtest (DSLT) und Immersionstests nach EN 16105 durchgeführt. Emissionsverläufe wurden sowohl für an-organische Komponenten als auch für organische Substanzen in den Eluaten ermittelt. Auslaugbare organische Substanzen wurden zuvor in Screeningtests identifiziert.
Um die mögliche Freisetzung von Stoffen aus Bauprodukten beurteilen zu können, ist es erforderlich, Emissionsverläufe zu beschreiben. Dazu sind die verwendeten Testverfahren geeignet. Um Baupro-dukte mit einem Blauen Engel als „Produkte mit geringer Auslaugung“ auszuloben, müssen die aus-laugbaren Substanzen komplett bekannt sein. Für organische Verbindungen ist das noch eine Heraus-forderung. Außerdem erfordert die Bewertung der Testergebnisse sowohl Übertragungsmodelle, die Vorhersagen über freisetzbare Stoffmengen unter Anwendungsbedingungen ermöglichen, als auch Vorgaben zu tolerierbaren Umweltkonzentrationen. Hier besteht noch Handlungsbedarf.
Leaching processes are responsible for the release of biocides from treated materials into the environment.
Adequate modeling of emission processes is required in order to predict emission values in the framework of the risk assessment of biocidal products intended for long-term service life. Regression approaches have been applied to data obtained from the long-term monitoring of biocide emissions in experiments involving semi-field conditions. Due to the complex interaction of different underlying mechanisms such as water and biocide diffusion and desorption, however, these attempts have proven to be of limited usefulness e at least, for the available biocide emission data. It seems that the behavior of the biocide emission curve depends to a considerable extent on whichever underlying mechanism is slowest at a given point in time, thus limiting the amount of biocide available for release. Building on results obtained in the past few years, the authors propose a criterion for determining which mechanism controls the leaching process at a given point in time based on the slope of the log-log emission curve. In addition, a first-order approximation of this slope value is presented which displays advantages both in terms of computability and interpretability. Finally, an algorithm for the determination of breakpoints in the slope of the log-log emission curve is presented for the demarcation of phases within which one mechanism acts as a limiting factor.
Construction products are often complex materials and often contain a large number of additives like plasticizers, solvents, stabilizers and pigments, which can be released to the environment during usage by leaching when the product is in contact with water. The impact of potentially hazardous substances on the environment depends on actual release rather than the total content in the products. Depending on the compound and on the matrix, only a small portion is transferred to the environment and becomes bioavailable.
Leaching tests were developed and standardized by the European Committee for Standardization (CEN) to determine the potential release of construction products.
-Background-
Laboratory leaching tests on treated wood were performed during a European robustness study in the framework of the validation of a tank leaching test procedure that has been proposed for construction products in order to determine the potential release of dangerous substances which can be transferred to soil and groundwater. The release of substances has to be determined also for materials treated with biocidal products according to the requirements of the European Biocidal Products Regulation. A similar leaching test procedure was already harmonised for treated wood for this purpose. Both test procedures were applied in parallel to wood treated with the same preservative to investigate whether the results of these tests can replace each other. Additional experiments were performed to further investigate unexpected effects of L/A ratio on leaching of copper and duration of storage of treated test specimens.
-Results-
Both procedures generate similar results concerning cumulative emissions of tebuconazole, copper, dissolved organic carbon and total nitrogen. The emission rates with time are in comparable ranges for both leaching protocols. Emissions of copper increased with decreasing L/A ratios. Strong correlation of copper concentrations and dissolved organic carbon as well as total nitrogen concentrations in eluates indicates that this observation is caused by co-elution of copper with organic substances. Duration of storage of treated test specimens affected emissions for the investigated wood preservative.
-Conclusions-
Based on these findings, results from both test procedures can be used to describe leaching characteristics and avoid double testing of treated wood to fulfil the requirements of the European regulations for either biocides or construction products. Leaching of substances from treated wood is a complex process that depends on its chemical composition and ageing processes.
Die Auswaschung von Bioziden wurde für eine Reihe von behandelten Materialien in Labor- und Freilandversuchen untersucht. Beobachtungen aus Freilanduntersuchungen und Ergebnisse aus Regressionsanalysen zum Einfluss von Witterungsfaktoren werden dargestellt. Verschiedene Untersuchungen zu Materialeigenschaften, die Einfluss auf die Auswaschbarkeit von Bioziden haben können, werden für zwei Farben verglichen. Ein Modellansatz zur Beschreibung von Laborversuchsdaten wird kurz erläutert.
Background: Biocidal products can be sources of active substances in surface waters caused by weathering of treated articles. Marketing and use of biocidal products can be limited according to the European Biocidal Products Regulation if unacceptable risks to the environment are expected. Leaching of active substances from treated articles was observed in field experiments to obtain information on leaching processes and investigate the suitability of a proposed test method.
Results: Leaching under weathering conditions proceeds discontinuously and tends to decrease with duration of exposure. It mainly depends on the availability of water, but is also controlled by transport processes within the materials and stability of the observed substances. Runoff amount proved to be a suitable basis to compare results from different experiments. Concentrations of substances are higher in runoff collected from vertical surfaces compared to horizontal ones, whereas the leached amounts per surface area are higher from horizontal surfaces. Gaps in mass balances indicate that additional processes such as degradation and evaporation may be relevant to the fate of active substances in treated articles. Leached amounts of substances were considerably higher when the materials were exposed to intermittent water contact under laboratory conditions as compared to weathering of vertically exposed surfaces.
Conclusions: Experiences from the field experiments were used to define parameters of a procedure that is now provided to fulfil requirements of the Biocidal Products Regulation. The experiments confirmed that the amount of water which is in contact with exposed surfaces is the crucial parameter determining leaching of substances.
Anwendungen von Bioziden in Materialien für Außenanwendungen sind mögliche Quellen für Biozide in Umweltkompartimenten infolge von witterungsbedingten Auswaschprozessen. Im Bericht werden Leachingprozesse und -parameter als auch Methoden zu deren Untersuchung unter Labor- und Freilandversuchsbedingungen beschrieben. Vorteile und Grenzen der verschiedenen Herangehensweisen zur Untersuchung von Leachingprozessen werden diskutiert. Standardisierte Auswaschtests sowie in der Fachliteratur publizierte Auswaschexperimente werden zusammenfassend dargestellt. Es wird beschrieben, wie Leachingdaten gemäß Technischem Leitfaden zur Biozidprodukten-Richtlinie 98/8/EG für eine Risikobewertung genutzt werden. Ein alternativer Ansatz zur mathematischen Modellierung von Leachingtest-Daten wurde erprobt und wird im Bericht erläutert. Potentiell lassen sich mit dem vorgeschlagenen Ansatz bestimmte gegenwärtig auftretende Schwierigkeiten bei der Risikobewertung umgehen.
Applications of biocides in outdoor materials are potential sources of biocides in environmental compartments due to leaching processes under weathering conditions. Leaching processes and parameters as well as methods to investigate leaching processes under laboratory and semi-field conditons are described in the report. Benefits and limitations of different test approaches are discussed. Standardised leaching tests as well as leaching experiments reported in scientific literature are listed. The application of leaching data for risk assessments according to the Technical Guidance Documents for the Biocidal Products Directive (98/8/EC) is described. An alternative approach for mathematical modelling of leaching data was tested and is Explained in the report. Certain difficulties that currently appear during risk assessments may be circumvented by the proposed approach.
Façade coatings are exposed to weathering. Driving rain events can cause façade runoff bearing the potential to release substances from the coating. In order to derive reliable and reproducible information about this so-called leaching (emission into water), a laboratory test method has been developed, that has been published as European Standard EN 16105:2011. An interlaboratory comparison has been performed with 8 participants in order to validate the test method. This article describes the test results that reveal statistics on the quality of the test method and allows further insights to the leaching mechanism in coatings.
Numerical simulation of the leaching behaviour of treated wood is the most pertinent and less expensive method for the prediction of biocides' release in water. Few studies based on mechanistic leaching models have been carried out so far. In this work, a coupled chemistry-mass transport model is developed for simulating the leaching behaviour of inorganic (Cu, B) and organic (Tebuconazole) biocides from CBA-amine treated wood. The model is based on experimental investigations (lab-scale leaching tests coupled with chemical and structural analysis). It considers biocides' interactions with wood solid components and with extractives (literature confirmed reactions), as well as transport mechanisms (diffusion, convection) in different compartments. Simulation results helped at identifying the main fixation mechanisms, like (i) direct complexation of Cu by wood-phenolic and -carboxylic sites (and not via monoethanolamine; complex) on lignin and hemicellulose and strong dependence on extractives' nature, (ii) pH dependent binding of tebuconazole on polarized –OH moieties on wood. The role of monoethanolamine is to provide a pore-solution pH of about 7.5, when copper solubility is found to be weakest. The capability of the developed model to simulate the chemical and transport behaviour is the main result of this study. Moreover, it proved that characterization leaching tests (pH dependency and dynamic tests), combined with appropriate analytical methods are useful experimental tools. Due to its flexibility for representing and simulating various leaching conditions, chemical-transport model developed could be used to further simulate the leaching behaviour of CBA treated wood at larger scales.