a b s t r a c tPlants employ a range of strategies to increase phosphorus (P) availability in soil. Current soil P extraction methods (e.g. Olsen P), however, often fail to capture the potential importance of rhizosphere processes in supplying P to the plant. This has led to criticism of these standard approaches, especially in nonagricultural soils of low P status and when comparing soil types across diverse landscapes. Similarly, more complex soil P extraction protocols (e.g. Hedley sequential fractionation) lack functional significance from a plant ecology perspective. In response to this, we present a novel procedure using a suite of established extraction protocols to explore the concept of a protocol that characterizes P pools available via plant and microbial P acquisition mechanisms. The biologically based P (BBP) extraction was conducted by using four extractions in parallel: (1) 10 mM CaCl 2 (soluble P); (2) 10 mM citric acid (chelate extractable P); (3) phytase and phosphatase solution (enzyme extractable organic P); (4) 1 M HCl (mineral occluded P). To test the protocol, we conducted the analyses on a total of 204 soil samples collected as part of a UK national ecosystem survey (Countryside Survey) in 1998 and repeated again in 2007. In the survey, Olsen P showed a net decline in national soil P levels during this 10 year period. In agreement with these results, soluble P, citrate extractable P and mineral occluded P were all found to decrease over the 10 year study period. In contrast, enzyme extractable organic P increased over the same period likely due to the accumulation of organic P in the mineral soil. The method illustrates a noted shift in P pools over the 10 year period, but no net loss of P from the system. This new method is simple and inexpensive and therefore has the potential to greatly improve our ability to characterise and understand changes in soil P status across complex landscapes.

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Enhanced methanol production is obtained over a non-promoted Cu–MgO–Al2O3 mixed oxide catalyst derived from a Cu–Mg–Al hydrotalcite precursor (HT) containing narrowly distributed small Cu NPs (2 nm). Conversions close to the equilibrium (∼20%) with a methanol selectivity of 67% are achieved at 230 °C, 20 bar, and a space velocity of 571 mL·gcat –1·h–1. Based on operando spectroscopic studies, the striking activity of this Cu-based catalyst is ascribed to the stabilization of Cu+ ions favored under reaction conditions due to lattice reorganization associated with the “HT-memory effect” promoted by water. Temperature-resolved infrared–mass spectrometry experiments have enabled the discernment of monodentate formate species, stabilized on Cu+ as the intermediate in methanol synthesis, in line with the results of density functional theory calculations. These monodentate formate species are much more reactive than bridge formate species, the latter ones behaving as intermediates in methane and CO formation. Moreover, poisoning of the Cu0 surface by strongly adsorbed species behaving as spectators is observed under reaction conditions. This work presents a detailed spectroscopic study highlighting the influence of the reaction pressure on the stabilization of active surface sites, and the possibility of enhancing methanol production on usually less active non-promoted nano-sized copper catalysts, provided that the proper support is selected, allowing the stabilization of doped Cu+. Thus, a methanol formation rate of 2.6 × 10–3 molMeOH·gcat –1·h–1 at 230 °C, 20 bar, and WHSV = 28 500 mL·gcat –1·h–1 is obtained on the Cu–MgO–Al2O3 HT-derived catalyst with 71% methanol selectivity, compared to 2.2 × 10–4 molMeOH·gcat –1·h–1 with 54% methanol selectivity obtained on a reference Cu/(Al2O3/MgO) catalyst not derived from a HT structure.