Biochar physicochemical parameters as a result of feedstock material and pyrolysis temperature: predictable for the fate of biochar in soil?

Biochar application is a widely investigated topic nowadays, and precisely described biochar parameters are key information for the understanding of its behaviour in soil and other media. Pore structure and surface properties determine biochar fate. However, there is lack of complex, investigative studies describing the influence of biomass properties and pyrolysis conditions on the pore structure of biochars. The aim of our study was to evaluate a wide range of gathered agriculture residues and elevated pyrolysis temperature on the biochar surface properties and pore composition, predicting biochar behaviour in the soil. The biomass of herbaceous and wood plants was treated by slow pyrolysis, with the final temperature ranging from 400 to 600 °C. Specific surface ranged from 124 to 511 cm2 g-1 at wood biochar and from 3.19 to 192 cm2 g-1 at herbaceous biochar. The main properties influencing biochar pore composition were increasing pyrolysis temperatures and lignin (logarithmically) and ash contents (linearly) of biomass. Increasing lignin contents and pyrolysis temperatures caused the highest biochar micropore volume. The total biochar pore volume was higher of wood biomass (0.08-0.3 cm-3 g-1). Biochars of wood origin were characterised by skeletal density ranging from 1.479 to 2.015 cm3 g-1 and herbaceous ones 1.506-1.943 cm3 g-1, and the envelope density reached 0.982 cm3 g-1 at biochar of wheat grain origin and was generally higher at biochars of herbaceous origin. Density was not pyrolysis temperature dependent.

RP-HPLC/MS-APCI analysis of odd-chain TAGs from Rhodococcus erythropolis including some regioisomers.

We used reversed phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (RP-HPLC/MS-APCI) for direct analysis of triacylglycerols (TAGs) from four different cultivations of Rhodococcus erythropolis CCM 2595. This technique enabled us to identify and quantify the specific molecular species of TAGs directly from lipid extracts of the bacterium, including the determination of their basic characteristics such as retention time and mass spectra. A total of 17 TAGs having at least one odd-numbered-chain FA (fatty acid) were found. This is the first time when odd-chain TAGs, predominantly with pentadecanoic, margaric, and margaroleic acids, were identified. Multiple linear regression analyses were used for predicting retention times of molecular species, predominantly of odd-chain TAGs. Cultivations on two different substrates at two different temperatures (20 and 30 degrees C) showed that only temperature had any effect on the content of TAGs. In cultivations with succinate as a carbon source the content of these TAGs increased by half (i.e., from 23.5 to 34.2%) when the cultivation temperature was lowered from 30 to 20 degrees C. The content of the PoPoMo, PoMoO and PPoMo (see Table 1) TAGs containing the odd-numbered-chain margaroleic acid rose from 0.0 to 7.1% while in cultivation on phenol as a carbon source the lowering of cultivation temperature caused an increase of these TAGs from 0.5 to 6.7%.

RP-HPLC/MS-APCI analysis of branched chain TAG prepared by precursor-directed biosynthesis with Rhodococcus erythropolis.

Reversed phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (RP-HPLC/MS-APCI) was used to analyze both synthetic triacylglycerols (TAG) having 1-3 branched fatty acids (FA) in the molecule, and natural TAG prepared by precursor directed biosynthesis from valine, leucine and isoleucine and the corresponding branched short-chain acids in cultivations of Rhodococcus erythropolis. The technique made it possible to identify and quantify TAG differing in a single branched-chain FA. Altogether 11 TAG were synthesized, out of which 8 were synthesized stereospecifically. Branched- and straight-chain-TAG were separated and identified while TAG differing only in iso or anteiso FA could not be separated. The APCI mass spectra of iso-, anteiso- and straight-chain TAG were completely identical. The natural material was found to contain 19 TAG having at least one branched FA. Cultivation on six different substrates showed, apart from the presumed and common incorporation of precursors to iso-even, iso-odd and anteiso FA, also some unusual features such as an increase in the content of odd-FA after the addition of Val (attributed to catabolism of Val to propionate) or the appearance of branched monounsaturated FA. The two-sample paired t test, when applied to the TAG, showed that only the pair Val and isobutyrate differ in incorporation into FA--see, e.g. proportions of M/M/O and brM/brM/O (1.2:1.2 and 1.9:1.2, respectively). Also, incorporation of Val (isobutyrate) yielded only TAG having two branched FA in the molecule, whereas Leu and Ile (isovalerate and 2-methyl-butyrate) gave only TAG with a single branched FA in the molecule.