Forming Micro-and Nano-Plastics from Agricultural Plastic Films for Employment in Fundamental Research Studies.

Microplastics (MPs) and nanoplastics (NPs) dispersed in agricultural ecosystems can pose a severe threat to biota in soil and nearby waterways. In addition, chemicals such as pesticides adsorbed by NPs can harm soil organisms and potentially enter the food chain. In this context, agriculturally utilized plastics such as plastic mulch films contribute significantly to plastic pollution in agricultural ecosystems. However, most fundamental studies of fate and ecotoxicity employ idealized and poorly representative MP materials, such as polystyrene microspheres. Therefore, as described herein, we developed a lab-scale multi-step procedure to mechanically form representative MPs and NPs for such studies. The plastic material was prepared from commercially available plastic mulch films of polybutyrate adipate-co-terephthalate (PBAT) that were embrittled through either cryogenic treatment (CRYO) or environmental weathering (W), and from untreated PBAT pellets. The plastic materials were then treated by mechanical milling to form MPs with a size of 46-840 µm, mimicking the abrasion of plastic fragments by wind and mechanical machinery. The MPs were then sieved into several size fractions to enable further analysis. Finally, the 106 µm sieve fraction was subjected to wet grinding to generate NPs of 20-900 nm, a process that mimics the slow size reduction process for terrestrial MPs. The dimensions and the shape for MPs were determined through image analysis of stereomicrographs, and dynamic light scattering (DLS) was employed to assess particle size for NPs. MPs and NPs formed through this process possessed irregular shapes, which is in line with the geometric properties of MPs recovered from agricultural fields. Overall, this size reduction method proved efficient for forming MPs and NPs composed of biodegradable plastics such as polybutylene adipate-co-terephthalate (PBAT), representing mulch materials used for agricultural specialty crop production.

Mitigation of Ammonia Emissions from Cattle Manure Slurry by Tannins and Tannin-Based Polymers.

With the extensive use of nitrogen-based fertilizer in agriculture, ammonia emissions, especially from cattle manure, are a serious environmental threat for soil and air. The European community committed to reduce the ammonia emissions by 30% by the year 2030 compared to 2005. After a moderate initial reduction, the last report showed no further improvements in the last four years, keeping the 30% reduction a very challenging target for the next decade. In this study, the mitigation effect of different types of tannin and tannin-based adsorbent on the ammonia emission from manure was investigated. Firstly, we conducted a template study monitoring the ammonia emissions registered by addition of the tannin-based powders to a 0.1% ammonia solution and then we repeated the experiments with ready-to-spread farm-made manure slurry. The results showed that all tannin-based powders induced sensible reduction of pH and ammonia emitted. Reductions higher than 75% and 95% were registered for ammonia solution and cattle slurry, respectively, when using flavonoid-based powders. These findings are very promising considering that tannins and their derivatives will be extensively available due to the increasing interest on their exploitation for the synthesis of new-generation "green" materials.

Extraction of information from laser-induced breakdown spectroscopy spectral data by multivariate analysis.

Laser-induced breakdown spectroscopy (LIBS) is being proposed more and more as a high-throughput technology to assess the elemental composition of materials. When a specific element is of interest, semiquantification is possible by building a calibration model using the emission line intensity of this element for known samples. However, a unique element has usually more than one emission line, and there are many examples where several emission lines used in combination give dramatically better results than any of the individual variables used alone. With a multivariate approach, models can be constructed that take into account all the emission lines related to a specific element; therefore more robust models can be developed. In this work, chemometric methods such as principal component analysis and partial least squares are proposed to resolve and extract useful information from the LIBS spectral data collected on biological materials.