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Chemical interactions involving chelates or metal ions

Plants can utilize iron form Fe‐N,N'‐di‐(2‐hydroxybenzoyl)‐ethylenediamine‐N,N'‐diacetic acid, a ferric chelate with 106 greater formation constant than Fe‐EDDHA.

Pages 1033-1050 | Published online: 21 Nov 2008
 

Abstract

HBED [N,N'‐di‐(2‐hydroxybenzoyl)‐ethylenediamine‐N,N'‐diacetic acid] was synthesized in 1967, but it only recently became available in the quantities needed for plant nutrition research. This chelator is a close relative of EDDHA, but has a Fe3+‐chelate formation or stability constant (at ionic strength, μ+ 0.1) of 39.68 compared to 33.91 for EDDHA. Even the Fe3+ selectivity (i.e. Fe3+/Ca2+ stability constant ratios) is greater for HBED than for EDDHA. These greater stabilities with Fe3+ appear to result from better steric fit of HBED to Fe3+. FeHBED has Fe3+ stability constant and Fe3/Fe2+ and Fe3+/Ca2+ stability constant ratios much lite the Fe3+ selective bacterial siderophores.

Soybean, corn, and nutsedge species were grown in complete Hoagland type nutrient solution containing 0 Fe, 10 μM FeHEDTA, 10 μM FeEDDHA (1:1 and 1:3 Fe:EDDHA ratios), or 10 μM FeHBED, and containing CaCO3 to control pH at 7.5. Soybean and nutsedge species obtained adequate Fe and remained green, while corn was severely chlorotic on all treatments except FeHEDTA. The results show the extreme ability of non‐graminae plant roots to reduce Fe3+ chelates and absorb iron in aerated solutions where Fe2+ can not persist long after Fe3+ chelates have been reduced. Nutsedge was found to be a typical Strategy‐1 species, unlike corn, even though the Cyperaceae and Poaceae are placed together in the order Cyperales by some taxonomic authorities.

GEOCHEM, a computer program designed to calculate equilibria for chemical species in soil solutions, was adapted to nutrient solutions to allow comparison of HBED with EDTA, DTPA, and EDDHA. It now appears that previous attempts to speciate EDDHA nutrient solutions used incorrect formation constants for CuEDDHA chelate species. Using published formation constants, GEOCHEM indicated that Cu would displace Fe across a wide pH range, but that other elements do not displace Fe at practical nutrient solution pH. The greater Fe3+ selectivity of HBED prevents Cu from displacing Fe from FeHBED. Chemical studies of Cu displacement of Fe from FeEDDHA at pH 5.5 (where the kinetics of Fe3+ exchange allow the reaction to be studied) showed that the formation constant for CuEDCHA is about 22.3 (μ = 0.1 M), not 23.9 as previously estimated. Cu can displace Fe from EDDHA within the normal nutrient solution pH range.

HBED has several advantages for use as an Fe‐chelator for nutrient solutions compared to EDDHA. EDDHA catalyzes oxidation of Mn2+ and Co2+ to strongly chelated Mn3+ and Co3+ species with unknown stability constants, but HBED does not. Thus, formation constants are available for nutrient elements with HBED, but not EDDHA. No element can displace Fe from FeHBED in practical nutrient solutions, but Cu can displace Fe from FeEDDHA. However, Fe in EDCHA is more easily available to plants than is Fe in FeHBED, probably because of stronger chelation of Fe2+ by HBED. HBED provides a more predictable reagent to control activities of micronutrient elements in nutrient solutions than does EDDHA. HBED is more expensive than EDDHA, but this should not interfere with use of HBED in plant nutrition research.

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