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.
Emissionen aus Bauprodukten beeinträchtigen die Qualität der Innenraumluft erheblich. Mit Hilfe des AgBB-Schemas werden die Emissionen flüchtiger organischer Verbindungen (VOC) aus Bauprodukten bewertet. Die gesundheitliche Bewertung nach dem AgBB-Schema erfordert produktspezifische Messverfahren.
Diese gibt es mittlerweile für eine Reihe von Produkten. Sie wurden durch Beteiligung verschiedener Forschungseinrichtungen und Messinstitute validiert und u. a. in die Vergabekriterien des Umweltzeichens Blauer Engel übernommen. Die Bewertung ist allerdings mit zumeist niedrigeren Grenzwerten strenger. VOC-Emissionen und Gerüche können beide zu gesundheitlichen Belastungen führen. So ist die sensorische Prüfung ein weiteres wichtiges Element bei der Bewertung von Bauprodukten und vorsorglich auch im AgBB-Schema verankert.
Hauptziel des Projektes ist es, eine Methode der sensorischen Bewertung und Grenzen für die Vergabe des Blauen Engels und für das AgBB-Schema abzuleiten. Auf Grundlage der durchgeführten Untersuchungen (siehe Kapitel 5 Ergebnisse und Diskussion) wird als Bewertungsmethode die empfundene Intensität und die Hedonik vorgeschlagen. Die Ableitung der Grenzwerte für die sensorische Bewertung am 28. Tag erfolgt über die zusätzliche Befragung der Probanden im Rahmen der vorliegenden Studie nach der Zumutbarkeit einer Probe.
Für den Blauen Engel könnte es je Produktgruppe unterschiedliche Grenzen der empfundenen Intensität und der Hedonik geben. Ein erster Vorschlag für mögliche Grenzen, hier zunächst einheitlich für alle
Produktgruppen, ist für die empfundene Intensität 7 pi (5 pi + 2 pi als Sicherheit, Kapitel 5.1.5) und für die Hedonik -1 (0 +/-0,8, gerundet auf -1) (siehe dazu Abbildung 6-2).
Emissions from building products can considerably impair the quality of indoor air. The AgBB scheme is employed to evaluate the emissions of volatile organic compounds (VOC) from building products. The hygienic evaluation according to the AgBB scheme requires product-specific measuring procedures.
These are available for a range of products. They have been validated in co-operation with several research and testing institutes and have been included in the criteria for awarding the Blue Angel ecolabel.
The evaluation is, however, stricter and generally has lower limits. VOC emissions and odours can cause health problems so testing using sensors is an important element in the evaluation of building products and has – for reasons of precaution – been set down in the AgBB scheme. The main goal of the project was to derive a method of evaluation using sensors and limits for awarding the Blue Angel and for the AgBB scheme. Based on the research conducted (see Chapter 5 Results and Discussion), perceived intensity and hedonics were suggested as a suitable Evaluation method. The derivation of limits for the evaluation using sensors on the 28th day was effected in the present study through the additional questioning of the test subjects on the reasonability of a sample.
For the Blue Angel, there could be different limits of perceived intensity and hedonics for each group of products. A preliminary suggestion for possible limits – for all product groups – is a perceived intensity of 7 pi (5 pi + 2 pi as confidence coefficient, Chapter 5.1.5) and -1 (0+/-0.8, rounded to -1) for the hedonic value.
Since semi-volatile organic compounds (SVOCs), including biocides and polychlorinated biphenyls (PCBs), occur indoors as well as outdoors, air sampling adsorbents and measuring methods for all these compounds are indispensable. This paper presents the initial steps in the development of such a method, the aim of which is the analysis of selected compounds in the above-mentioned classes using low air sampling volumes and air-exchange rates close to zero, as is common in museum showcases. For measurements under easily controlled conditions, a micro-chamber system was used at different temperatures. A surface modified styrene divinylbenzene (SDVB) polymer was selected as the air sampling adsorbent for the elution experiments. After successfully performing pretests using the micro-chamber system with target compound solutions, the emissions of these compounds from self-soaked wood samples and con-taminated wood samples were investigated for method development.
The aim of this study was the development of a low volume air sampling strategy for biocides and polychlorinated biphenyls (PCB) at low air change rates in modern, air-tight showcases as they are present in museums. Lindane, pentachlorophenol, dichlofluanid, tolyfluanid, isodrin, p,p-dichlorodiphenyl trichloroethane and permethrin were the biocides and PCB 28 and PCB 153 were the PCBs studied, all of which are semi volatile organic compounds (SVOC). Their occurrences in the museum environment originate from various sources e.g. preventive treatment of organic exhibits or organic building materials. Exhibits are long-term exposed to these pollutants due to storing in showcases or other storage equipment at low air change rates. To achieve air sampling under the aforementioned conditions the influences of temperature, air circulation, air change rate and relative humidity on the emission behavior of the selected biocides and PCBs had to be determined. This was carried out with pre-soaked wood samples in low volume air sampling experiments using 27 L test showcases and 23 L and 24 L emission test chambers and also diffusive sampling with glass as the sampling material.
Biocides are used to protect materials that might be damaged by fungal, microbial or insect activity. The aim of this study is to develop a method for the measurement of these organic compounds, which generally have low or moderate vapor pressures. The biocides considered in this study are permethrin, dichlofluanid, tolylfluanid, iodpropinylbutylcarbamat, octylisothiazolinone, tebuconazole and propiconazole. The emission from two commercial products (plastic foil, wool carpet) containing biocides and of seven types of biocidal formulations applied to wood or clay tiles were investigated in 20-l glass emission test chambers. Each chamber test was performed over a period of 100200 days, and one investigation was conducted over several years. Compared to volatile organic compounds, low-volatility compounds show totally different emission curves in chamber tests; maximal emission values may be reached in days or weeks. A period of 3 months is sometimes necessary for the determination of area-specific emission rates (SERa's). The SERa's (?g m-2 h-1) from biocide-containing products were determined for permethrin (0.006), propiconazole (0.3), dichlofluanid (2.0), tolylfluanid (1.0), octylisothiazolinone (2.5) and iodpropinylbutylcarbamat (2). In most cases, the SERa stayed at its maximum value or declined slowly over the test period. Additionally, a chamber test begun in 1994 with a piece of wood treated with a typical mixture of biocides dissolved in a technical solvent was continued. SERa's (?g m-2 h-1) for dichlofluanid (0.20), tebuconazole (0.49) and permethrin (0.08) remained detectable after the period of nearly 9 years during which the sample remained continuously in the chamber. This test proved the very slow decrease of emission of low-volatility compounds like permethrin and tebuconazole.
In this study 50 construction products were tested in emission test chambers according to the requirements of the AgBB-scheme: 7 acrylic and 6 silicone sealants, 6 paste-like synthetic resin plasters, 13 wood based products, 4 adhesives, 5 lacquers, 6 wall paints and 3 further construction products. VOC and odour emissions were tested on the 1st, 3rd, 10th, and 28th day. In addition to the VOC-measurements, a test procedure was developed to evaluate odour emission of construction products.This test is planned to be implemented into the AgBB-Scheme. A direct evaluation by a sensory panel in the emission test chamber was not possible. So the odour samples were collected in 300- litre tedlar bags which were evaluated later. Odour intensity of the samples was compared with different acetone concentrations. Within this study an interlaboratory comparison was conducted using the newly developed odour test method. Additionally, VVOC emissions, detection of carcinogenic compounds, repeatability of emission test chamber tests, and other issues are presented. This project has shown that construction products can be evaluated in accordance with the AgBB scheme. A sensory evaluation is intended to be introduced in the AgBB scheme. A method for this evaluation is described in this study. The test procedure should be enhanced and validated for practical utilisation.
The European biocides directive (98/8/EG) demand the control of emissions into the envi-ronment like soil, water and air. In this study a method for measuring the input of biocides into the indoor air from materials should be developed. The emission of two products containing biocides (plastic foil, wool carpet) and six different types of biocide containing formulations applied on wood or ceramic tiles were investigated in 20 or 23 l glass emission chambers. Each chamber test was performed over a period of 100 up to 200 days. SVOC show totally different emission curves in chamber tests compared to volatile organic com-pounds (VOC). They reach their maximum value after some days or weeks. Thus a period of 3 months is sometimes necessary for exact measurements. Area specific emission rates (SERa in µg/m²h) for permethrin (0.006), propiconazole (0.2), dichlofluanid (1.5), tolylfluanid (1.2), octylisothiazolinone (2.5) and for iodpropinylbutyl-carbamat (1.7) were determined.
Do particleboards produced with recycled wood contribute to indoor air pollution with biocides?
(2003)
EN 16516 sets specifications for the determination of emissions into indoor air from construction products. Reliable, accurate and International System of Unit (SI)-traceable measurement results of the emissions are the key to consumer protection. Such measurement results can be obtained by using metrologically traceable reference materials. Gas-phase standards of volatile organic compounds (VOCs) in air can be prepared by a variety of dynamic methods according to the ISO 6145 series. However, these methods are not always applicable for semi-VOCs (SVOCs) due to their high boiling point and low vapour pressure. Therefore, a novel dynamic gas mixture generation system has been developed. With this system gas-phase standards with trace level VOCs and SVOCs in air can be prepared between 10 nmol mol−1 and 1000 nmol mol−1. The VOCs and SVOCs in this study have normal boiling points ranging from 146 °C to 343 °C. Metrologically traceable reference materials of the gas-phase standard were obtained by sampling of the VOC gas-phase standard into Tenax TA® sorbent material in SilcoNert® coated stainless steel tubes. Accurately known masses between 10 ng and 1000 ng per VOC were sampled. These reference materials were used to validate the dynamic system. Furthermore, the storage and stability periods of the VOCs in the reference materials were determined as these are crucial characteristics to obtain accurate and SI-traceable reference materials. In a round robin test (RRT), the reference materials were used with the aim of demonstrating the feasibility of providing SI-traceable standard reference values for SVOCs for interlaboratory comparison purposes. Based on the results from the validation, the storage and stability studies and the RRT, gas-phase standards and reference materials of VOCs and SVOCs with relative expanded uncertainties between 5% and 12% (k = 2) have been developed. These reference standards can be used as calibrants, reference materials or quality control materials for the analysis of VOC emissions.