Satellite imagery as a management tool for monitoring water clarity across freshwater ponds on Cape Cod, Massachusetts.

Water clarity serves as both an indicator and a regulator of biological function in aquatic systems. Large-scale, consistent water clarity monitoring is needed for informed decision-making. Inland freshwater ponds and lakes across Cape Cod, a 100-km peninsula in Massachusetts, are of particular interest for water clarity monitoring. Secchi disk depth (SDD), a common measure of water clarity, has been measured intermittently for over 200 Cape Cod ponds since 2001. Field-measured SDD data were used to estimate SDD from satellite data, leveraging the NASA/USGS Landsat Program and Copernicus Sentinel-2 mission, spanning 1984 to 2022. Random forest machine learning models were generated to estimate SDD from satellite reflectance data and maximum pond depth. Spearman rank correlations (rs) were "strong" for Landsat 5 and 7 (rs = 0.78 and 0.79), and "very strong" for Landsat 8, 9, and Sentinel-2 (rs = 0.83, 0.86, and 0.80). Mean absolute error also indicated strong predictive capacity, ranging from 0.65 to 1.05 m, while average bias ranged from -0.20 to 0.06 m. Long- and recent short-term changes in satellite-estimated SDD were assessed for 193 ponds, selected based on surface area and the availability of maximum pond depth data. Long-term changes between 1984 and 2022 established a retrospective baseline using the Mann-Kendall test for trend and Theil-Sen slope. Generally, long-term water clarity improved across the Cape; 149 ponds indicated increasing water clarity, and 8 indicated deteriorating water clarity. Recent short-term changes between 2021 and 2022 identified ponds that may benefit from targeted management efforts using the Mann-Whitney U test. Between 2021 and 2022, 96 ponds indicated deteriorations in water clarity, and no ponds improved in water clarity. While the 193 ponds analyzed here constitute only one quarter of Cape Cod ponds, they represent 85% of its freshwater surface area, providing the most spatially and temporally comprehensive assessment of Cape Cod ponds to date. Efforts are focused on Cape Cod, but can be applied to other areas given the availability of local field data. This study defines a framework for monitoring and assessing change in satellite-estimated SDD, which is important for both local and regional management and resource prioritization.

Fe(II)-catalyzed recrystallization of goethite revisited.

Results from enriched (57)Fe isotope tracer experiments have shown that atom exchange can occur between structural Fe in Fe(III) oxides and aqueous Fe(II) with no formation of secondary minerals or change in particle size or shape. Here we derive a mass balance model to quantify the extent of Fe atom exchange between goethite and aqueous Fe(II) that accounts for different Fe pool sizes. We use this model to reinterpret our previous work and to quantify the influence of particle size and pH on extent of goethite exchange with aqueous Fe(II). Consistent with our previous interpretation, substantial exchange of goethite occurred at pH 7.5 (≈ 90%) and we observed little effect of particle size between nanogoethite (average size of 81 × 11 nm; ≈ 110 m(2)/g) and microgoethite (average size of 590 × 42 nm; ≈ 40 m(2)/g). Despite ≈ 90% of the bulk goethite exchanging at pH 7.5, we found no change in mineral phase, average particle size, crystallinity, or reactivity after reaction with aqueous Fe(II). At a lower pH of 5.0, no net sorption of Fe(II) was observed and significantly less exchange occurred accounting for less than the estimated proportion of surface Fe atoms in the particles. Particle size appears to influence the amount of exchange at pH 5.0 and we suggest that aggregation and surface area may play a role. Results from sequential chemical extractions indicate that (57)Fe accumulates in extracted Fe(III) goethite components. Isotopic compositions of the extracts indicate that a gradient of (57)Fe develops within the goethite with more accumulation of (57)Fe occurring in the more easily extracted Fe(III) that may be nearer to the surface.

Influence of chloride and Fe(II) content on the reduction of Hg(II) by magnetite.

Abiotic reduction of inorganic mercury by natural organic matter and native soils is well-known, and recently there is evidence that reduced iron (Fe) species, such as magnetite, green rust, and Fe sulfides, can also reduce Hg(II). Here, we evaluated the reduction of Hg(II) by magnetites with varying Fe(II) content in both the absence and presence of chloride. Specifically, we evaluated whether magnetite stoichiometry (x = Fe(II)/Fe(III)) influences the rate of Hg(II) reduction and formation of products. In the absence of chloride, reduction of Hg(II) to Hg(0) is observed over a range of magnetite stoichiometries (0.29 < x < 0.50) in purged headspace reactors and unpurged low headspace reactors, as evidenced by Hg recovery in a volatile product trap solution and Hg L(III)-edge X-ray absorption near edge spectroscopy (XANES). In the presence of chloride, however, XANES spectra indicate the formation of a metastable Hg(I) calomel species (Hg2Cl2) from the reduction of Hg(II). Interestingly, Hg(I) species are only observed for the more oxidized magnetite particles that contain lower Fe(II) content (x < 0.42). For the more reduced magnetite particles (x ≥ 0.42), Hg(II) is reduced to Hg(0) even in the presence of high chloride concentrations. As previously observed for nitroaromatic compounds and uranium, magnetite stoichiometry appears to influence the rate of Hg(II) reduction (both in the presence and absence of chloride) confirming that it is important to consider magnetite stoichiometry when assessing the fate of contaminants in Fe-rich subsurface environments.

Fe atom exchange between aqueous Fe2+ and magnetite.

The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.