The rate of reactions between humic acid (HA) and iodide (I(-)) and iodate (IO3(-)) have been investigated in suspensions spiked with (129)I at concentrations of 22, 44 and 88 μg L(-1) and stored at 10 °C. Changes in the speciation of (129)I(-), (129)IO3(-) and mixed ((129)I(-) + (129)IO3(-)) spikes were monitored over 77 days using liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS). In suspensions spiked with (129)I(-) 25% of the added I(-) was transformed into organic iodine (Org-(129)I) within 77 days and there was no evidence of (129)IO3(-) formation. By contrast, rapid loss of (129)IO3(-) and increase in both (129)I(-) and Org-(129)I was observed in (129)IO3(-)-spiked suspensions. However, the rate of Org-(129)I production was greater in mixed systems compared to (129)IO3(-)-spiked suspensions with the same total (129)I concentration, possibly indicating IO3(-)I(-) redox coupling. Size exclusion chromatography (SEC) demonstrated that Org-(129)I was present in both high and low molecular weight fractions of the HA although a slight preference to bond with the lower molecular weight fractions was observed indicating that, after 77 days, the spiked isotope had not fully mixed with the native (127)I pool. Iodine transformations were modelled using first order rate equations and fitted rate coefficients determined. However, extrapolation of the model to 250 days indicated that a pseudo-steady state would be attained after ∼200 days but that the proportion of (129)I incorporated into HA was less than that of (127)I indicating the presence of a recalcitrant pool of (127)I that was unavailable for isotopic mixing.

Iodine is an essential trace element for humans and grazing animals and is often deficient. Our aim was to investigate the role of soil properties in retaining and 'fixing' iodine in soils and thereby controlling its phyto-availability to grass. Soils were spiked with labelled 129 IO3and rye grass (Lolium perenne L.) was grown to measure iodine uptake by grass as a function of yield, soil properties and continuous 127 I inputs from irrigation water. Iodine-129 added at the start of the uptake trial was rapidly fixed (t½ c. 40 hr) into non-labile humus-bound forms in soil. The 129 I/ 127 I isotopic ratio in grass, compared to the ratio in soil, declined over time confirming progressive 129 I fixation into the soil solid phase. The rate of fixation was controlled by soil properties. A model describing iodine dynamics and uptake accounted for c. 75% of the variation in iodine concentration in grass. For most of the soils studied, the main source of iodine in herbage probably arises from the transient availability of periodic rainfall inputs rather than from soil sources. This is expected to improve biofortification strategies. Highlights Vegetation I concentration may be controlled by recent I inputs rather than (re)supply from soil  Iodine is rapidly fixed into non-labile humus-bound forms in soils (t½ c. 40 hr)  Rate of iodine fixation is controlled by soil properties  Irrigation water inputs of iodine will likely provide the most effective biofortification strategy.