Characterization of Fourier Transform Infrared, Cavity Ring-Down Spectroscopy, and Optical Feedback Cavity-Enhanced Absorption Spectroscopy Instruments for the Analysis of Ammonia in Biogas and Biomethane.

Novel traceable analytical methods and reference gas standards were developed for the detection of trace-level ammonia in biogas and biomethane. This work focused on an ammonia amount fraction at an upper limit level of 10 mg m-3 (corresponding to approximately 14 µmol mol-1) specified in EN 16723-1:2016. The application of spectroscopic analytical methods, such as Fourier transform infrared spectroscopy, cavity ring-down spectroscopy, and optical feedback cavity-enhanced absorption spectroscopy, was investigated. These techniques all exhibited the necessary ammonia sensitivity at the required 14 µmol mol-1 amount fraction. A 29-month stability study of reference gas mixtures of 10 µmol mol-1 ammonia in methane and synthetic biogas is also reported.

Copper release rate needed to inhibit fouling on the west coast of Sweden and control of copper release using zinc oxide.

How zinc oxide influences copper release has been tested and the lowest release rate of copper from various combinations of copper and zinc in a paint matrix evaluated, whilst still deterring macrofouling, including barnacles and bryozoans. Copper (I) oxide was added to a generic AF paint in 0, 8.5, 11.7 or 16.3 wt% copper oxide in combination with 0, 10 or 20 wt% zinc oxide and applied on PMMA panels. The results show that zinc influences the release rate of copper. When 10 and 20 wt% zinc was added, the total amount of copper released significantly increased by on average 32 and 47% respectively. All treatments that included copper were successful in deterring macrofouling, including the treatment with the lowest average Cu release rate, ie 4.68 µg cm-2 day-1.

In situ release rates of Cu and Zn from commercial antifouling paints at different salinities.

Antifouling paints are environmentally risk assessed based on their biocidal release rates to the water phase. In situ release rates of copper (Cu) and zinc (Zn) were derived for five commercial paints in two recreational marinas with different salinities (5 and 14 PSU) using an X-Ray Fluorescence spectrometer (XRF). Salinity was found to significantly affect the Cu release, with twice the amount of Cu released at the higher salinity, while its influence on the Zn release was paint-specific. Site-specific release rates for water bodies with salinity gradients, e.g. the Baltic Sea, are therefore necessary for more realistic risk assessments of antifouling paints. Furthermore, the in situ release rates were up to 8 times higher than those generated using standardized laboratory or calculation methods. The environmental risk assessment repeated with the field release rates concludes that it is questionable whether the studied products should be allowed on the Swedish market.

A novel XRF method to measure environmental release of copper and zinc from antifouling paints.

The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.