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.

Water erosion is the major reason for the loss of soil organic carbon in the Northeast China, which leads to the soil quality deterioration and adjacent water pollution. In this study, the effect of extraction temperature, pH value, and salt on the water extractable organic matter (WEOM) was determined by means of the UV absorbance, fluorescence excitationemission matrix, and derived fluorescence indexes. In general, the carbon content and aromaticity of WEOM increased with the increasing of extraction temperature, with the exception that there was no significant difference in the amount at 0 and 20°C. More fluorophores, especially microbially-derived organic matter were extracted at high temperature. The pH values of extractant, including 5, 7, and 10, showed no effect on the carbon amount of WEOM, whereas the aromaticity and microbially-derived component gradually increased with the increasing of pH values. The fluorescence intensity of humic acid-like fluorophore was stronger in neutral and alkali condition than that in acidic condition. The addition of 10 mmol L-1 CaCl2 significantly decreased the carbon amount of recovered WEOM. Moreover, it significantly decreased the aromaticity of WEOM and the quantity of fulvic acid-like and humic acid-like fluorophores, whereas increased the percentage of tyrosine-like and tryptophan-like fluorophores in the total fluorophores and the amount of microbially-derived organic matter. Generally, 10 mmol L-1 KCl showed the same influence trend, but with low influence degree.