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Meteoric waters move along pathways in the subsurface that differ as a function of lithology because of the effects of chemical and physical weathering. To explore how this affects stream chemistry, we investigated watersheds around an igneous intrusion in the Luquillo Mountains (Puerto Rico). We analyzed streams on 1) unmetamorphosed country rock (volcaniclastic sedimentary strata, VC) surrounding an igneous intrusion, 2) the quartz-diorite intrusion (QD), and 3) the metamorphosed aureole rock (hornfels-facies volcaniclastics, HF). These lithologies differ physically and chemically but weather under the same tropical rain forest conditions. The sedimentary VC lithology is pervasively fractured while the massive QD and HF lithologies are relatively unfractured. However, the QD fractures during weathering to produce spheroidally-weathered corestones surrounded by cm-thick rindlets of increasingly weathered rock. Meteoric waters flow pervasively through the network of already-fractured VC rock and the spheroidally weathered rindlets on the QD, but only access a limited fraction of the HF, explaining why streams draining HF are the most dilute in the mountains. This results in various thicknesses of regolith from thick (VC) to moderate (QD) to thin or nonexistent (HF). The pervasive fractures allow groundwater to flow deeply through the VC and then return to the mainstem river (Río Mameyes) at lower elevations. These “rock waters” drive concentrations of rock-derived solutes (silica, base cations, sulfate, phosphate) higher in the lower reaches of the stream. Water also flows through weathering-induced fractures on the QD at high elevations where rindletted corestones are present in stacks, and this water flux dissolves plagioclase and hornblende and oxidizes biotite. This “QD rock water” is not generated at lower elevations in the Río Icacos watershed, where stacks of corestones are absent, and contributions to stream solutes derive from weathering of feldspar- and hornblende-depleted saprolite. The stream chemistry in the QD-dominated watershed (Río Icacos) thus varies from concentrated QD-rock water at channel heads below steep ridgelines toward more diluted “saprolite water” downstream. These observations emphasize the importance of lithology and fracture patterns in dictating water flowpaths, stream chemistry, and regolith development in headwater catchments. 

Extreme rainfall events in the humid-tropical Luquillo Mountains, Puerto Rico export the bulk of suspended sediment and particulate organic carbon. Using 25 years of river carbon and suspended sediment data, which targeted hurricanes and other large rainstorms, we estimated biogenic particulate organic carbon yields of 65 ± 16 tC km⁻²yr⁻¹for the Icacos and 17.7 ± 5.1 tC km⁻²yr⁻¹for the Mameyes rivers. These granitic and volcaniclastic catchments function as substantial atmospheric carbon-dioxide sinks, largely through export of river biogenic particulate organic carbon during extreme rainstorms. Compared to other regions, these high biogenic particulate organic carbon yields are accompanied by lower suspended sediment yields. Accordingly, particulate organic carbon export from these catchments is underpredicted by previous yield relationships, which are derived mainly from catchments with easily erodible sedimentary rocks. Therefore, rivers that drain petrogenic-carbon-poor bedrock require separate accounting to estimate their contributions to the geological carbon cycle.

 

The Central Siberian Plateau is undergoing rapid climate change that has resulted in increased frequency of forest fires and subsequent alteration of watershed carbon and nutrient dynamics. Across a watershed chronosequence (3 to >100 years since wildfire) we quantified the effects of fire on quantity and composition of dissolved organic matter (DOM), stream water nutrient concentrations, as well as in-stream nutrient uptake. Wildfires increased concentrations of nitrate for a decade, while decreasing concentrations of dissolved organic carbon and nitrogen (DOC and DON) and aliphatic DOM contribution for five decades. These post-wildfire changes in stream DOM result in lower uptake efficiency of in-stream nitrate in recently burned watersheds. Nitrate uptake (as uptake velocity) is strongly dependent on DOM composition (e.g. polyphenolics), ambient dissolved inorganic nitrogen (DIN), and DOC to DIN ratios. Our observations and experiments suggest that a decade-long pulse of inorganic nitrogen and a reduction of DOC export occur following wildfires in streams draining the Central Siberian Plateau. Increased fire frequency in the region is thus likely to both decrease DOM and increase nitrate delivery to the main stem Yenisei River, and ultimately the Arctic Ocean, in the coming decades.