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The hydrogen isotopic composition of lake water (δ2Hlw) contains hydrologic information and can be used as a recorder of lake water hydrology, including the extent of evaporation of the lake system. Initial studies indicate that the hydrogen isotopes of highly branched isoprenoids (δ2HHBI), synthesized by lake diatoms and preserved in lake sediments are a promising proxy for constraining past δ2Hlw values that are free from terrestrial in- fluences. However, there are many aspects of this proxy, including the seasonality of HBI production, that are unknown and need to be addressed more fully before the proxy can by widely applied. To determine when HBIs are produced throughout the year, and whether there are seasonal biases in δ2Hlw reconstructions, we deployed two sediment traps at Brown’s Lake, in northeastern Ohio. We present HBI concentrations, δ2HHBI values, HBI carbon isotopes and bulk sediment carbon isotopes from sediment traps collected monthly for 26 months to investigate seasonality of HBIs. We observed HBIs in each of the monthly sediment traps throughout the study interval with an increase in HBI concentration during September and October, suggesting that HBIs are made throughout the year with greater production during fall. We calculated the difference between δ2HHBI and δ2Hlw values (ε2HHBI/lw) and observe a range in ε2HHBI/lw values of up to 64‰, which we speculate is related to changes in the diatom communities that synthesize HBIs throughout the year and between different years. Different diatom communities may have different biosynthetic pathways or metabolisms that result in isotope effects. This study is the first that examines the seasonality of HBIs in lake sediments and provides framework for interpreting the seasonality of hydroclimate records generated from δ2HHBI values in temperate eutrophic lakes. 

Diatom-derived highly branched isoprenoid lipids (HBIs) are found extensively in marine sediments, but to date are only reported in a few lacustrine sediments. To expand on prior lake studies, we collected lake surface sediment samples, water samples, and filtered photic zone water from 50 lakes from the Great Plains to the northeastern United States. Samples were collected in May and June and a few sites were revisited in September and October. Studied lakes vary in climate, water chemistry (e.g., pH, salinity, alkalinity), size, and trophic states. They also vary in their diatom species compositions with 344 diatom taxa reported. We characterized HBI assemblages in each lake and found 11 different HBI compounds including one C20:0 HBI, five C20:1 HBI isomers, C21:0 HBI, C25:2 HBI, two C25:3 HBIs, and C25:4 HBI. C20:0 HBI was present in all but two lakes and was often the most abundant HBI present. HBIs were also detected in nearly all the water filter samples indicating they are produced in the photic zone. C20:0 HBI was present in all freshwater lakes, but not present or at very low con- centration in the highest salinity lakes, which were dominated by C21:0 HBI and C25 HBIs. Many of the lakes were dominated by diatom genera and species that are not known to be HBI-producing genera, suggesting there are unrecognized HBI-producing diatom taxa. This inventory, illustrating the widespread presence and diversity of HBIs from lakes across large differences in water chemistries and climate, further suggests that HBIs may be useful diatom biomarkers for paleoclimate applications. 

The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question by exam- ining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERC- ZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr􏱝1 in Fushan 􏱞 0.2–0.4 mm yr􏱝1 in ERCZO 􏱞 0.01–0.025 mm yr􏱝1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr􏱝1 in Fushan > 1.9 m yr􏱝1 in ERCZO > 1.1 m yr􏱝1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100􏱟, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate condi- tions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales. 

Abstract The spatiotemporal dynamics of plant water sources are hidden and poorly understood. We document water source use ofQuercus garryanagrowing in Northern California on a profile of approximately 50 cm of soil underlain by 2–4 m of weathered bedrock (sheared shale mélange) that completely saturates in winter, when the oaks lack leaves, and progressively dries over the summer. We determined oak water sources by combining observations of water stable isotope composition, vadose zone moisture and groundwater dynamics, and metrics of tree water status (potential) and use (sapflow). During the spring, oak xylem water is isotopically similar to the seasonal groundwater and shallow, evaporatively enriched soil moisture pools. However, as soils dry and the water table recedes to the permanently saturated, anoxic, low‐conductivity fresh bedrock boundary,Q. garryanashifts to using a water source with a depleted isotopic composition that matches residual moisture in the deep soil and underlying weathered bedrock vadose zone. Sapflow rates remain high as late‐summer predawn water potentials drop below−2.5 MPa. Neutron probe surveys reveal late‐summer rock moisture declines under the oaks in contrast to constant rock moisture levels under grass‐dominated areas. We therefore conclude that the oaks temporarily use seasonal groundwater when it occupies the weathered profile but otherwise use deep unsaturated zone moisture after seasonal groundwater recedes. The ample moisture, connected porosity, and oxygenated conditions of the weathered bedrock vadose zone make it a key tree water resource during the long summer dry season of the local Mediterranean climate. 

Abstract Bedrock vadose zone water storage (i.e., rock moisture) dynamics are rarely observed but potentially key to understanding drought responses. Exploiting a borehole network at a Mediterranean blue oak savanna site—Rancho Venada—we document how water storage capacity in deeply weathered bedrock profiles regulates woody plant water availability and groundwater recharge. The site is in the Northern California Coast Range within steeply dipping turbidites. In a wet year (water year 2019; 647 mm of precipitation), rock moisture was quickly replenished to a characteristic storage capacity, recharging groundwater that emerged at springs to generate streamflow. In the subsequent rainless summer growing season, rock moisture was depleted by about 93 mm. In two drought years that followed (212 and 121 mm of precipitation) the total amount of rock moisture gained each winter was about 54 and 20 mm, respectively, and declines were documented exceeding these amounts, resulting in progressively lower rock moisture content. Oaks, which are rooted into bedrock, demonstrated signs of water stress in drought, including reduced transpiration rates and extremely low water potentials. In the 2020–2021 drought, precipitation did not exceed storage capacity, resulting in variable belowground water storage, increased plant water stress, and no recharge or runoff. Rock moisture deficits (rather than soil moisture deficits) explain these responses. 

Abstract Earth System Models (ESMs) are essential tools for understanding and predicting global change, but they cannot explicitly resolve hillslope‐scale terrain structures that fundamentally organize water, energy, and biogeochemical stores and fluxes at subgrid scales. Here we bring together hydrologists, Critical Zone scientists, and ESM developers, to explore how hillslope structures may modulate ESM grid‐level water, energy, and biogeochemical fluxes. In contrast to the one‐dimensional (1‐D), 2‐ to 3‐m deep, and free‐draining soil hydrology in most ESM land models, we hypothesize that 3‐D, lateral ridge‐to‐valley flow through shallow and deep paths and insolation contrasts between sunny and shady slopes are the top two globally quantifiable organizers of water and energy (and vegetation) within an ESM grid cell. We hypothesize that these two processes are likely to impact ESM predictions where (and when) water and/or energy are limiting. We further hypothesize that, if implemented in ESM land models, these processes will increase simulated continental water storage and residence time, buffering terrestrial ecosystems against seasonal and interannual droughts. We explore efficient ways to capture these mechanisms in ESMs and identify critical knowledge gaps preventing us from scaling up hillslope to global processes. One such gap is our extremely limited knowledge of the subsurface, where water is stored (supporting vegetation) and released to stream baseflow (supporting aquatic ecosystems). We conclude with a set of organizing hypotheses and a call for global syntheses activities and model experiments to assess the impact of hillslope hydrology on global change predictions.