Phosphorus (P) is a finite natural resource and is increasingly considered to be a challenge for global sustainability. Agriculture in China plays a key role in global sustainable P management. Rhizosphere and soil-based P management are necessary for improving P-use efficiency and crop productivity in intensive agriculture in China. A previous study has shown that the future demand for phosphate fertilizer by China estimated by the LePA model (legacy phosphorus assessment model) can be greatly reduced by soil-based P management (the building-up and maintenance approach). The present study used the LePA model to predict the phosphate demand by China through combined rhizosphere and soil-based P management at county scale under four P fertilizer scenarios: (1) same P application rate as in 2012; (2) rate maintained same as 2012 in low-P counties or no P fertilizer applied in high-P counties until targeted soil Olsen-P (TPOlsen) level is reached, and then rate was the same as P-removed at harvest; (3) rate in each county decreased to 1–7 kg ha^–1 yr^–1 after TPOlsen is reached in low-P counties, then increased by 0.1–9 kg ha^–1 yr^–1 until equal to P-removal; (4) rate maintained same as 2012 in low-P counties until TPOlsen is reached and then equaled to P-removal, while the rate in high-P counties is decreased to 1–7 kg ha^–1 yr^–1 until TPOlsen is reached and then increased by 0.1–9 kg ha^–1 yr^–1 until equal to P-removal. Our predictions showed that the total demand for P fertilizer by whole China was 693 Mt P2O5 and according to scenario 4, P fertilizer could be reduced by 57.5% compared with farmer current practice, during the period 2013–2080. The model showed that rhizosphere P management led to a further 8.0% decrease in P fertilizer use compared with soil-based P management. The average soil Olsen-P level in China only needs to be maintained at 17 mg kg^–1 to achieve high crop yields. Our results provide a firm basis for government to issue-relevant policies for sustainable P management in China.

The adsorption of Cu(II) from aqueous solution onto humic acid (HA) which was isolated from cattle manure (CHA), peat (PHA), and leaf litter (LHA) as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy (XAS) was used to examine the coordination environment of the Cu(II) adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy (NMR). The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu(II) on CHA, PHA, and LHA were 229.4, 210.4, and 197.7 mg g–1, respectively. The adsorption of Cu(II) on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH>7. The adsorption of Cu(II) was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L–1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L–1 NaNO3. The Cu(II) adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu(II) concentrations of 15 to 40 mg L–1. For all the Cu(II) adsorption samples, each Cu atom was surrounded by 4 O/N atoms at a bond distance of 1.95 Å in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu(II) was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu(II) was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu(II). These results are important to achieve better understanding of the behavior of Cu(II) in soil and water bodies in the presence of organic materials.