Metal speciation in xylem and phloem exudates

Summary Two computer programs based on simultaneous chemical equilibria were compared for calculation of chemical species in xylem exudates. The first program, CHELATE, was developed to calculate the chemical species in xylem exudates while GEOCHEM was developed to calculate the speciation of natural aquatic systems. The output of the two programs should be similar since they are based on similar calculations. Data input to the programs consisted of concentration data for Ca, Cu, Fe, Mg, Mn, Zn, NH₄, PO₄, pH and 28 organic ligands reported for xylem exudates from soybean (Glycine max (L.) Merr.) and tomato (Lycopersicon esculentum Mill.) plants grown in nutrient solution¹⁷. The organic ligands included amino acids and low molecular weight organic acids (e.g., citric and malic). With the exception of Fe, there were large differences between CHELATE and GEOCHEM in the calculated speciation of nearly all metals in the xylem exudates. In general, there was better agreement between the programs for the speciation of alkaline earth metals than for transition metals. Discrepancies between the two programs were attributed to differences in 1) species considered and 2) stability constants. GEOCHEM considered a greater number of possible complexes. In addition, stability constants for some complexes differed by as much as 10 fold between the two programs. When the data base for GEOCHEM and CHELATE were the same, the output from CHELATE and GEOCHEM was almost identical. Thus, computations performed by the two programs are equally valid, but it is essential that the data base used in chemical models be verified before interpreting the output. Average concentration data for Al, Au, Ca, Cu, Fe, K, La, Mg, Mn, Na, Rb, Zn, Cl, MoO₄, PO₄, SO₄, HVO₄, pH and 18 organic ligands in phloem exudates from Yucca (Yucca flaccida Haw.) were complied from available literature and analyzed by GEOCHEM. Amino acids were the predominant organic ligand analyzed. Calculations revealed that alkali metals existed almost totally as the free ionic species (≥99%) whereas alkaline earth metals were transported as complexes with organic acids (oxalic, malic, and asparagine). Aluminum and Fe were present as hydroxyl species while <1% of micronutrients were transported as the free ion. Major micronutrient species were Cu-glutamine, Mn-asparagine and Zn-alanine. Information on calculated species present in phloem exudates could be useful to guide studies for isolation of metal-ligand complexes in phloem exudates.