Effects of Ca2+ and Mg2+ on Cu binding in hydrophilic and hydrophobic dissolved organic matter fractions extracted from agricultural soil

Dissolved organic matter (DOM) has significant effects on soil copper (Cu) bioavailability. However, little is known about Cu interactions and major cation binding toward hydrophilic and hydrophobic DOM components extracted from soil solutions. In this study, we investigated the influence of major cations (Ca2+/Mg2+) on Cu complexing characteristics on different hydrophilic and hydrophobic DOM fractions using absorbance spectroscopy at different Cu2+ concentrations in the absence/presence of Ca2+/Mg2+. Different compositional hydrophobic and hydrophilic DOM fraction proportions occurred at three agricultural soil sites, with the hydrophobic acid (HOA) fraction accounting for the highest proportion. The addition of Cu2+ generated distinct ultraviolet (UV) bands/peaks (processed by differential linear and differential logarithmic transformation) of three hydrophilic DOM fractions, whereas Cu2+ induced less and weak specific peaks in the differential spectra and differential logarithmic of the HOA fractions, indicating hydrophilic DOM fractions tend to have a higher density of Cu2+ complexation sites. In the presence of either Ca2+/Mg2+, increased depression caused by Cu2+ binding on different DOM fractions was observed with increasing 10, 100, and 1000 μM Ca2+/Mg2+ levels, with more significant variations in peaks/banks for hydrophilic base (HIB) and HOA fractions, and less for hydrophilic acid (HIA) and hydrophilic neutral (HIN) fractions. In our study, the spectral parameters ΔS225−275 and ΔS275−325 were successfully used to quantify Cu amounts bonded to HIA and HIB, respectively. They exhibited strong linear relationships with correlation coefficients (R2) of 0.96 for HIA and 0.87 for HIB, respectively. Furthermore, Mg2+ exhibited stronger competition with Cu for HIA and HIB binding sites when compared with Ca2+. [Display omitted] •Hydrophilic fractions tend to have a higher density of Cu2+ complexation sites compared with hydrophobic acid fractions.•Cu-DOM fractions binding was depressed by Ca2+ and Mg2+, especially for hydrophilic base and hydrophobic acid fractions.•The spectral parameter ΔS225−275 and ΔS275−325 successfully quantified amount of Cu bounded onto HIA and HIB, respectively.•Mg2+ exhibited stronger competition with Cu for hydrophilic acid and base fractions binding sites compared with Ca2+.