The Mackenzie River Basin (MRB) delivers large quantities of organic carbon (OC) into the Arctic Ocean, with significant implications for the global C budgets and ocean biogeochemistry. The amount and properties of OC in the Mackenzie River's delta have been well monitored in the last decade, but the spatial variability in OC sources transported by its different tributaries is still unclear. Here we present new data on the radiocarbon (14C) content of dissolved and particulate OC (Δ14C‐DOC and Δ14C‐POC) across the mainstem and major tributaries of the MRB, comprising 19 different locations, to identify factors controlling spatial patterns in riverine OC sources. The Δ14C‐DOC and Δ14C‐POC varied across a large range, from −179.9‰ to 62.9‰, and −728.8‰ to −9.0‰, respectively. Our data reveal a positive spatial coupling between the Δ14C of DOC and POC across the MRB, whereby the most 14C‐depleted waters were issued from the mountainous west bank of the MRB. This 14C‐depleted DOC and POC likely originates from a combination of petrogenic sources, connected with the presence of kerogens in the bedrock, and biogenic sources, mobilized by thawing permafrost. Our analysis also reveals intriguing relationships between Δ14C of DOC and POC with turbidity, water stable isotope ratio and catchment elevation, indicating that hydrology and geomorphology are key to understanding riverine OC sources in this landscape. A closer examination of the specific mechanisms giving rise to these relationships is recommended. For now, this study provides a road map of the key OC sources in this rapidly changing river basin.

Lentic water bodies (lakes and reservoirs) offer favorable conditions for silica (SiO2) burial in sediments. Recent global estimates suggest that (1) lentic SiO2 trapping is a globally important SiO2 flux, and (2) through reservoir construction, humans have dramatically altered river dissolved SiO2 (DSi) transport and coastal DSi delivery. However, regional to global scale patterns and controls of DSi removal in lentic systems are poorly constrained. Here we use 27 published lake and reservoir DSi budgets to develop insights into patterns and controls of lentic DSi retention and to develop a new, spatially explicit, global model of lentic DSi removal called SiRReLa (Silica Retention in Reservoirs and Lakes). In our analysis, lentic DSi removal (kg SiO2 yr−1) was significantly and positively related to DSi loading (P < 0.0001; r2 = 0.98), and DSi removal efficiency was significantly and positively related to water residence time (P < 0.0001; r2 = 0.68). In addition, DSi settling rates were, on average, 6.5-fold higher in eutrophic systems than in non-eutrophic systems (median settling velocities: 11.1 and 1.7 m yr−1 for eutrophic and non-eutrophic systems, respectively; P < 0.01). SiRReLa, which incorporates these insights, performed quite well in predicting both total DSi removal (kg SiO2 yr−1; Nash Sutcliffe Efficiency (N.S.E) = 0.88) and DSi removal efficiency (% Si removed; N.S.E. = 0.75), with no detectable bias in the model. Global application of SiRReLa confirms that lentic systems are important sinks for DSi, removing 89.1 Tg DSi yr−1 from watersheds globally, roughly 19–38% of all DSi inputs to surface waters. Small lakes and reservoirs (<50 km2) were critical in the analysis, retaining 81% (72 Tg DSi yr−1) of the globally retained total. Furthermore, although reservoirs occupy just 6% of the global lentic surface area, they retained approximately 35% of the total DSi removed by lentic systems. Regional hot spots for lentic DSi removal were identified and imply that lentic systems can remove the vast majority of DSi across a large fraction of Earth's land surface. Finally, a sensitivity analysis indicates that future improvements in DSi trapping and transport models should focus on improving estimates of DSi input to surface waters.

Air-sea exchange of gaseous elemental mercury (Hg0) is not well constrained, even though it is a major component of the global Hg cycle. Lack of Hg0 flux measurements to validate parameterizations of the Hg0 transfer velocity contributes to this uncertainty. We measured the Hg0 flux on the Baltic Sea coast using micrometeorological methods (gradient-based and relaxed eddy accumulation [REA]) and also simulated the flux with a gas exchange model. The coastal waters were typically supersaturated with Hg0 (mean ± 1σ = 13.5 ± 3.5 ng m−3; ca. 10% of total Hg) compared to the atmosphere (1.3 ± 0.2 ng m−3). The Hg0 flux calculated using the gas exchange model ranged from 0.1–1.3 ng m−2 h−1 (10th and 90th percentile) over the course of the campaign (May 10–June 20, 2017) and showed a distinct diel fluctuation. The mean coastal Hg0 fluxes determined with the two gradient-based approaches and REA were 0.3, 0.5, and 0.6 ng m−2 h−1, respectively. In contrast, the mean open sea Hg0 flux measured with REA was larger (6.3 ng m−2 h−1). The open sea Hg0 flux indicated a stronger wind speed dependence for the Hg0 transfer velocity compared to commonly used parameterizations. Although based on a limited data set, we suggest that the wind speed dependence of the Hg0 transfer velocity is more consistent with gases that have less water solubility than CO2 (e.g., O2). These pioneering flux measurements using micrometeorological techniques show that more such measurements would improve our understanding of air-sea Hg exchange.

The Ross Sea, Antarctica, is a highly productive region of the Southern Ocean. Significant new sources of iron (Fe) are required to sustain phytoplankton blooms in the austral summer. Atmospheric deposition is one potential source. The fractional solubility of Fe is an important variable determining Fe availability for biological uptake. To constrain aerosol Fe inputs to the Ross Sea region, fractional solubility of Fe was analyzed in a snow pit from Roosevelt Island, eastern Ross Sea. In addition, aluminum, dust, and refractory black carbon (rBC) concentrations were analyzed, to determine the contribution of mineral dust and combustion sources to the supply of aerosol Fe. We estimate exceptionally high dissolved Fe (dFe) flux of 1.2 × 10⁻⁶ g m⁻² y⁻¹ and total dissolvable Fe flux of 140 × 10⁻⁶ g m⁻² y⁻¹ for 2011/2012. Deposition of dust, Fe, Al, and rBC occurs primarily during spring-summer. The observed background fractional Fe solubility of ~0.7% is consistent with a mineral dust source. Radiogenic isotopic ratios and particle size distribution of dust indicates that the site is influenced by local and remote sources. In 2011/2012 summer, relatively high dFe concentrations paralleled both mineral dust and rBC deposition. Around half of the annual aerosol Fe deposition occurred in the austral summer phytoplankton growth season; however, the fractional Fe solubility was low. Our results suggest that the seasonality of dFe deposition can vary and should be considered on longer glacial-interglacial timescales.