Iron (Fe) bioavailability depends upon its solubility and oxidation state, which are strongly influenced by complexation with natural organic matter (NOM). Despite observations of Fe(II)-NOM associations under conditions favorable for Fe oxidation, the molecular mechanisms by which NOM influences Fe(II) oxidation remain poorly understood. In this study, we used X-ray absorption spectroscopy to determine the coordination environment of Fe(II) associated with NOM (as-received and chemically reduced) at pH 7, and investigated the effect of NOM complexation on Fe(II) redox stability. Linear combination fitting of extended X-ray absorption fine structure (EXAFS) data using reference organic ligands demonstrated that Fe(II) was complexed primarily by carboxyl functional groups in reduced NOM. Functional groups more likely to preserve Fe(II) represent much smaller fractions of NOM-bound Fe(II). Fe(II) added to anoxic solutions of as-received NOM oxidized to Fe(III) and remained organically complexed. Iron oxidation experiments revealed that the presence of reduced NOM limited Fe(II) oxidation, with over 50% of initial Fe(II) remaining after 4 h. These results suggest reduced NOM may preserve Fe(II) by functioning both as redox buffer and complexant, which may help explain the presence of Fe(II) in oxic circumneutral waters.

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Accurately predicting the effect of temperature on soil C storage remains a crucial objective in the effort to understand, mitigate, and adapt to climate change. Associations between soil organic C and short‐range order minerals like the iron hydroxide ferrihydrite contribute substantially to C sequestration, but little is known about how these associations respond to changes in temperature. We investigated the effects of temperature (7, 25, and 45 °C) and dissolved organic matter (DOM) source and fraction on DOM sorption to ferrihydrite‐coated sand in continuous flow and batch systems at circumneutral pH. Our findings demonstrate a positive relationship between temperature and adsorption, especially between 25 and 45 °C. For aquatic DOM, desorption also increased appreciably with temperature, whereas desorption of peat and soil DOM was less sensitive. More aquatic DOM adsorbed compared with soil DOM at all temperatures, but flow studies revealed that aquatic DOM also desorbed at higher rates. Modeling of DOM breakthrough curves using the advection‐diffusion equation with a modified Freundlich isotherm suggested the partition coefficient increased over time. Specific ultraviolet absorbance values of initial column effluents were low, suggesting that aromatic‐rich compounds preferentially adsorbed to the mineral surface. Our results indicate that some circumstances may favor the accumulation of DOM on iron mineral surfaces as temperature increases, potentially removing organic substrates from the accessible dissolved C pool. However, the stability of new associations likely depends on the chemical characteristics of DOM and the conditions under which it adsorbed.

Methods for surveying and analyzing channel bed topography commonly lack a rigorous characterization of their appropriateness for project objectives. We compare four survey methods: a hand level, two different methods of surveying with a laser rangefinder, and a realtime kinematic GNSS (RTK-GNSS) to explore their accuracy in determining channel bed slope and roughness for a study reach in a small, dry, steep channel. Additionally, we evaluate the variability among four operators for each survey technique. Two methods of calculating reach slope were computed: a regression on the channel profile and a calculation using only survey endpoints. Using data from the RTK-GNSS as our accuracy reference, the hand level and twoperson laser rangefinder surveying systems performed with high accuracy (<5% error in estimating slope, <10% error in estimating roughness), while the one-person laser rangefinder survey system performed with considerably lower accuracy (up to 54% error in roughness and slope). Variability between operators was found to be very low (coefficients of variation ranged from 0.001 to 0.046) for all survey systems except the one-person laser rangefinder system, suggesting that survey data collected by different operators can be validly compared. Due to reach-scale concavity, calculating slope using a regression produced significantly different values than those obtained by using only survey endpoints, suggesting that caution must be taken in choosing the most appropriate method of calculating slope for a given project objective. We present recommendations for choosing appropriate survey and analysis methods to accomplish various surveying objectives.