Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples.

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g(-1) for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g(-1)). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.

Use of biochar as bulking agent for the composting of poultry manure: effect on organic matter degradation and humification.

The aim of this study was to evaluate the use of biochar (produced by slow pyrolysis of Eucalyptus grandis biomass) as bulking agent for the composting of poultry manure. Three composting mixtures were prepared by the turned-pile system by mixing poultry manure with different organic wastes used as bulking agent (biochar, coffee husk and sawdust) in a proportion of 1:1 (fresh weight). Despite the inert nature of biochar, the composting mixture prepared with biochar underwent an organic matter degradation of 70% of the initial content. The organic matter of the poultry manure-biochar mixture was characterised by a high polymerisation degree of the humic-like substances, with a relative high proportion of humic acids in relation to fulvic acids. At the end of the composting process, the humic acid fraction represented more than 90% of the alkali extractable fraction, reflecting the intense humification of this material. Enrichment of poultry manure with biochar reduced the losses of nitrogen in the mature composts, although the use of sawdust would be more efficient in preserving the organic matter and nitrogen in the mature compost.