Humin is the most recalcitrant and least understood fraction of soil organic matter. By definition, humin is that fraction not extracted by traditional aqueous alkaline soil extractants. Here we show that > or = 70% of the traditional humin fraction is solubilized when 0.1 M NaOH + 6 M urea and dimethyl sulfoxide (DMSO) + 6% H2SO4 are used in series after conventional extraction. Multidimensional solution-state NMR is applied in this study to gain an understanding of the major constituents present in these "solubilized humin fractions". The spectra indicated strong contributions from five main categories of components, namely, peptides, aliphatic species, carbohydrates, peptidoglycan, and lignin. Diffusion edited spectroscopy indicated that all species are present as macromolecules (or stable aggregate species). Although the distribution of the components is generally similar, peptidoglycan is present at significant levels supporting a higher microbial contribution to humin than to humic and fulvic fractions. The abundance of plant- and microbial-derived materials found does not exclude "humic" materials (e.g., oxidized lignin) or the presence of novel compounds at lower concentrations but suggests that a large proportion of humin is formed from classes of known compounds and parent biopolymers.

Biochar (carbonized biomass for agricultural use) has been used worldwide as soil amendment and is a technology of particular interest for Brazil, since its "inspiration" is from the historical Terra Preta de Índios (Amazon Dark Earth), and also because Brazil is the world's largest charcoal producer, generating enormous residue quantities in form of fine charcoal and due to the availability of different residual biomasses, mainly from agroindustry (e.g., sugar-cane bagasse; wood and paper-mill wastes; residues from biofuel industries; sewage sludge etc), that can be used for biochar production, making Brazil a key actor in the international scenario in terms of biochar research and utilization). In the last decade, numerous studies on biochar have been carried out and now a vast literature, and excellent reviews, are available. The objective of this paper is therefore to deliver a critical review with some highlights on biochar research, rather than an exhaustive bibliographic review. To this end, some key points considered critical and relevant were selected and the pertinent literature "condensed", with a view to guide future research, rather than analyze trends of the past.

Neste trabalho faz-se a divulgação do potencial de carvões e resíduos orgânicos parcialmente carbonizados visando obter materiais que mimetizam a matéria orgânica do solo das Terras Pretas de Índio da Amazônia, e que sirvam como condicionadores de solo e seqüestrem carbono de forma recalcitrante e reativa. Pesquisas desenvolvidas por grupos brasileiros e estrangeiros têm contribuído para o entendimento do surgimento e utilização das Terras Pretas de Índio da Amazônia. Aqui são divulgados resultados de estudos químicos no sentido do desenvolvimento do conhecimento científico e tecnológico e de inovação no aproveitamento de subprodutos orgânicos, principalmente de indústrias de biocombustíveis, carvão vegetal metalúrgico e outros, buscando imitar a excelente performance da chamada Terras Pretas de Índio da Amazônia.The potential of charcoal and of partially combusted organic waste to mimic the soil organic matter of the Terras Pretas de Índios (Amazonian Dark Earths) from the Amazon Region is discussed. These materials serve as soil conditioners and as sequesterers of carbon in recalcitrant and in reactive forms. Studies carried out by Brazilian and by international groups have contributed to the emergence of an awareness of the compositions and of the uses of these materials. In this contribution we report on chemical studies that are leading to the development of a scientific and technological awareness, and of innovations that will have value in finding novel uses in applications to soil of chars from organic wastes such as those from the biofuel industry, and from metallurgical and various coal plant residues.

There is an increasing realisation that biomass and organic wastes are valuable feedstocks for second generation biorefining processes that give rise to platform chemicals to substitute for dwindling petrochemical resources, and for pyrolysis processes that produce syngas, bio-oil, and biochar from biomass, organic wastes, and the biorefining residuals of the future. The experimental work described has focused on physical properties and compositions of biochars produced from miscanthus (Miscanthus x giganteus), willow (Salix spp) and pine (Pinus sylvestris) at 500°C and at 400, 500, and 600°C in the case of the miscanthus. Although the morphologies of the cell structures were maintained in the pyrolysis, the surface area of the miscanthus biochar was greatly increased by heating at 600°C for 60 min. Nuclear magnetic resonance spectra showed the disappearance of evidence for the carbohydrate and lignin plant components as the pyrolysis temperature was raised, and the compositions of miscanthus biochars after heating for 10 and for 60 min at 600°C were very similar and composed of fused aromatic structures and with no traces of the aliphatic components in the starting materials. In greenhouse and growth chamber experiments the growth of maize (Zea mays L) seedlings was found to be inhibited by soil amendments with biochar from miscanthus formed at 400°C for 10 min, but stimulated by miscanthus char formed at 600°C for 60 min. In the course of discussion the relevance of the results obtained is related to the roles that soil amendments with biochar can have on soil fertility, carbon sequestration, on the emissions of greenhouse gases from soil, on fertilizer requirements, and on waste management. It is clear that biochar soil amendments can have definite agronomic and environmental benefits, but it will be essential to have clear guidelines for biochar production from various feedstocks and under varying pyrolysis parameters. It will be equally important to have a classification system for biochars that clearly indicate the product compositions that will meet acceptable standards. A case can be made for sets of standard biochars from different substrates that meet the required criteria.

No abstract

ABSTRACT. The compositions of humic acids (HAs) isolated from cultivated and forest 'Terra Preta de Índio' or Amazonian Dark Earth (ADE) soils (formed as the result of pre-Columbian anthropogenic activity) were compared with those from adjacent non-anthropogenic soils (NAS) using elemental and thermogravimetric analyses, and a variety of solid state nuclear magnetic resonance (NMR) techniques. The thermogravimetric index (TGI, or the ratio of the weight lost in the range 378 to 623K, indicative of polysaccharides and the decarboxylation of acidic groups, to that in the range 623 to 923K, indicative of combustion of aromatic structures and cleavages of C-C bonds) was greater for the anthropogenic soils than for the control soils indicating polycyclic aromatic components in the former. The cultivated anthropogenic soils (CAS) were more enriched in C and depleted in H than the anthropogenic soils under forest (ASF), as the result of the selective degradation of aliphatic structures and the possible enrichment of H-deficient condensed aromatic structures.

No abstract

No abstract