Fate of Soil Organic Carbon and Polycyclic Aromatic Hydrocarbons in a Vineyard Soil Treated with Biochar.

The effect of biochar addition on the levels of black carbon (BC) and polcyclic aromatic hydrocarbons (PAHs) in a vineyard soil in central Italy was investigated within a two year period. Hydropyrolysis (HyPy) was used to determine the contents of BC (BCHyPy) in the amended and control soils, while the hydrocarbon composition of the semi-labile (non-BCHyPy) fraction released by HyPy was determined by gas chromatography-mass spectrometry, together with the solvent-extractable PAHs. The concentrations of these three polycyclic aromatic carbon reservoirs changed and impacted differently the soil organic carbon over the period of the trial. The addition of biochar (33 ton dry biochar ha(-1)) gave rise to a sharp increase in soil organic carbon, which could be accounted for by an increase in BCHyPy. Over time, the concentration of BCHyPy decreased significantly from 36 to 23 mg g(-1) and as a carbon percentage from 79% to 61%. No clear time trends were observed for the non-BCHyPy PAHs varying from 39 to 34 µg g(-1) in treated soils, not significantly different from control soils. However, the concentrations of extractable PAHs increased markedly in the amended soils and decreased with time from 153 to 78 ng g(-1) remaining always higher than those in untreated soil. The extent of the BCHyPy loss was more compatible with physical rather than chemical processes.

Effect of biochar amendment on organic matter and dissolved organic matter composition of agricultural soils from a two-year field experiment.

Dissolved organic matter (DOM) is an important organic matter fraction that plays a key role in many biological and chemical processes in soil. The effect of biochar addition on the content and composition of soil organic matter (SOM) and DOM in an agricultural soil in Italy was investigated within a two-year period. UV-Vis spectroscopy and analytical pyrolysis have been applied to study complex components in DOM soil samples. Additionally, analytical pyrolysis was used to provide qualitative information of SOM at molecular level and the properties of biochar before and one year after amendment. A method was developed to quantify biochar levels by thermogravimetric analysis that enabled to identify deviations from the amendment rate. The water-soluble organic carbon (WSOC) concentrations in the amended soils were significantly lower than those in the control soils, indicating that biochar decreased the leaching of DOM. DOM in treated soils was characterized by a higher aromatic character according to analytical pyrolysis and UV-Vis spectroscopy. Moreover, a relatively high abundance of compounds with N was observed in pyrolysates of treated soils, suggesting that biochar increased the proportion of microbial DOM. The results from thermal and spectroscopy techniques are consistent in highlighting significant changes in DOM levels and composition due to biochar application with important effects on soil carbon storage and cycling.

Changes in the pattern of polycyclic aromatic hydrocarbons in soil treated with biochar from a multiyear field experiment.

The influence of biochar added to an agricultural soil on polycyclic aromatic hydrocarbon (PAH) levels, PAH diagnostic ratios and soil properties was investigated in a five-year field experiment. The experiment was carried out in an Italian vineyard and included two biochar treatments: 16.5 t ha-1 of biochar applied in 2009 (soil B); 16.5 t ha-1 in 2009 and further 16.5 t ha-1 in 2010 (soil BB). A set of 75 samples that included five replicates and a control soil (untreated) was characterized in terms of organic carbon, pH, cation exchange capacity (CEC), bulk density and concentration of PAHs. Biochar addition to soil caused an increase in organic carbon, pH and CEC, and a decrease of bulk density. After almost two years the first application of biochar, PAH concentrations were higher in soil B (56 ng g-1) and BB (153 ng g-1) in comparison to control soil (24 ng g-1). Thereafter, PAH concentrations decreased significantly, but the original PAHs levels were reached only in soil B after five years. The naphthalene/(naphthalene + phenanthrene) ratios were higher in the treated soils in accordance to the dominance of naphthalene in the original biochar. The cross plots naphthalene/(naphthalene + phenanthrene) vs. fluoranthene/(fluoranthene + pyrene) enabled to trace the signature of biochar PAHs up to five years after its first application. Diagnostic ratios can be a useful tool to study the persistence of PAHs introduced in soil by biochar when the pattern of these contaminants in biochar and original soil are different.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison.

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

Relationships between Chemical Characteristics and Phytotoxicity of Biochar from Poultry Litter Pyrolysis.

Three biochars were prepared by intermediate pyrolysis from poultry litter at different temperatures (400, 500, and 600 °C with decreasing residence times) and compared with biochars from corn stalk prepared under the same pyrolysis conditions. The phytotoxicity of these biochars was estimated by means of seed germination tests on cress (Lepidium sativum L.) conducted in water suspensions (at 2, 5, and 40 g/L) and on biochars wetted according to their water-holding capacity. Whereas the seeds germinated after 72 h in water suspensions with corn stalk biochar were similar to the control (water only), significant inhibition was observed with poultry litter biochars. In comparison to corn stalk, poultry litter generated biochars with higher contents of ash, ammonium, nitrogen, and volatile fatty acids (VFAs) and a similar concentration of polycyclic aromatic hydrocarbons (PAHs). Results from analytical pyrolysis (Py-GC-MS) indicated that nitrogen-containing organic compounds (NCCs) and aliphatic components were distinctive constituents of the thermally labile fraction of poultry litter biochar. The inhibition of germination due to poultry litter biochar produced at 400 °C (PL400) was suppressed after solvent extraction or treatment with active sludge. A novel method based on solid-phase microextraction (SPME) enabled the identification of mobile organic compounds in PL400 capable of being released in air and water, including VFAs and NCCs. The higher phytotoxicity of poultry litter than corn biochars was tentatively attributed to hydrophilic biodegradable substances derived from lipids or proteins removable by water leaching or microbial treatments.