Characterization of the Fe(III)—fulvic acid reaction by Mössbauer spectroscopy

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Abstract
SUMMARY: Fulvic acids have been isolated from a sandy loam (Countesswells series) and a clay soil (Tipperty series) and the products of their reaction with different amounts of iron over a range of pH from 0.5 to 11 analyzed by Mössbauer spectroscopy. Three distinct types of spectral component were detected at 77 K, a sextet from magnetically dilute Fe(III) and doublets from Fe(II) and Fe(III), the last arising from both organic complexes and poorly crystalline oxide species.In iron‐fulvic acid mixtures the proportion of iron as Fe(II) increased as the pH was lowered from 5 to 1 by the addition of hydrochloric or nitric acid at all Fe to fulvic acid ratios (1:5 to 1:500). When the pH was lowered below 1 the amounts of Fe(II) decreased with the lower Fe to fulvic acid ratios, but increased with the higher ratios. The amounts of the Fe(III) component contributing to a doublet signal decreased with decreasing Fe:fulvic acid ratios.At low iron concentrations the iron appears to be strongly bound to the fulvic acid, but when the iron content is of the order of 1–2% uncomplexed Fe(III) species can be present. At pH > 2 these are hydrolysed ions which form poorly‐crystalline oxides at higher pH. This was confirmed by analysis of spectra at 4.2 K. At pH < 2 free ions are present in solution.In solutions with high fulvic acid contents (greater than 100‐fold excess) the reactions with iron are completely reversible, but in solutions with a lower proportion of fulvic acid to iron, where free ions are present, there is a lack of reversibility.