New insights into the production, characterization and potential uses of vineyard pruning waste biochars.

Vineyard pruning waste (VP) can be converted into a useful char using pyrolysis as part of a valorization strategy. This study analyzed the effect of temperature (300 and 600 °C) and residence time (1 and 3 h) on an ample number of properties of VP derived biochars, including potential negative environmental impacts. The results showed a clear influence of temperature on biochar's properties and a weaker effect of residence time. Increasing temperature raised soil pH, electrical conductivity (EC), ash and C contents, aromaticity, specific surface area, solid density, mesoporosity and partial graphitization. However, higher pyrolysis temperature reduced O/C and N/C ratios, total N, P and Mg, and polycyclic aromatic hydrocarbons (PAHs). Particularly, the concentration of water extractable organic carbon (WEOC) decreased dramatically with pyrolysis temperature. Moreover, the WEOC fraction of biochars pyrolyzed at 300 °C exhibited a larger aromaticity than those pyrolyzed at 600 °C. Prolonged residence time increased ash content and fixed carbon (FC) and decreased H/C and O/C ratios; however, most frequently this parameter affected biochar properties following opposite trends for the two pyrolysis temperatures. Hydrophysical properties were adequate to consider VP derived biochars as growing media component. PAH concentration was much lower than thresholds following international standards. The germination index increased with temperature and decreased with residence time, so that phytotoxicity was observed in VP and in biochars pyrolyzed for 3 h. Our research demonstrates that, besides temperature, residence time can be useful to modulate the properties of biochars and that prolonged time effect is temperature-dependent.

Long-Term Uptake of Phenol-Water Vapor Follows Similar Sigmoid Kinetics on Prehydrated Organic Matter- and Clay-Rich Soil Sorbents.

Typical experimental time frames allowed for equilibrating water-organic vapors with soil sorbents might lead to overlooking slow chemical reactions finally controlling a thermodynamically stable state. In this work, long-term gravimetric examination of kinetics covering about 4000 h was performed for phenol-water vapor interacting with four materials pre-equilibrated at three levels of air relative humidity (RHs 52, 73, and 92%). The four contrasting sorbents included an organic matter (OM)-rich peat soil, an OM-poor clay soil, a hydrophilic Aldrich humic acid salt, and water-insoluble leonardite. Monitoring phenol-water vapor interactions with the prehydrated sorbents, as compared with the sorbent samples in phenol-free atmosphere at the same RH, showed, for the first time, a sigmoid kinetics of phenol-induced mass uptake typical for second-order autocatalytic reactions. The apparent rate constants were similar for all the sorbents, RHs and phenol activities studied. A significant part of sorbed phenol resisted extraction, which was attributed to its abiotic oxidative coupling. Phenol uptake by peat and clay soils was also associated with a significant enhancement of water retention. The delayed development of the sigmoidal kinetics in phenol-water uptake demonstrates that long-run abiotic interactions of water-organic vapor with soil may be overlooked, based on short-term examination.

Spatial and seasonal patterns of fluorescent organic matter in Lake Kinneret (Sea of Galilee) and its catchment basin.

Lake Kinneret (Sea of Galilee) is one of the major water resources in Israel. The origin and characteristics of natural organic matter (NOM) in the lake and its tributary rivers were studied using fluorescence excitation emission matrices (EEM) and parallel factor analysis. Two humic-like and one proteinous components were sufficient to describe EEM variability among 167 water samples collected between 2/2005 and 9/2006. The two humic-like components showed different relations in lake and riverine samples. Their vertical distribution in the lake was affected by seasonal stratification and distance from water surface, presumably reflecting the release of humic-like matter from sediments, its production via NOM transformation in the bottom layers, and its photodegradation in the upper layers. Vertical distribution of the proteinous component, indicating biological activity at upper water layers, did not correlate with that of the humic-like components. Dissolved organic carbon concentrations did not show any vertical stratification, emphasizing the power of EEM to explore NOM dynamics.