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Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nano-fabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nm-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously: Namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities”, such as defects, nanoconfinement, and other non-typical chemical structures. Third, progress in computational chemistry have yielded new insights that allow a move beyond simple schematics leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges, as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration. 

Accelerating erosion of the Alaska Beaufort Sea coast is increasing inputs of organic matter from land to the Arctic Ocean, and improved estimates of organic matter stocks in eroding coastal permafrost are needed to assess their mobilization rates under contemporary conditions. We collected three permafrost cores (4.5–7.5 m long) along a geomorphic gradient near Drew Point, Alaska, where recent erosion rates average 17.2 m year −1 . Down-core patterns indicate that organic-rich soils and lacustrine sediments (12–45% total organic carbon; TOC) in the active layer and upper permafrost accumulated during the Holocene. Deeper permafrost (below 3 m elevation) mainly consists of Late Pleistocene marine sediments with lower organic matter content (∼1% TOC), lower C:N ratios, and higher δ 13 C values. Radiocarbon-based estimates of organic carbon accumulation rates were 11.3 ± 3.6 g TOC m −2  year −1 during the Holocene and 0.5 ± 0.1 g TOC m −2  year −1 during the Late Pleistocene (12–38 kyr BP). Within relict marine sediments, porewater salinities increased with depth. Elevated salinity near sea level (∼20–37 in thawed samples) inhibited freezing despite year-round temperatures below 0°C. We used organic matter stock estimates from the cores in combination with remote sensing time-series data to estimate carbon fluxes for a 9 km stretch of coastline near Drew Point. Erosional fluxes of TOC averaged 1,369 kg C m −1  year −1 during the 21st century (2002–2018), nearly doubling the average flux of the previous half-century (1955–2002). Our estimate of the 21st century erosional TOC flux year −1 from this 9 km coastline (12,318 metric tons C year −1 ) is similar to the annual TOC flux from the Kuparuk River, which drains a 8,107 km 2 area east of Drew Point and ranks as the third largest river on the North Slope of Alaska. Total nitrogen fluxes via coastal erosion at Drew Point were also quantified, and were similar to those from the Kuparuk River. This study emphasizes that coastal erosion represents a significant pathway for carbon and nitrogen trapped in permafrost to enter modern biogeochemical cycles, where it may fuel food webs and greenhouse gas emissions in the marine environment. 

Permafrost cores (4.5-7.5 m long) were collected April 10th-19th, 2018, along a geomorphic gradient near Drew Point, Alaska to characterize active layer and permafrost geochemistry and material properties. Cores were collected from a young drained lake basin, an ancient drained lake basin, and primary surface that has not been reworked by thaw lake cycles. Measurements of total organic carbon (TOC) and total nitrogen (TN) content, stable carbon isotope ratios (δ13C) and radiocarbon (14C) analyses of bulk soils/sediments were conducted on 45 samples from 3 permafrost cores. Porewaters were extracted from these same core sections and used to measure salinity, dissolved organic carbon (DOC), total dissolved nitrogen (TDN), anion (Cl-, Br-, SO4 2-, NO3 -), and trace metal (Ca, Mn, Al, Ba, Sr, Si, and Fe) concentrations. Radiogenic strontium (87Sr/86Sr) was measured on a subset of porewater samples. Cores were also sampled for material property measurements such as dry bulk density, water content, and grain size fractions.