Photochemical Degradation of Short-Chain Chlorinated Paraffins in Aqueous Solution by Hydrated Electrons and Hydroxyl Radicals

Short-chain chlorinated paraffins (SCCPs) are a complex mixture of polychlorinated alkanes (C10-C13, chlorine content 40-70%), and have been categorized as persistent organic pollutants. However, there are knowledge gaps about their environmental degradation, particularly the effectiveness and mechanism of photochemical degradation in surface waters. Photochemically-produced hydrated electrons (e-(aq)) have been shown to degrade highly chlorinated compounds in environmentally-relevant conditions more effectively than hydroxyl radicals (·OH), which can degrade a wide range of organic pollutants. This study aimed to evaluate the potential for e-(aq) and ·OH to degrade SCCPs. To this end, the degradation of SCCP model compounds was investigated under laboratory conditions that photochemically produced e-(aq) or ·OH. Resulting SCCP degradation rate constants for e-(aq) were on the same order of magnitude as well-known chlorinated pesticides. Experiments in the presence of ·OH yielded similar or higher second-order rate constants. Trends in e-(aq) and ·OH SCCP model compounds degradation rate constants of the investigated SCCPs were consistent with that of other chlorinated compounds, with higher chlorine content producing in higher rate constants for e-(aq) and lower for ·OH. Above a chlorine:carbon ratio of approximately 0.6, the e-(aq) second-order rate constants were higher than rate constants for ·OH reactions. Results of this study furthermore suggest that SCCPs are likely susceptible to photochemical degradation in sunlit surface waters, facilitated by dissolved organic matter that can produce e-(aq) and ·OH when irradiated.

Evaluation of the Heat Produced by the Hydrothermal Liquefaction of Wet Food Processing Residues and Model Compounds

Hydrothermal liquefaction has proven itself as a promising pathway to the valorisation of low-value wet food residues. The chemistry is complex and many questions remain about the underlying mechanism of the transformation. Little is known about the heat of reaction, or even the thermal effects, of the hydrothermal liquefaction of real biomass and its constituents. This paper explores different methods to evaluate the heat released during the liquefaction of blackcurrant pomace and brewers’ spent grains. Some model compounds have also been evaluated, such as lignin, cellulose and glutamic acid. Exothermic behaviour was observed for blackcurrant pomace and brewers’ spent grains. Results obtained in a continuous reactor are similar to those obtained in a batch reactor. The heat release has been estimated between 1 MJ/kg and 3 MJ/kg for blackcurrant pomace and brewers’ spent grains, respectively. Liquefaction of cellulose and glucose also exhibit exothermic behaviour, while the transformation of lignin and glutamic acid present a slightly endothermic behaviour.

MOF-derived Ru@ZIF-8 catalyst with the extremely low metal Ru loading for selective hydrogenolysis of C-O bonds in lignin model compounds under mild conditions

Lignin hydrogenolysis to produce chemicals and biofuels is a challenge due to the stable C-O ether bonds structure. The metal-organic frameworks (MOF) materials with excellent structural and chemical versatility have...

Determination of chemical shifts in 6-condensed syringylic lignin model compounds

A small library of 6-substituted syringyl model compounds with aliphatic, carboxylic, phenylic, benzylic alcohols and brominated substituents were prepared. The influence of the substituents on the chemical shifts of the compounds was analyzed. All of model compounds showed a characteristic increase in the 13C NMR chemical shift of the methoxy group vicinal to the substitution. This 13C NMR peak and its corresponding correlation peak in HSQC could potentially be used to identify 6-condensation in syringylic lignin samples.