Oligo-Condensation Reactions of Silanediols with Conservation of Solid-State-Structural Features.

Oligo- and polysiloxanes are usually prepared by condensation reactions in solvents without control of stereochemistry. Here we present a solventless thermal condensation of stable organosilanols. We investigated the condensation reactions of organosilanediols with different organic substituents, having in common at least one aromatic group. The condensation kinetics of the precursors observed by NMR spectroscopy revealed a strong dependence on temperature, time, and substitution pattern at the silicon atom. SEC measurements showed that chain length increases with increasing condensation temperature and time and lower steric demand of the substituents, which also influences the glass transition temperatures (Tg) of the resulting oligo- or polymers. X-ray diffraction studies of the crystalline silanediols and their condensation products revealed a structural correlation between the substituent location in the crystalline precursors and the formed macromolecules induced by the hydrogen bonding pattern. In certain cases, it is possible to carry out topotactic polymerization in the solid-state, which has its origin in the crystal structure.

Approach to assess the performance of waste management systems towards a circular economy: waste management system development stage concept (WMS-DSC).

In this paper a novel holistic approach to assess the performance of waste management systems (WMSs) is presented. The so called WMS development stage concept (WMS-DSC) can be used by practitioners or decision makers to assess primarily the WMS at the municipal level. The WMS categorization into development stages notably enables a clear identification of symptoms, the causes of possible waste mismanagement and potential measures for improvement. The concept can be used to (i) assess the status quo of a WMS and, based on this, identify possible measures for implementation; (ii) check whether relevant system conditions to implement a specific measure are met; (iii) monitor the progress of a WMS; and (iv) compare the WMSs of different cities. The concept consists of five development stages: stage 1 - absence or lack of essential elements of waste management; stage 2 - reliable collection and improved landfill sites; stage 3 - separate collection and sorting; stage 4 - expansion of the recycling industry; and stage 5 - circular economy (CE), waste as a resource. While stage 1 describes the absence of or a very immature and malfunctioning WMS, stage 5 stands for a fully implemented CE. By equating the highest stage to the objectives that have evolved today globally for a sustainable CE, this concept can be used to identify targets and the most suitable steps for an individual WMS towards a future best practice of CE.•A holistic approach to assess waste management systems' performance is presented.•A benchmarking tool to estimate the circular economy (CE) evolvement in cities.•Usable for cities both in the Global North and South to identify CE potentials.

Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes.

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in 29 Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. 1 H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.

High-throughput 16S rRNA gene sequencing of the microbial community associated with palm oil mill effluents of two oil processing systems.

Palm Oil Mill Effluents (POME) are complex fermentative substrates which habour diverse native microbial contaminants. However, knowledge on the microbiota community shift caused by the anthropogenic effects of POME in the environment is up to date still to be extensively documented. In this study, the bacterial and archaeal communities of POME from two palm oil processing systems (artisanal and industrial) were investigated by Illumina MiSeq Platform. Despite the common characteristics of these wastewaters, we found that their microbial communities were significantly different with regard to their diversity and relative abundance of their different Amplicon Sequence Variants (ASV). Indeed, POME from industrial plants harboured as dominant phyla Firmicutes (46.24%), Bacteroidetes (34.19%), Proteobacteria (15.11%), with the particular presence of Spirochaetes, verrucomicrobia and Synergistetes, while those from artisanal production were colonized by Firmicutes (92.06%), Proteobacteria (4.21%) and Actinobacteria (2.09%). Furthermore, 43 AVSs of archaea were detected only in POME from industrial plants and assigned to Crenarchaeota, Diapherotrites, Euryarchaeota and Nanoarchaeaeota phyla, populated mainly by many methane-forming archaea. Definitively, the microbial community composition of POME from both type of processing was markedly different, showing that the history of these ecosystems and various processing conditions have a great impact on each microbial community structure and diversity. By improving knowledge about this microbiome, the results also provide insight into the potential microbial contaminants of soils and rivers receiving these wastewaters.

Techno-economic and environmental assessment of methane oxidation layer measures through small-scale clean development mechanism - The case of the Seychelles.

Unclosed coastal landfills in small island developing states are major sources of greenhouse gases and other environmental impacts. This is a major problem for sustainable waste management systems mainly due to the lack of economic resources. The clean development mechanism (CDM) appears as a possibility to facilitate sustainable financing. Implementing a methane oxidation layer (MOL) emerges as a feasible technical option for this kind of small landfills since landfill gas extraction is usually not viable. This paper presents a techno-economic and environmental assessment of MOL implementation in the Providence landfill (Seychelles) as a small-scale CDM measure. Results show that the MOL measure could avoid by 2030 between 94 and 20 kt CO2 eq. Concerning profitability, results clearly show that it depends on the existence of stabilized biomass material within the island. Thus, the MOL measure starts to be profitable in some scenarios for certified emission reductions (CER) prices higher than 26 €/t CO2 eq. that seem possible depending on the emissions' market development. When not profitable under CDM, the MOL measure might be used to reduce CO2 emissions from the domestic climate effort under the Paris Agreement since the unitary abatement costs is between 10 and 423 €/t CO2 eq. Moreover, the MOL measure contributes to the sustainable development goals (SDG) achievement - mainly SDG8, SDG13, and SDG14. Finally, results call for a prompt action in Seychelles since the sooner the MOL is implemented after the landfill is closed, the more profitable.

Potential of medium chain fatty acids production from municipal solid waste leachate: Effect of age and external electron donors.

A large quantity of leachate is generated during municipal solid waste collection operation and in landfills due to the large amount of organic waste and high humidity. The content of medium chain fatty acids (MCFAs) in the leachate is a low cost feedstock for bio-based chemical and fuel production processes. The aim of this study is to investigate the MCFA production potential of three leachate ages through chain elongation process under uncontrolled pH batch test. Moreover, the effect of using different external electron donors (ethanol, methanol and a mixture of both) is studied. The experiment consists of characterizing the samples then adding external electron donors with a specific ratio to leachate samples under mesophilic temperature. For this investigation, also a statistical analysis is done, which shows the production of MCFAs is highly influenced by leachate age. The results indicate that the production of even-numbered acids increase from 600 to 1,000 mg/L by the end of the ethanol chain elongation experiment for young leachate. However, a higher MCFA production of more than 1,000 mg/L is achieved by using the mixture of methanol and ethanol as electron donor. Furthermore, all methanol chain elongation experiments lead to an odd-numbered production of MCFAs, such as pentanoic and heptanoic acids. These results confirm the potential improvement of MCFA production from leachate through choosing the optimal leachate age and electron donor. Overall, producing MCFAs from leachate is a good example of circular bio-economy because waste is used to produce biochemicals, which closes the material cycle.

Extraction of medium chain fatty acids from organic municipal waste and subsequent production of bio-based fuels.

This paper provides an overview on investigations for a new technology to generate bio-based fuel additives from bio-waste. The investigations are taking place at the composting plant in Darmstadt-Kranichstein (Germany). The aim is to explore the potential of bio-waste as feedstock in producing different bio-based products (or bio-based fuels). For this investigation, a facultative anaerobic process is to be integrated into the normal aerobic waste treatment process for composting. The bio-waste is to be treated in four steps to produce biofuels. The first step is the facultative anaerobic treatment of the waste in a rotting box namely percolate to generate a fatty-acid rich liquid fraction. The Hydrolysis takes place in the rotting box during the waste treatment. The organic compounds are then dissolved and transferred into the waste liquid phase. Browne et al. (2013) describes the hydrolysis as an enzymatically degradation of high solid substrates to soluble products which are further degraded to volatile fatty acids (VFA). This is confirmed by analytical tests done on the liquid fraction. After the percolation, volatile and medium chain fatty acids are found in the liquid phase. Concentrations of fatty acids between 8.0 and 31.5 were detected depending on the nature of the input material. In the second step, a fermentation process will be initiated to produce additional fatty acids. Existing microorganism mass is activated to degrade the organic components that are still remaining in the percolate. After fermentation the quantity of fatty acids in four investigated reactors increased 3-5 times. While fermentation mainly non-polar fatty acids (pentanoic to octanoic acid) are build. Next to the fermentation process, a chain-elongation step is arranged by adding ethanol to the fatty acid rich percolate. While these investigations a chain-elongation of mainly fatty acids with pair numbers of carbon atoms (acetate, butanoic and hexanoic acid) are demonstrated. After these three pre-treatments, the percolate is brought to a refinery to extract the non-polar fatty acids using bio-diesel, which was generated from used kitchen oil at the refinery. The extraction tests in the lab have proved that the efficiency of the liquid-liquid-extraction is directly linked with the chain length and polarity of the fatty acids. By using a non-polar bio-diesel mainly the non-polar fatty acids, like pentanoic to octanoic acid, are extracted. After extraction, the bio-diesel enriched with the fatty acids is esterified. As a result bio-diesel with a lower viscosity than usual is produced. The fatty acids remaining in the percolate after the extraction can be used in another fermentation process to generate biogas.