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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.
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.
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.
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.
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.
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).