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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.
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.
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.
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.