Several Al-substituted goethites were synthesized by hydrolysis of Fe3+ salt solutions. The kinetics of the reductive dissolution of these goethites in dithionite-ethylenediaminetetra acetic acid (D-EDTA) was studied at pH 5.5, at 303, 323 and 333 K. The initial dissolution rate (R) per unit of surface area decreases with Al substitution. In the sample with greater Al content (G″7), the kinetic profiles of the dissolved Fe fraction vs. time gave a small positive intercept. The kinetic profile of R as a function of EDTA initial concentration shows a significant weakening in the presence of Al. The maximum is flatter and wider in Al-substituted goethite than that of pure goethite. In sample G″7, where the Al content is 11.3 mol.% the maximum is obtained when the [D]:[EDTA] initial ratio is ∼4.5 vs. 2 in un-substituted goethite. These results can be attributed to the lesser density of the more active dimeric sites, the presence of more strongly bonded Al-O-Fe with regard to Fe-O and the small value for the ≡ Al-EDTA surface species constant. Activation energy (Ea) increases with Al substitution. Its value is doubled from GO (pure goethite) to G″7 (11.3 mol.% of Al). The frequency factor (A) acts in the opposite sense to Ea, but it is not sufficient to outweigh the effect of Ea.

Sediment magnetic properties of a short core from Sharkey Lake, MN, record the effects of Euroamerican settlement and climate change over the last 150 yr. The onset of European-style farming led to increased erosion, reflected in high values of concentration-dependent parameters such as magnetic susceptibility (ĸ), Isothermal Remanent Magnetization (IRM), and Anhysteretic Remanent Magnetization (ARM). These high values are only partially due to increased supply of terrigenous material to the lake, and recent sediment contains an additional component of authigenic fine (single-domain) magnetite, most likely magnetosomes from magnetotactic bacteria. High organic productivity in the lake during the 1920s to 1940s drought increased this authigenic component resulting in highly magnetic fine-grained sediment. A comparison with older Holocene sediment from the same lake shows that, over time, most of the fine magnetic signal is lost after deposition, leading to decreases in magnetization and a bimodal grain size distribution of ultrafine, superparamagnetic grains and coarser multidomain particles, evident from measurements of ARM/IRM ratios, hysteresis measurements, and low-temperature analyses. The effects of dissolution and the superposition of climate and land-use signals complicate the use of recent sediments as modern analogs for sediment magnetic analyses.