Use of high metal-containing biogas digestates in cereal production - Mobility of chromium and aluminium.

Biogas digestate use as organic fertilizer has been widely promoted in recent years as a part of the global agenda on recycling waste and new sustainable energy production. Although many studies have confirmed positive effects of digestates on soil fertility, there is still lack of information on the potential adverse effects of digestates on natural soil heavy metal content, metal leaching and leaching of other pollutants. We have investigated the release of aluminium (Al) and chromium (Cr) from different soils treated with commercial digestates high in mentioned potentially problematic metals in a field experiment, while a greenhouse and a laboratory column experiment were used to address mobility of these metals in two other scenarios. Results obtained from the field experiment showed an increase in total concentrations for both investigated metals on plots treated with digestates as well as a significant increase of water-soluble Al concentrations. Factors that were found to be mostly affecting the metal mobility were dissolved organic carbon (DOC), pH and type of soil. Metal binding and free metal concentrations were modelled using the WHAM 7.0 software. Results indicated that the use of digestates with high metal content are comparable to use of animal manure with respect to metal leaching. Data obtained through chemical modelling for the samples from the field experiment suggested that an environmental risk from higher metal mobility has to be considered for Al. In the greenhouse experiment, measured concentrations of leached Cr at the end of the growing season were low for all treatments, while the concentration of leached Al from digestates was higher. The high irrigation column leaching experiment showed an increased leaching rate of Cr with addition of digestates.

Fate of copper, nickel and zinc after biogas digestate application to three different soil types.

Soil application of organic residues from anaerobic digestion of municipal food waste and/or sewage sludge may introduce considerable amounts of heavy metals into the environment. In a column leaching experiment, mobility and release of Cu, Ni and Zn were investigated in three contrasting soils (sand, silt, loam) fertilized with biogas digestates of different origin. The effect of commercial digestates, based on food waste and sewage sludge, was compared to that of experimental digestates based on animal manure and whey permeate with or without fish ensilage, as well as untreated manure, mineral fertilizer and an untreated control. Manure and digestates were added to the columns as fresh material at equal amounts of available nitrogen. The experiment simulated high-intensity rainfall over a period of 7 days. In general, soil treated with the commercial digestates with higher original metal content showed less environmental impact in terms of Ni, Cu and Zn leaching than that treated with experimental digestates with lower original metal content and less than when animal manure or mineral fertilizer was applied. Although effects of digestate application on metal mobility in soils were seen in conditions of extreme precipitation, the leached concentrations of metals were below limitations published by the WHO but still significantly higher than that measured for control soils.

Non-enzymatic ribonucleotide reduction in the prebiotic context.

Model studies of prebiotic chemistry have revealed compelling routes for the formation of the building blocks of proteins and RNA, but not DNA. Today, deoxynucleotides required for the construction of DNA are produced by reduction of nucleotides catalysed by ribonucleotide reductases, which are radical enzymes. This study considers potential non-enzymatic routes via intermediate radicals for the ancient formation of deoxynucleotides. In this context, several mechanisms for ribonucleotide reduction, in a putative H2 S/HS(.) environment, are characterized using computational chemistry. A bio-inspired mechanistic cycle involving a keto intermediate and HSSH production is found to be potentially viable. An alternative pathway, proceeding through an enol intermediate is found to exhibit similar energetic requirements. Non-cyclical pathways, in which HSS(.) is generated in the final step instead of HS(.) , show a markedly increased thermodynamic driving force (ca. 70 kJ mol(-1) ) and thus warrant serious consideration in the context of the prebiotic ribonucleotide reduction.

Design of superbasic guanidines: the role of multiple intramolecular hydrogen bonds.

New organic superbases have been designed using the concept of multiple intramolecular hydrogen bonds. Substituents capable of forming strong intramolecular H-bonds were selected on the basis of the energy of stabilization that occurs upon the formation of a complex between N,N',N"-trimethylguanidine and small model molecules. The proton affinities and the corresponding pK(a) values in acetonitrile of the new superbases are examined by Density Functional Theory (DFT). It is shown that N,N',N"-substitution of guanidine with appropriate substituents results in new organic superbases with gas phase proton affinities between 286 and 293 kcal mol(-1), thus being 15 to 20 kcal mol(-1) more basic than parental superbase N,N',N"-tris[(3-dimethylamino)propyl]-guanidine (tris-DMPG), whereas estimated pK(a) values in acetonitrile range between 29.5 and 33.2.