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This study demonstrates the effects of structural variations of lignins isolated via an organosolv process from different woody and herbaceous feedstocks on their thermal stability profiles. The organosolv lignins were first analysed for impurities, and structural features were determined using the default set of gel permeation chromatography, FT-IR spectroscopy, quantitative 31 P NMR spectroscopy and semi-quantitative 1 H- 13 C HSQC analysis. Pyrolysis-, O 2 - and CO 2 -reactivity of the organosolv lignins were investigated by thermogravimetric analysis (TGA), and volatile formation in various heating cycles was mapped by head-space GC-MS analysis. Revealed reactivities were correlated to the presence of identified impurities and structural features typical for the organosolv lignins. Data suggest that thermogravimetric analysis can eventually be used to delineate a lignin character when basic information regarding its isolation method is available. [ABSTRACT FROM AUTHOR]

Background: Hydrothermal carbonization (HTC) of dairy processing waste was performed to investigate the effect of temperature and initial pH on the yield and composition of the solid (hydrochar) and liquor produced. All hydrochars met the EU requirements of organo-mineral solid fertilizers defined in the Fertilizing Products Regulation in terms of phosphorus (P) and mineral content. Methods: Laboratory scale HTC was performed using pressurized reactors, and the products (solid and liquid) were collected, stored and analyzed for elemental composition and nutrient content using Inductively coupled plasma optical emission spectroscopy (ICP-OES), ultraviolet-visible spectrophotometry (UV-Vis) and other analytic techniques. Results: Maximum hydrochar yield (60.67%) was observed at T=180℃ and pH=2.25, whereas the maximum P-recovery was 80.38% at T=220℃ and pH=4.6. The heavy metal content of the hydrochars was mostly compliant with EU limitations, except for Ni at T=220℃ and pH=8.32. Meanwhile, further study of Chromium (Cr) species is essential to assess the fertilizer quality of the hydrochars. For the liquid product, the increase in temperature beyond 200℃, coupled with an increase in initial acidity (pH=2.25) drove P into the liquor. Simultaneously, increasing HTC temperature and acidity increased the concentration of NO 3 - and NH 4 + in the liquid products to a maximum of 278 and 148 mg/L, respectively, at T=180℃ and pH=4.6. Furthermore, no direct relation between final pH of liquor and NH 4 + concentration was observed. Conclusions: HTC allows for the production of hydrochar as a potential fertilizer material that requires further processing. Adjusting HTC conditions enhanced P-recovery in the hydrochar, while retrieving higher nitrate concentrations in the liquid product. Optimizing HTC for the production of qualified hydrochars requires further treatment of Cr content, studying the availability of P in the products and enhancing the hydrochar yield for economic feasibility., Competing Interests: No competing interests were disclosed., (Copyright: © 2023 Khalaf N et al.)

Dairy processing sludge (DPS) and DPS-derived secondary products such as struvite, biochar, hydrochar and ash (collectively known as SRUBIAS) are emerging as alternatives to fertilizers produced from mined rock phosphate. However, little is known about how these products affect soil P availability and daily P turnover rates.. A lack of such information prevents precision nutrient management planning using these products out on farms. This study used a novel isotope dilution technique (IPD) with 33 P as a tracer to compare P turnover in soils amended with chemically (alum-treated DPS and struvite) and thermally (biochar, hydrochar, ash) treated DPS. Results showed that thermally treated products exhibited poor agronomic performance as P fertilizers, potentially inhibiting P availability when applied to soils. For example, a P deficient soil amended with hydrochar treatment at the highest application rates did not record a build-up of available P to agronomic target values. In ash and biochar treated P deficient soils, available P increased but only with very high application rates of 150 and 80 mg P kg -1 . The application of these products as fertilizers could have negative implications for both environmental and agronomic goals. Conversely, chemically treated fertilisers demonstrated better agronomic performance. The same agronomic target value was reached with application rates of only 20 mg P kg -1 soil for DPS and 50 mg P kg -1 soil for struvite. However, the techniques deployed revealed that these products exhibited slower rates of available and exchangeable P build-up when compared with chemical fertilisers. This suggests that these bio-based alternatives require higher application rates or earlier application times compared to conventional chemical fertilizers. Regulations providing advice on P use in agricultural soils need to account for slower P turnover in soils receiving recycled fertilizers. The IPD technique is transferrable to all wastes to examine their performance as fertilizers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This review sheds light on the catalytic valorisation of agroforestry biomass through levulinic acid and formic acid towards γ-valerolactone and other higher-value chemicals. γ-Valerolactone is produced by the hydrogenation of levulinic acid, which can be achieved through an internal hydrogen transfer reaction with formic acid in the presence of catalyst. By reviewing corresponding catalysts, the paper underlines the most efficient steps constituting an integrated sustainable process that eliminates the need for external H 2 sources while producing biofuels as an alternative energy source. Furthermore, the review emphasizes the role of catalysts in the hydrogenation of levulinic acid, with special focus on heterogeneous catalysts. The authors highlighted the dual role of different catalysts by comparing their activity, morphology, electronic structure, synergetic relation between support and doped species, as well as their deactivation and recyclability. Acknowledging the need for green and sustainable H 2 production, the review extends to cover the role of photo catalysis in dissociating H 2 -donor solvents for reducing levulinic acid into γ-valerolactone under mild temperatures. To wrap up, the critical discussion presented enables readers to hone their knowledge about different schools and emphasizes research gaps emerging from experimental work. The review concludes with a comprehensive table summarizing the recent catalysts reported between the years 2017-2021., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

The dairy industry produces vast quantities of dairy processing sludge (DPS), which can be processed further to develop second generation products such as struvite, biochars and ashes (collectively known as STRUBIAS). These bio-based fertilizers have heterogeneous nutrient and metal contents, resulting in a range of possible application rates. To avoid nutrient losses to water or bioaccumulation of metals in soil or crops, it is important that rates applied to land are safe and adhere to the maximum legal application rates similar to inorganic fertilizers. This study collected and analysed nutrient and metal content of all major DPS (n = 84) and DPS-derived STRUBIAS products (n = 10), and created an application calculator in MS Excel™ to provide guidance on maximum legal application rates for ryegrass and spring wheat across plant available phosphorus (P) deficient soil to P-excess soil. The sample analysis showed that raw DPS and DPS-derived STRUBIAS have high P contents ranging from 10.1 to 122 g kg -1 . Nitrogen (N) in DPS was high, whereas N concentrations decreased in thermo-chemical STRUBIAS products (chars and ash) due to the high temperatures used in their formation. The heavy metal content of DPS and DPS-derived STRUBIAS was significantly lower than the EU imposed limits. Using the calculator, application rates of DPS and DPS-derived STRUBIAS materials (dry weight) ranged from 0 to 4.0 tonnes ha -1 y -1 for ryegrass and 0-4.5 tonnes ha -1 y -1 for spring wheat. The estimated heavy metal ingestion to soil annually by the application of the DPS and DPS-derived STRUBIAS products was lower than the EU guideline on soil metal accumulation. The calculator is adaptable for any bio-based fertilizer, soil and crop type, and future work should continue to characterise and incorporate new DPS and DPS-derived STRUBIAS products into the database presented in this paper. In addition, safe application rates pertaining to other regulated pollutants or emerging contaminants that may be identified in these products should be included. The fertilizer replacement value of these products, taken from long-term field studies, should be factored into application rates., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)