Stream Dissolved Organic Carbon Concentrations Research Articles

Disentangling the responses of dissolved organic carbon and nitrogen concentrations to overlapping drivers in a northeastern United States forested watershed

The concurrent reduction in acid deposition and increase in precipitation impact stream solute dynamics in complex ways that make predictions of future water quality difficult. To understand how changes in acid deposition and precipitation have influenced dissolved organic carbon (DOC) and nitrogen (N) loading to streams, we investigated trends from 1991 to 2018 in stream concentrations (DOC, ~3,800 measurements), dissolved organic nitrogen (DON, ~1,160 measurements), and dissolved inorganic N (DIN, ~2,130 measurements) in a forested watershed in Vermont, USA. Our analysis included concentration-discharge (C-Q) relationships and Seasonal Mann-Kendall tests on long-term, flow-adjusted concentrations. To understand whether hydrologic flushing and changes in acid deposition influenced long-term patterns by liberating DOC and dissolved N from watershed soils, we measured their concentrations in the leachate of 108 topsoil cores of 5 cm diameter that we flushed with solutions simulating high and low acid deposition during four different seasons. Our results indicate that DOC and DON often co-varied in both the long-term stream dataset and the soil core experiment. Additionally, leachate from winter soil cores produced especially high concentrations of all three solutes. This seasonal signal was consistent with C-Q relation showing that organic materials (e.g., DOC and DON), which accumulate during winter, are flushed into streams during spring snowmelt. Acid deposition had opposite effects on DOC and DON compared to DIN in the soil core experiment. Low acid deposition solutions, which mimic present day precipitation, produced the highest DOC and DON leachate concentrations. Conversely, high acid deposition solutions generally produced the highest DIN leachate concentrations. These results are consistent with the increasing trend in stream DOC concentrations and generally decreasing trend in stream DIN we observed in the long-term data. These results suggest that the impact of acid deposition on the liberation of soil carbon (C) and N differed for DOC and DON vs. DIN, and these impacts were reflected in long-term stream chemistry patterns. As watersheds continue to recover from acid deposition, stream C:N ratios will likely continue to increase, with important consequences for stream metabolism and biogeochemical processes.

Machine‐Learning Reveals Equifinality in Drivers of Stream DOC Concentration at Continental Scales

AbstractResearch at long‐term catchment monitoring sites has generated a great volume, variety, and velocity of data for analysis of stream water chemistry dynamics. To harness the potential of these big data and extract patterns that are indicative of underlying functional relationships, machine learning tools have advantages over traditional statistical methods, and are increasingly being applied for dimension reduction, feature extraction, and trend identification. Still, as examples of complex systems, catchments are characterized by multivariate factor interactions and equifinality that are not easily identified by most machine‐learning methods. Using dissolved organic carbon (DOC) dynamics as an illustration, we applied a new evolutionary algorithm (EA) to extract geologic, topographic, meteorologic, hydrologic, and land use attributes that were correlated to mean stream DOC concentration in forested catchments distributed across the continental United States. The EA reduced dimensionality of our attribute dataset to identify the combination of factors, and their specific value ranges, that interacted to drive membership in High or Low mean DOC clusters. High mean DOC concentrations were associated with two distinct geographic locations of variable climatic and vegetative conditions, indicating equifinality. Our findings underscore the importance of critical zone structure in mediating hydrological and biogeochemical processes to govern DOC dynamics at the catchment scale. This multi‐scale, pattern‐to‐process approach is being applied to refine hypotheses for process‐based modeling of DOC dynamics in forested headwater streams at catchment to site scales.

Woody debris dominates the exports of carbon and nitrogen from headwater streams in an alpine forest

AbstractThe exports of carbon and nitrogen with water flowing in the headwater streams could be important components of material mitigation in forest ecosystems. Plant debris is a major source of dissolved organic matter for headwater streams, but few studies have investigated the differences between the impacts of woody debris and non‐woody debris inputs on headwater streams in terms of carbon and nitrogen exports. Here, we assessed the effects of plant debris (i.e., woody debris, non‐woody debris and mixed debris) on the concentrations and exports of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) in the headwater streams of an alpine forest on the eastern Tibetan Plateau. Woody and non‐woody debris only weakly affected the DOC and TDN concentrations in the headwater streams. Compared with those in the reference stream excluding plant debris, woody debris increased the exports of DOC and TDN by 19% and 13%, whereas non‐woody debris decreased the exports of DOC and TDN by 22% and 25%, respectively. However, when fall approached, the role of non‐woody debris reversed to enhance the stream‐water exports of DOC and TDN. The effect of non‐woody debris during the fall season differed from that during the overall growing season, indicating that restricting non‐woody debris inputs might improve the ability of the stream to retain forest carbon and nitrogen. Notwithstanding the relatively limited experimental period, this work revealed the critical importance of plant debris for carbon and nutrients within water conservation regions like alpine forests.

Groundwater flow paths drive longitudinal patterns of stream dissolved organic carbon (DOC) concentrations in boreal landscapes

Abstract. Preferential groundwater flow paths can influence dissolved organic carbon (DOC) concentration and export in the fluvial network because they facilitate the inflow of terrestrial DOC from large upslope contributing areas to discrete sections of the stream, referred to as discrete riparian inflow points (DRIPs). However, the mechanisms by which DRIPs influence longitudinal patterns of stream DOC concentrations are still poorly understood. In this study, we ask how DRIPs affect longitudinal patterns of stream DOC concentrations under different hydrologic conditions, as they can simultaneously act as major sources of terrestrial DOC and important locations for in-stream processes. To answer this question, we tested four model structures that account for different representations of hydrology (distributed inflows of DRIPs vs. diffuse groundwater inflow) and in-stream processes (no DOC uptake vs. in-stream DOC uptake downstream of DRIPs) to simulate stream DOC concentrations along a 1.5 km headwater reach for 14 sampling campaigns with flow conditions ranging from droughts to floods. Despite the magnitude and longitudinal patterns of stream DOC concentration varying across campaigns, at least one model structure was able to capture longitudinal trends during each campaign. Specifically, our results showed that during snowmelt periods or high-flow conditions (>50 L s−1), accounting for distributed inputs of DRIPs improved simulations of stream DOC concentrations along the reach, because groundwater inputs from DRIPs diluted the DOC in transport. Moreover, accounting for in-stream DOC uptake immediately downstream of DRIPs improved simulations during five sampling campaigns that were performed during spring and summer, indicating that these locations served as a resource of DOC for aquatic biota. These results show that the role of DRIPs in modulating DOC concentration, cycling, and export varies over time and depends strongly on catchment hydrology. Therefore, accounting for DRIPs can improve stream biogeochemistry frameworks and help inform management of riparian areas under current and future climatic conditions.

Analysis of spatiotemporal variation in dissolved organic carbon concentrations for streams with cropland-dominated watersheds

It remains a challenge to understand how dissolved organic carbon (DOC) is cycled from farmlands to rivers due to the complex interaction between farming practices, the baseflow hydrology of predominantly flat lowlands, and seasonal environmental influences such as snowpack. To address this, field DOC concentrations were measured monthly throughout the year at sub-basin scales across the Chippewa River Watershed, which falls within the Corn Belt of the Midwestern United States. These DOC dynamics in stream water from croplands were benchmarked against the data sampled from hilly forested areas in the Connecticut River Watershed. The Soil Water Assessment Tool (SWAT) simulation was applied to provide potential predictive variables associated with daily baseflow. Our study outlines a framework using the combination of primary field data, hydrological modeling, and knowledge-based reclassification of Land Use/Land Cover (LULC) data to analyze the viability of modeling the spatial and temporal variations of cropland stream DOC concentrations. Calibration of the SWAT model resulted in the overall daily Nash–Sutcliffe model efficiency coefficient (NSE) of 0.67 and the corresponding R2 = 0.89. Our main results show: 1) baseflow DOC concentrations from croplands were substantially higher throughout the year relative to other landcover areas, especially for spring runoff/snowmelt scenarios, 2) an empirical analysis explained ~82 % of the spatial gradient of annual mean observed DOC concentrations, and 3) with the addition of hydrological simulated variables, a linear model explained ~81 % of monthly and 54 % of daily variations of observed DOC concentrations for cropland sub-basins. Our study identified key factors regulating the spatiotemporal DOC concentrations in cropland streamflow; the contribution here promotes to strengthen future analytical models that link watershed characteristics to carbon cycling processes in a large freshwater ecosystem.

Riparian Microtopography Affects Event‐Driven Stream DOC Concentrations and DOM Quality in a Forested Headwater Catchment

AbstractThe transport of dissolved organic carbon (DOC) from the soils to inland waters plays an important role in the global carbon cycle. Widespread increases in DOC concentrations have been observed in surface waters over the last few decades, affecting carbon balances, ecosystem functioning and drinking water treatment. However, the primary hydrological controls on DOC mobilization are still uncertain. The aim of this study was to investigate the role of microtopography in the riparian zone for DOC export and DOM quality. DOC concentration and DOM quality in the shallow groundwater of a riparian zone and in streamflow in a forested headwater catchment was investigated using fluorescence and absorbance characteristics. We found higher DOC concentrations with a higher aromaticity in the microtopographical depressions, which were influenced by highly dynamic shallow groundwater levels, than in the flat forest soil. As a result of the frequent wet‐dry cycles in the upper soil layers, aromatic DOC accumulated in the shallow groundwater within and below the microtopographical depressions. Rising groundwater levels during precipitation events led to the connection of the microtopographical depressions to the stream, resulting in a change toward more aromatic DOC in the stream. Increasing stream DOC concentrations were accompanied by increasing concentrations of iron and aluminum, suggesting the coupled release of these metals with DOC from the riparian zone. Our results highlight the importance of the interplay between microtopography and groundwater level dynamics in the riparian zone for DOC export from headwater catchments.

Co‐occurrence of browning and oligotrophication in a boreal stream network

AbstractThe relative supply of carbon (C), nitrogen (N), and phosphorus (P) to freshwater ecosystems is of fundamental importance to aquatic productivity, nutrient cycling, and food web dynamics. In northern landscapes, ongoing climate change, as well as legacies from atmospheric deposition, have the potential to drive changes in how these elements are recycled on land and exported to streams. While it is well established that dissolved organic carbon (DOC) concentrations have increased in many high latitude streams, the simultaneous trends for N and P and the ratios among these resources, are not well documented. We used data from 13 sites in a boreal stream network to analyze decadal‐scale changes in dissolved inorganic N (DIN), dissolved organic N (DON), and dissolved inorganic P (DIP) concentrations and partition these trends seasonally. We observed widespread declines for DIP and DIN in streams, regardless of catchment characteristics. DIN decline was strongest during the growing season, and together with increases in DOC/DON at several sites, suggests increasing N retention by plants and soil microbes across this landscape. By contrast, declines for DIP occurred primarily during late autumn and winter, indicating that key biogeochemical changes are also occurring during non‐growing season. Linking these trends to increases in DOC concentration in streams revealed changes in the ratio of energy to nutrient supply for the majority of sites, becoming richer in carbon and poorer in limiting nutrients over time. Overall, our observations from this stream network point to ongoing oligotrophication, with possible consequences for aquatic ecosystems in boreal landscapes.

A systematic increase in the slope of the concentration discharge relation for dissolved organic carbon in a forested catchment in Vermont, USA

The production, mobilization and fluvial transport of dissolved organic carbon (DOC) in temperate forests are important components of the carbon cycle that are influenced by ongoing changes in climate. Numerous studies have reported temporal trends in stream water DOC concentrations and have attributed changes in concentrations to climatic and hydrologic variables. Fewer studies have reported trends in concentration-discharge (C-Q) relations for DOC. The goal of this study was to detect and quantify changes in DOC concentration and slope of the C-Q relation from 1991 to 2018 in an intensively sampled forested research watershed in northern Vermont. Stream water DOC concentration and slope of the C-Q relation increased over time as did precipitation, stream discharge, and air temperature. The increases in DOC concentration and slope of the C-Q were substantially greater in the summer and fall (autumn) than in winter and spring. The largest increases in the magnitude of C-Q slopes occurred in the December, October and September. The increases in slope of the C-Q relation in summer and fall were larger for baseflow than for storm flow. The increases in DOC concentration and slope of the C-Q relation over time may be related to increasing temperature, longer growing seasons, and associated increases in production and microbial decomposition of soil organic matter that supplies DOC for mobilization to streams. The results suggest that in a changing climate, C-Q relations may not necessarily be stationary and therefore analyses that attempt to estimate future DOC concentrations and loads should consider potentially changing C-Q relations over time.

Shifting stoichiometry: Long-term trends in stream-dissolved organic matter reveal altered C:N ratios due to history of atmospheric acid deposition.

Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past 50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long‐term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy‐nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by‐products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.

Low hydrological connectivity after summer drought inhibits DOC export in a forested headwater catchment

Abstract. Understanding the controls on event-driven dissolved organic carbon (DOC) export is crucial as DOC is an important link between the terrestrial and the aquatic carbon cycles. We hypothesized that topography is a key driver of DOC export in headwater catchments because it influences hydrological connectivity, which can inhibit or facilitate DOC mobilization. To test this hypothesis, we studied the mechanisms controlling DOC mobilization and export in the Große Ohe catchment, a forested headwater in a mid-elevation mountainous region in southeastern Germany. Discharge and stream DOC concentrations were measured at an interval of 15 min using in situ UV-Vis (ultraviolet–visible) spectrometry from June 2018 until October 2020 at two topographically contrasting subcatchments of the same stream. At the upper location (888 m above sea level, a.s.l.), the stream drains steep hillslopes, whereas, at the lower location (771 m a.s.l.), it drains a larger area, including a flat and wide riparian zone. We focus on four events with contrasting antecedent wetness conditions and event size. During the events, in-stream DOC concentrations increased up to 19 mg L−1 in comparison to 2–3 mg L−1 during baseflow. The concentration–discharge relationships exhibited pronounced but almost exclusively counterclockwise hysteresis loops which were generally wider in the lower catchment than in the upper catchment due to a delayed DOC mobilization in the flat riparian zone. The riparian zone released considerable amounts of DOC, which led to a DOC load up to 7.4 kg h−1. The DOC load increased with the total catchment wetness. We found a disproportionally high contribution to the total DOC export of the upper catchment during events following a long dry period. We attribute this to the low hydrological connectivity in the lower catchment during drought, which inhibited DOC mobilization, especially at the beginning of the events. Our data show that not only event size but also antecedent wetness conditions strongly influence the hydrological connectivity during events, leading to a varying contribution to DOC export of subcatchments, depending on topography. As the frequency of prolonged drought periods is predicted to increase, the relative contribution of different subcatchments to DOC export may change in the future when hydrological connectivity will be reduced more often.

Hydrological and catchment controls on event‐scale dissolved organic carbon dynamics in boreal headwater streams

AbstractHydrological events transport large proportions of annual or seasonal dissolved organic carbon (DOC) loads from catchments to streams. The timing, magnitude and intensity of these events are very sensitive to changes in temperature and precipitation patterns, particularly across the boreal region where snowpacks are declining and summer droughts are increasing. It is important to understand how landscape characteristics modulate event‐scale DOC dynamics in order to scale up predictions from sites across regions, and to understand how climatic changes will influence DOC dynamics across the boreal forest. The goal of this study was to assess variability in DOC concentrations in boreal headwater streams across catchments with varying physiographic characteristics (e.g., size, proportion of wetland) during a range of hydrological events (e.g., spring snowmelt, summer/fall storm events). From 2016 to 2017, continuous discharge and sub‐daily chemistry grab samples were collected from three adjacent study catchments located at the International Institute for Sustainable Development‐Experimental Lakes Area in northwestern Ontario, Canada. Catchment differences were more apparent in summer and fall events and less apparent during early spring melt events. Hysteresis analysis suggested that DOC sources were proximal to the stream for all events at a catchment dominated by a large wetland near the outlet, but distal from the stream at the catchments that lacked significant wetland coverage during the summer and fall. Wetland coverage also influenced responses of DOC export to antecedent moisture; at the wetland‐dominated catchment, there were consistent negative relationships between DOC concentrations and antecedent moisture, while at the catchments without large wetlands, the relationships were positive or not significant. These results emphasize the utility of sub‐daily sampling for inferring catchment DOC transport processes, and the importance of considering catchment‐specific factors when predicting event‐scale DOC behaviour.

Stream Water Chemistry in Mixed-Conifer Headwater Basins: Role of Water Sources, Seasonality, Watershed Characteristics, and Disturbances

Understanding the transport of dissolved organic carbon (DOC) and nitrogen (N) as water flows through headwater basins is important for predicting downstream water quality. With increased recognition of climatic impact on nutrient transport, more studies are needed in headwater basins experiencing a Mediterranean-type climate, such as those of the Sierra Nevada, California. We analyzed water samples collected over 5 years from eight low-order and mixed-conifer watersheds to elucidate the temporal variation of water chemistry and evaluate their responses to prolonged drought and low-intensity forest thinning. We observed higher stream DOC concentrations in October compared to other months within water years prior to drought and thinning, suggesting the importance of antecedent moisture conditions on seasonal C export. In unthinned watersheds, stream DOC concentrations were lower (62%) and DOC aromaticity was higher (68 and 92%, depending on the index used) during drought compared to non-drought years. In thinned watersheds during drought years, stream water had higher DOC concentrations (66–94% in three consecutive years following thinning) and dissolved inorganic N (24%, in the third year following thinning) compared to unthinned watersheds during drought. Additionally, lower stream DOC concentrations were found in watersheds with higher elevations and lower drainage densities in the year with near-average precipitation; however, these correlations were not significant in years with greater or extremely low precipitation. Taken together, our results suggest that stream concentrations of DOC and dissolved N in Mediterranean headwater basins are extremely variable over time due to the high temporal climatic variabilities and periodic management practices.

Effects of bedrock groundwater discharge on spatial variability of dissolved carbon, nitrogen, and phosphorous concentrations in stream water within a forest headwater catchment

AbstractThe quantitative evaluation of the effects of bedrock groundwater discharge on spatial variability of stream dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorous (DIP) concentrations has still been insufficient. We examined the relationships between stream DOC, DIN and DIP concentrations and bedrock groundwater contribution to stream water in forest headwater catchments in warm‐humid climate zones. We sampled stream water and bedrock springs at multiple points in September and December 2013 in a 5 km2 forest headwater catchment in Japan and sampled groundwater in soil layer in small hillslopes. We assumed that stream water consisted of four end members, groundwater in soil layer and three types of bedrock groundwater, and calculated the contributions of each end member to stream water from mineral‐derived solute concentrations. DOC, DIN and DIP concentrations in stream water were compared with the calculated bedrock groundwater contribution. The bedrock groundwater contribution had significant negative linear correlation with stream DOC concentration, no significant correlation with stream DIN concentration, and significant positive linear correlation with stream DIP concentration. These results highlighted the importance of bedrock groundwater discharge in establishing stream DOC and DIP concentrations. In addition, stream DOC and DIP concentrations were higher and lower, respectively, than those expected from end member mixing of groundwater in soil layer and bedrock springs. Spatial heterogeneity of DOC and DIP concentrations in groundwater and/or in‐stream DOC production and DIP uptake were the probable reasons for these discrepancies. Our results indicate that the relationships between spatial variability of stream DOC, DIN and DIP concentrations and bedrock groundwater contribution are useful for comparing the processes that affect stream DOC, DIN and DIP concentrations among catchments beyond the spatial heterogeneity of hydrological and biogeochemical processes within a catchment.

From Highs to Lows: Changes in Dissolved Organic Carbon in a Peatland Catchment and Lake Following Extreme Flow Events

The concentration of dissolved organic carbon (DOC) in freshwater catchments has implications for carbon availability in downstream lakes and for water supplies. The links between catchment hydrology and stream and lake DOC concentrations are, however, still not fully understood. Much of the literature has been from catchments with organo-mineral soils, with fewer studies from upland peat sites. We used high-frequency fluorescence data, a proxy for DOC, to investigate 1. the relationship between stream discharge and concentration in a blanket peat catchment during extreme high flows and 2. the relationship between inflow and in-lake estimated DOC concentrations. We found that for approximately two thirds of extreme events, there was a decrease in stream DOC concentration (i.e., a dilution) on the rising limb rather than an increase (i.e., a flushing out of DOC from terrestrial stores). Flushing events dominated only in summer when concentrations in the stream were also increasing. In comparison to the stream, concentrations in the downstream lake were less variable, and peaks and troughs were damped and lagged. Replicating these patterns and processes in DOC models would be critical in order to provide appropriate simulations in response to shorter- and longer-term changes in climate, and thus inform future catchment and lake management.

High-frequency analysis of dissolved organic carbon storm responses in headwater streams of contrasting forest harvest history

Dissolved organic carbon (DOC) in streams is critically important for aquatic ecosystems and human water use, and is affected by changes in land use and climate. The effects of land use change (e.g. forest harvest) on DOC are not fully understood. Past studies of the effects of forestry on DOC have found mixed results, and covariate effects complicate mechanistic understanding and may underlie regional differences. DOC is typically highest during storm events, and detailed time-resolved measurements of DOC over longer periods are just becoming feasible with advances in in situ sensors. In this paper, we investigated high frequency measurements of DOC concentration in headwater streams of contrasting forest harvest history in the UBC Malcolm Knapp Research Forest near Maple Ridge, British Columbia. We found base flow DOC concentration to be lower in the clear-cut stream (Clear cut: 2.26 ± 0.43 mg/L; Forested: 4.30 ± 0.83 mg/L). This may be due to reductions in carbon inputs like leaf litter, although the difference in drainage area, slope, and the presence of a bog lake in the forested catchment may also account for some of the observed difference. We found the DOC response to storms to be larger and faster at the clear-cut site (mean increase DOC: Clear-cut: 2.42 mg/L, Forested: 1.99 mg/L; mean rate of change DOC: Clear-cut: 0.16 mg/L/h, Forested: 0.11 mg/L/h). Elevated storm responses may be due to changes in flow paths related to forest harvesting. We found low antecedent flow and greater storm intensity to significantly predict elevated DOC storm response. This is important in the context of future climate scenarios, which predict lower summer flows and more intense storms in this region. Overall, this work contributes to our understanding of the intersection between effects of land use change and climate on water quality, with a focus on drinking water treatment implications.

Drivers of seasonal- and event-scale DOC dynamics at the outlet of mountainous peatlands revealed by high-frequency monitoring

Abstract. Peatlands store ∼ 20 %–30 % of the global soil organic carbon stock and are an important source of dissolved organic carbon (DOC) for inland waters. Recent improvements for in situ optical monitoring revealed that the DOC concentration in streams draining peatlands is highly variable, showing seasonal variation and short and intense DOC concentration peaks. This study aimed to statistically determine the variables driving stream DOC concentration variations at seasonal and event scales. Two mountainous peatlands (one fen and one bog) were monitored in the French Pyrenees to capture their outlet DOC concentration variability at a high-frequency rate (30 min). Abiotic variables including precipitation, stream temperature and water level, water table depth, and peat water temperature were also monitored at high frequency and used as potential predictors to explain DOC concentration variability. Results show that at both sites DOC concentration time series can be decomposed into a seasonal baseline interrupted by many short and intense peaks of higher concentrations. The DOC concentration baseline is driven, at the seasonal scale, by peat water temperature. At the event scale, DOC concentration increases are mostly driven by a rise in the water table within the peat at both sites. Univariate linear models between DOC concentration and peat water temperature or water table increases show greater efficiency at the fen site. Water recession times were derived from water level time series using master recession curve coefficients. They vary greatly between the two sites but also within one peatland site. They partly explain the differences between DOC dynamics in the studied peatlands, including peat porewater DOC concentrations and the links between stream DOC concentration and water table rise within the peatlands. This highlights that peatland complexes are composed of a mosaic of heterogeneous peat units distinctively producing or transferring DOC to streams.

Geologic Controls on Source Water Drive Baseflow Generation and Carbon Geochemistry: Evidence of Nonstationary Baseflow Sources Across Multiple Subwatersheds

AbstractThe contributions and composition of baseflow sources across an extended recession period were quantified for six subwatersheds of varying size in a structurally complex watershed in coastal California using endmember mixing analysis and related to catchment characteristics (e.g., topography, geology, land use, and soil characteristics). Both shallow subsurface and deep groundwater reservoirs were important contributors for streamflow during low flow periods, and the composition of baseflow sources across subwatersheds was directly related to geologic indices. A binary classification of underlying bedrock permeability (e.g., low vs. high) best explained the changes in shallow subsurface water and deeper groundwater inputs through the seasonal recession. Dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and specific UV absorbance at 254 nm (SUVA254) were used to provide additional insight into endmember characteristics and their contributions to baseflow. Stream water DIC concentrations were broadly controlled by mixing of groundwater and shallow subsurface water endmembers with relatively constant DIC concentrations, while stream water DOC concentrations reflected both spatial and temporal changes in shallow subsurface water DOC. Results from this study show (1) the importance of considering baseflow as a dynamic mixture of water from multiple sources, (2) the effect of geology on source composition at the subwatershed scale during low flow conditions, and (3) the impact of shifting baseflow sources on stream water dissolved carbon concentrations and the utility of using dissolved carbon concentrations to obtain additional insight into temporal variability in baseflow sources.

Influence of Dissolved Organic Matter Sources on In-Stream Net Dissolved Organic Carbon Uptake in a Mediterranean Stream

Studies exploring how different sources of dissolved organic matter (DOM) influence in-stream dissolved organic carbon (DOC) uptake at the ecosystem scale are scarce in the literature. To fill this knowledge gap, we examined the relationship between DOM sources and in-stream net DOC uptake (UDOC) in a sub-humid Mediterranean stream. We considered four reach-scale scenarios occurring under natural conditions that differed in predominant DOM sources (groundwater, leaf litter, and/or upstream water). Results showed that groundwater inputs favored in-stream net DOC uptake, while leaf litter inputs promoted in-stream net DOC release. However, there was no clear effect of DOM source mixing on the magnitude of UDOC. Further, the variability in UDOC within and among scenarios was mostly explained by stream DOC concentration, suggesting that DOC availability limits microbial activity in this stream. DOM composition became a controlling factor of UDOC variability only during the leaf litter period, when stream DOC concentration was the highest. Together, these results suggest that the capacity of headwater forested streams to process DOC is closely tied to the availability of different DOM sources and how they vary over time and along the river network.

The impact of lime additions on mercury dynamics in stream chemistry and macroinvertebrates: a comparison of watershed and direct stream addition management strategies.

Acid deposition has declined across eastern North America and northern Europe due to reduced emissions of sulfur and nitrogen oxides. Ecosystem recovery has been slow with limited improvement in surface water chemistry. Delayed recovery has encouraged acid-neutralization strategies to accelerate recovery of impaired biological communities. Lime application has been shown to increase pH and dissolved organic carbon (DOC), which could also drive increased mobilization of mercury (Hg) to surface waters. A four-year study was conducted within Honnedaga Lake's watershed in the Adirondack region of New York to compare the effects of watershed and direct channel lime additions on Hg in stream water and macroinvertebrates. All treatments sharply increased stream pH and DOC concentrations, but large differences in the duration of impacts were apparent. The watershed treatment resulted in multi-year increases in concentrations and loads of total Hg (150%; 390%), DOC (190%; 350%) and nutrients, whereas total Hg and DOC increased for short periods (72-96 h) after channel treatments. No response of Hg in macroinvertebrates was evident following the watershed treatment, but a potential short-term and spatially constrained increase occurred after the channel treatment. Our observations indicate that both treatment approaches mobilize Hg, but that direct channel liming mobilizes considerably less than watershed liming over any period longer than a few days. During the final study year, increased methyl Hg concentrations were observed across reference and treated streams, which may reflect an extended dry period, highlighting that climate variation may also affect Hg dynamics.

Temperature controls production but hydrology regulates export of dissolved organic carbon at the catchment scale

Abstract. Lateral carbon flux through river networks is an important and poorly understood component of the global carbon budget. This work investigates how temperature and hydrology control the production and export of dissolved organic carbon (DOC) in the Susquehanna Shale Hills Critical Zone Observatory in Pennsylvania, USA. Using field measurements of daily stream discharge, evapotranspiration, and stream DOC concentration, we calibrated the catchment-scale biogeochemical reactive transport model BioRT-Flux-PIHM (Biogeochemical Reactive Transport–Flux–Penn State Integrated Hydrologic Model, BFP), which met the satisfactory standard of a Nash–Sutcliffe efficiency (NSE) value greater than 0.5. We used the calibrated model to estimate and compare the daily DOC production rates (Rp; the sum of the local DOC production rates in individual grid cells) and export rate (Re; the product of the concentration and discharge at the stream outlet, or load). Results showed that daily Rp varied by less than an order of magnitude, primarily depending on seasonal temperature. In contrast, daily Re varied by more than 3 orders of magnitude and was strongly associated with variation in discharge and hydrological connectivity. In summer, high temperature and evapotranspiration dried and disconnected hillslopes from the stream, driving Rp to its maximum but Re to its minimum. During this period, the stream only exported DOC from the organic-poor groundwater and from organic-rich soil water in the swales bordering the stream. The DOC produced accumulated in hillslopes and was later flushed out during the wet and cold period (winter and spring) when Re peaked as the stream reconnected with uphill and Rp reached its minimum. The model reproduced the observed concentration–discharge (C–Q) relationship characterized by an unusual flushing–dilution pattern with maximum concentrations at intermediate discharge, indicating three end-members of source waters. A sensitivity analysis indicated that this nonlinearity was caused by shifts in the relative contribution of different source waters to the stream under different flow conditions. At low discharge, stream water reflected the chemistry of organic-poor groundwater; at intermediate discharge, stream water was dominated by the organic-rich soil water from swales; at high discharge, the stream reflected uphill soil water with an intermediate DOC concentration. This pattern persisted regardless of the DOC production rate as long as the contribution of deeper groundwater flow remained low (<18 % of the streamflow). When groundwater flow increased above 18 %, comparable amounts of groundwater and swale soil water mixed in the stream and masked the high DOC concentration from swales. In that case, the C–Q patterns switched to a flushing-only pattern with increasing DOC concentration at high discharge. These results depict a conceptual model that the catchment serves as a producer and storage reservoir for DOC under hot and dry conditions and transitions into a DOC exporter under wet and cold conditions. This study also illustrates how different controls on DOC production and export – temperature and hydrological flow paths, respectively – can create temporal asynchrony at the catchment scale. Future warming and increasing hydrological extremes could accentuate this asynchrony, with DOC production occurring primarily during dry periods and lateral export of DOC dominating in major storm events.