Abstract: Identifying priority areas is an essential step in developing management strategies to reduce pesticide loads in surface water. A spatially explicit model-based approach was developed to detect priority areas for diffuse pesticide pollution at catchment scale. The method uses available datasets and considers different pesticide pathways in the environment post-application. The approach was applied in a catchment area in SE Flanders (Belgium) as a case study. Calculated risk areas were obtained using detailed landscape data and combining pesticide emissions and hydrological connectivity. The risk areas obtained were further compared with an alternative observation-based method, developed specifically for this study site that includes long-term field observations and local expert knowledge. Both methods equally classified 50% of the areas. The impact of crop rotation on the calculated risk was analysed. High-risk areas were identified and added to a cumulative map over all five years to evaluate temporal variations. The model-based approach was used for the initial identification of risk areas at the study site. The tool helps to prioritise zones and detect particular fields to target landscape mitigation measures to reduce diffuse pesticide pollution reaching surface water bodies.

Abstract: Natural deep eutectic solvents (NADES) show great promise as media for enzymatic reactions in areas where (bio)compatibility with natural or medicinal products is a must. While in theory they can be tailored to the intended reaction to ensure optimized yields, the knowledge to date is predominantly empirical, with some mechanistic reports providing a fragmented view at best. Therefore, it is not easy to explain experimental observations, let alone make predictions. The aim of this study was to develop a structured, holistic understanding of the effects of NADES media on enzymatic reactions, distinguishing between effects on solubility, solvation, viscosity, inhibition and denaturation. Experimental and computational chemistry methods were combined to separately study the interactions between enzyme, substrate, and NADES as reaction media. The initial enzyme activity and the final conversion of vinyl laurate transesterification by immobilized Candida antarctica lipase were studied experimentally. The direct effect of NADES on the same enzyme was modeled by molecular dynamics simulation. The effect of solubility was studied by both experimental and computational methods. To predict the solubility and viscosity of NADES, data-driven models were developed by combining group contribution and machine learning methods, based on the accumulated experimental knowledge on NADES found in the literature. Finally, the composed relationships and prediction models were applied to the practical example of deacetylation of mannosylerythritol lipids (MELs). The experimental findings show that the chosen NADES system has a significant effect on both the apparent initial activity and the final conversion. However, in the simulations, the enzyme retains its original structure; moreover, NADES has an additional stabilizing effect on the enzyme. In addition, changes in the molar ratio of the compounds in NADES do not show a significant effect on the stability of the enzyme. These results indicate that the main effect of NADES on the reaction is mainly related to the substrate-solvent interactions (solvation energy) and the viscosity of the system. On the other hand, the experimental results only confirmed the significance of solvation, viscosity did not show a clear correlation with the studied reaction parameters. The machine learning models built for solubility and viscosity gave quantitative predictions of these properties. The accumulated knowledge was used to optimize the yield in the deacetylation reaction of MELs. The combination of these methods provides fundamental knowledge about the effect of NADES on biocatalysis, but the results are also applicable to other uses of NADES.

Abstract: Novel emerging biorefinery technologies have gained interest and have the potential to tackle several sustainability challenges in our society. A lignin-first biorefinery process – reductive catalytic fractionation (RCF) – is currently under development with the aim to process wood into high-value end-products that replace highly polluting fossil oil-based products. However, such emerging technologies are not matured yet, holding a certain degree of technological, economic, and environmental uncertainty. Hence, an appropriate assessment method is required to assess techno-economic feasibility and environmental impacts of emerging uncertain technologies (e.g lignin-first RCF process). This dissertation aims to develop an integrated techno-environmental economic assessment framework to assess emerging technologies dynamically and prospectively from economic and environmental points of view. First, a techno-economic assessment (TEA) is performed to assess the economic feasibility and the most influential economic and technological parameters of the lignin-first RCF biorefinery taking the whole wood value chain into account. By making the relations across the wood value chain, the scale of the biorefinery, wood species, and output prices highly determine the economic feasibility. The economic feasibility can be reached by a sufficient capacity level which depends on wood species-specific conditions. Also, waste wood proves to be the most profitable feedstock in comparison to virgin wood. Second, an analytical real options analysis (ROA) is performed taking two correlated market uncertainties and the value of flexibility into account to identify the optimal investment decision in an RCF biorefinery. Two different investment options, separated and united investments in harvesting equipment and RCF biorefinery, are analyzed. In both scenarios, market uncertainty postpones the investment. When both investment decisions are united, the probability of investment increases in comparison to separated investments. The study reveals that RCF has the potential to stimulate investments within the wood value chain. Third, a consequential life cycle assessment (LCA) is performed to assess the carbon emissions and the environmental consequences of the lignin-first RCF process and its products. The study reveals that at the current stage RCF products have higher carbon emissions than their alternative counterparts. Several options to improve the environmental performance are discussed such as different RCF technology configurations, targeting different RCF products with the ability to replace higher polluting alternative counterparts on the markets. Other discussion points such as transportation type and the distance, (in-)direct land-use change, the use stage and disposal stages implications, and a more comprehensive environmental view of the RCF products, show the potential to improve the environmental performance of the RCF technology. Overall, the study shows that the RCF process can be environmentally desirable if the appropriate RCF configuration and products are chosen. Finally, the above-mentioned methods – techno-economic assessment, analytical real options analysis, and consequential life cycle assessment – are uniquely integrated within the newly developed integrated assessment framework. The framework has the aim to complement the shortcomings and combine the advantages of all three methods. The framework assesses emerging technologies to give predictive insights about the time-specific economic and environmental performance under the newly developed three threshold conditions: technological readiness, economic feasibility, and environmental desirability. The developed integrated assessment framework assesses dynamically and prospectively the RCF biorefinery implementation under Belgian conditions. It reveals that the economic feasibility increases and carbon emissions decrease over time. The RCF biorefinery fulfills all three threshold conditions – technological readiness, economic feasibility, and environmental desirability – consecutively. The newly developed integrated assessment framework offers decision support to several stakeholders of emerging technologies starting from low technology readiness level (TRL). Practitioners such as the technology developers, researchers, and policymakers can use the framework to evaluate emerging technologies that deal with high levels of technological, economic, and environmental uncertainties. The framework assesses emerging technologies on a detailed level to give decision-makers in-depth insights into the intertwined nature of the technological, economic, and environmental dimensions. It offers insights into the expected time-specific economic and environmental performances, potential, and challenges of the emerging technology to further improve the technology and direct R&Ds along the right path.

Abstract: In this paper, we consider the bulky knots and bulky links, which appear after cutting of a Generalized MöbiusListing GMLn2 body (with the radial cross section a convex plane 2-symmetric figure with two vertices) along a different Generalized MöbiusListing surfaces GMLn2 situated in it. The aim of this report is to investigate the number and geometric structure of the independent objects that appear after such a cutting process of GMLn2 bodies. In most cases we are able to count the indices of the resulting mathematical objects according to the known classification for the standard knots and links.

Abstract: The quartic force fields of FNO and CINO have been computed at the CCSD(T)/cc-pVTZ level. Using an ''augmented'' basis set dramatically improves results for FNO but has no significant effect for CINO. The best computed force field for FNO yields harmonic frequencies and fundamentals in excellent agreement with experiment. Overall, the force fields proposed in the present work are probably the most reliable ones ever published for these molecules. Total atomization energies have been computed using basis sets of spdfg quality: our best estimates are Sigma D-0 = 208.5 +/- 1 and 185.4 +/- 1 kcal/mol for FN0 and CINO, respectively. The computed value for FNO suggests a problem with the established experimental heat of formation. Thermodynamic tables in JANAF style at 100-2000 K are presented for both FNO and CINO.