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  1. Abstract Headwater catchments have strong impacts on downstream waterways, near‐shore ecosystems, and the quality of water available for growing human populations. Thus, understanding how water and solutes are exported through these upland landscapes is critically important. A growing body of literature highlights the interaction of topography, climate, and the critical zone structure as a key control on streamflow and chemical export. However, more focused work is needed to pinpoint how variability in subsurface structure across lithologically complex regions impacts streamflow and chemical signals at catchment outlets. Here, we aim to better understand how lithology and subsurface critical zones modulate streamflow response and solute export patterns in two central coastal California headwater catchments that are similar in topography, vegetation, and climate but have different lithologies. We monitored streamflow and collected surface water samples at the catchment outlets for dissolved major ions and organic carbon (DOC) for two consecutive water years. The catchment with mélange bedrock displayed much flashier hydrologic behavior with 7.8 times higher peak flow values and 1.9 times higher mean event concentrations of DOC, suggesting shorter and shallower hydrologic flow paths that likely arise from regions of shallower bedrock. Despite distinct hydrologic behavior and DOC export, dissolved major ion concentrations were broadly similar and chemostatic, which may be driven by rapid chemical reactions in the critical zone of both catchments. Our work contributes to building an integrated understanding of how subtle differences in catchment structure can have profound impacts on how water and solutes are routed through headwater catchments. 
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  2. Abstract The creation of fractures in bedrock dictates water movement through the critical zone, controlling weathering, vadose zone water storage, and groundwater recharge. However, quantifying connections between fracturing, water flow, and chemical weathering remains challenging because of limited access to the deep critical zone. Here we overcome this challenge by coupling measurements from borehole drilling, groundwater monitoring, and seismic refraction surveys in the central California Coast Range. Our results show that the subsurface is highly fractured, which may be driven by the regional geologic and tectonic setting. The pervasively fractured rock facilitates infiltration of meteoric water down to a water table that aligns with oxidation in exhumed rock cores and is coincident with the adjacent intermittent first‐order stream channel. This work highlights the need to incorporate deep water flow and weathering due to pervasive fracturing into models of catchment water balances and critical zone weathering, especially in tectonically active landscapes. 
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  3. Abstract Quantifying evapotranspiration (ET) is critical to accurately predict vegetation health, groundwater recharge, and streamflow generation. Hillslope aspect, the direction a hillslope faces, results in variable incoming solar radiation and subsequent vegetation water use that drive ET. Previous work in watersheds with a single dominant vegetation type (e.g., trees) have shown that equator‐facing slopes (EFS) have higher ET compared to pole‐facing slopes (PFS) due to higher evaporative demand. However, it remains unclear how differences in vegetation type (i.e., grasses and trees) influence ET and water partitioning between hillslopes with opposing aspects. Here, we quantified ET and root‐zone water storage deficits between a PFS and EFS with contrasting vegetation types within central coastal California. Our results suggest that the cooler PFS with oak trees has higher ET than the warmer EFS with grasses, which is counter to previous work in landscapes with a singule dominant vegetation type. Our root‐zone water storage deficit calculations indicate that the PFS has a higher subsurface storage deficit and a larger seasonal dry down than the EFS. This aspect difference in subsurface water storage deficits may influence the subsequent replenishment of dynamic water storage, groundwater recharge and streamflow generation. In addition, larger subsurface water deficits on PFS may reduce their ability to serve as hydrologic refugia for oaks during multi‐year droughts. This research provides a novel integration of field‐based and remotely‐sensed estimates of ET required to properly quantify hillslope‐scale water balances. These findings emphasize the importance of resolving hillslope‐scale vegetation structure within Earth system models, especially in landscapes with diverse vegetation types. 
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  4. Abstract The structure of the critical zone (CZ) is a product of feedbacks among hydrologic, climatic, biotic, and chemical processes. Past research within snow‐dominated systems has shown that aspect‐dependent solar radiation inputs can produce striking differences in vegetation composition, topography, and soil depth between opposing hillslopes. However, far fewer studies have evaluated the role of microclimates on CZ development within rain‐dominated systems, especially below the soil and into weathered bedrock. To address this need, we characterized the CZ of a north‐facing and south‐facing slope within a first‐order headwater catchment located in central coast California. We combined terrain analysis of vegetation distribution and topography with soil pit characterization, geophysical surveys and hydrologic measurements between slope‐aspects. We documented denser vegetation and higher shallow soil moisture on north facing slopes, which matched previously documented observations in snow‐dominated sites. However, average topographic gradients were 24° and saprolite thickness was approximately 6 m across both hillslopes, which did not match common observations from the literature that showed widespread asymmetry in snow‐dominated systems. These results suggest that dominant processes for CZ evolution are not necessarily transferable across regions. Thus, there is a continued need to expand CZ research, especially in rain‐dominated and water‐limited systems. Here, we present two non‐exclusive mechanistic hypotheses that may explain these unexpected similarities in slope and saprolite thickness between hillslopes with opposing aspects. 
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