Marcus B. Wallin

Temporal and spatial variability of dissolved inorganic carbon in a boreal stream network: Concentrations and downstream fluxes

[1] Carbon dioxide (CO 2 ) and dissolved inorganic carbon (DIC) concentrations and export were analyzed throughout a 67 km 2 boreal stream network in northern Sweden. 700 DIC and CO 2 samples from 14 subcatchments were collected in 2006 and 2007. All sites were consistently supersaturated in CO 2 with respect to the atmosphere. Temporal variability of DIC and CO 2 concentration was best correlated with discharge, with concentrations generally diluting at high discharge. However, the variability in CO 2 concentration was also dependent on the specific pH range of the stream, as variability was greatest in acidic headwater streams and lowest in larger circumneutral streams. In the larger ones the increase in the CO 2 proportion of DIC at increased discharge counteracts the dilution of CO 2 . The shift toward proportionally more CO 2 of the DIC at higher discharge is caused by decline in pH. Spatial patterns showed that DIC and CO 2 concentrations were best correlated with peatland coverage of the subcatchment. The highest concentrations were found in headwater streams draining peatlands. The downstream export of DIC from the catchment outlet constitutes 19% of the total downstream export of carbon (DIC + DOC), or 0.7 (±0.09) g C m -2 yr -1 . This study demonstrates the importance of including fluvial fluxes of inorganic carbon in landscape carbon budgets via runoff, and also highlights the need to account for stream evasion of CO 2 to the atmosphere in such estimates since it can be larger than the downstream DIC export.

Representative regional sampling of carbon dioxide and methane concentrations in hemiboreal headwater streams reveal underestimates in less systematic approaches

Boreal headwater streams have been identified as hot spots for evasion of greenhouse gases (GHGs). This study was the first to systematically determine the concentrations of CO2 and CH4 in hemiboreal headwater streams. The use of a headspace sampling method focusing on GHGs in combination with a statistically representative selection of more than 200 streams across two regions in Sweden was the basis for defining the base flow concentrations of CO2 and CH4. All streams were supersaturated relative to the atmosphere in CO2 and the majority in CH4 for the 82% of streams in which CH4 was detected. The spatial variability in both CO2 and CH4 was high but positively related to total organic carbon, mean annual temperature, and proportion of peatland in the catchment. There were, however, regional differences in the spatial controls, which are something that predictive models need to consider. The data set allowed for comparison between a headspace and an alkalinity-based method for determining CO2. More than 50% of the streams contained no alkalinity which made the alkalinity-based determination of CO2 impossible. In addition, half of the streams with alkalinity had alkalinities low enough (<0.07 meq L−1) to make the CO2 determination very uncertain. The streams with low pH and no alkalinity contained median CO2 concentrations that were 45% higher than the streams containing alkalinity. Therefore, large-scale generalizations about CO2 in such headwaters will be significantly underestimated if (1) headwaters are underrepresented and (2) the headwaters are sampled but CO2 is calculated from their alkalinity.

Carbon dioxide evasion from headwater systems strongly contributes to the total export of carbon from a small boreal lake catchment

Inland waters are hotspots for carbon (C) cycling and therefore important for landscape C budgets. Small streams and lakes are particularly important; however, quantifying C fluxes is difficult and has rarely been done for the entire aquatic continuum, composed of connected streams and lakes within the same catchment. We investigated carbon dioxide (CO2) evasion and fluvial fluxes of dissolved inorganic carbon and dissolved organic carbon (DIC and DOC) in stream and lake systems within the 2.3 km2 catchment of a small boreal lake. Our results show pronounced spatial and temporal variability in C fluxes even at a small spatial scale. C loss from the catchment through CO2 evasion from headwaters for the total open water-sampling period was 9.7 g C m−2 catchment, dominating the total catchment C loss (including CO2 evasion, DIC, and DOC export from the lake, which were 2.7, 0.2, and 5.2 g C m−2 catchment, respectively). Aquatic CO2 evasion was dominated by headwater streams that occupy ~0.1% of the catchment but contributed 65% to the total aquatic CO2 evasion from the catchment. The importance of streams was mainly an effect of the higher gas transfer velocities than compared to lakes (median, 67 and 2.2 cm h−1, respectively). Accurately estimating the contribution of C fluxes from headwater streams, particularly the temporal and spatial dynamics in their gas transfer velocity, is key to landscape-scale C budgets. This study demonstrates that CO2 evasion from headwaters can be the major pathway of C loss from boreal catchments, even at a small spatial scale.

Large Carbon Dioxide Fluxes from Headwater Boreal and Sub-Boreal Streams

Half of the worlds forest is in boreal and sub-boreal ecozones, containing large carbon stores and fluxes. Carbon lost from headwater streams in these forests is underestimated. We apply a simple stable carbon isotope idea for quantifying the CO2 loss from these small streams; it is based only on in-stream samples and integrates over a significant distance upstream. We demonstrate that conventional methods of determining CO2 loss from streams necessarily underestimate the CO2 loss with results from two catchments. Dissolved carbon export from headwater catchments is similar to CO2 loss from stream surfaces. Most of the CO2 originating in high CO2 groundwaters has been lost before typical in-stream sampling occurs. In the Harp Lake catchment in Canada, headwater streams account for 10% of catchment net CO2 uptake. In the Krycklan catchment in Sweden, this more than doubles the CO2 loss from the catchment. Thus, even when corrected for aquatic CO2 loss measured by conventional methods, boreal and sub-boreal forest carbon budgets currently overestimate carbon sequestration on the landscape.

Temporal control on concentration, character, and export of dissolved organic carbon in two hemiboreal headwater streams draining contrasting catchments

Although lateral carbon (C) export from terrestrial to aquatic systems is known to be an important component in landscape C balances, most existing global studies are lacking empirical data on the soil C export. In this study, the concentration, character, and export of dissolved organic carbon (DOC) were studied during 2 years in two hemiboreal headwater streams draining catchments with different soil characteristics (mineral versus peat soils). The streams exposed surprisingly similar strong air temperature controls on the temporal variability in DOC concentration in spite of draining such different catchments. The temporal variability in DOC character (determined by absorbance metrics, specific ultraviolet absorbance 254 (SUVA254) as a proxy for aromaticity and a254/a365 ratio as a proxy for mean molecular weight) was more complex but related to stream discharge. While the two streams showed similar ranges and patterns in SUVA254, we found a significant difference in median a254/a354, suggesting differences in the DOC character. Both streams responded similarly to hydrological changes with higher a254/a365 at higher discharge, although with rather small differences in a254/a365 between base flow and high flow (<0.3). The DOC exports (9.6–25.2 g C m−2 yr−1) were among the highest reported so far for Scandinavia and displayed large interannual and intraannual variability mainly driven by irregular precipitation/discharge patterns. Our results show that air temperature and discharge affect the temporal variability in DOC quantity and character in different ways. This will have implications for the design of representative sampling programs, which in turn will affect the reliability of future estimates of landscape C budgets.

Evaluating a fast headspace method for measuring DIC and subsequent calculation of pCO2 in freshwater systems

Abstract A variety of different sampling and analysis methods are found in the literature for determining carbon dioxide (CO2) in freshwaters, methods that rarely have been evaluated or compared. Here we present an evaluation of an acidified headspace method (AHS) in which the dissolved inorganic carbon (DIC) is measured from an acidified sample and the partial pressure (pCO2) is calculated from DIC using pH and water temperature. We include information on practical sampling, accuracy, and precision of the DIC/pCO2 determination and a storage test of samples. The pCO2 determined from the AHS method is compared to that obtained from the more widely used direct headspace method (DHS) in which CO2 is equilibrated between the water and gas phases at ambient pH. The method was tested under both controlled laboratory conditions as well as wintertime field sampling. The accuracy of the DIC detection was on average 99% based on prepared standard solutions. The pCO2 determination in lab, using the DHS method as a reference, showed no significant difference, although the discrepancy between the methods was larger in samples with <1000 μatm. The precision of the pCO2 determination was on average ±4.3%, which was slightly better than the DHS method (±6.7%). In the field, the AHS method determined on average 10% higher pCO2 than the DHS method, which was explained by the extreme winter conditions (below −20 °C) at sampling that affected the sampling procedure of the DHS method. Although samples were acidified to pH 2, respiration processes were still occurring (at a low rate), and we recommend that analyses are conducted within 3 days from sampling. The AHS method was found to be a robust method to determine DIC and pCO2 in acidic to pH-neutral freshwater systems. The simple and quick sampling procedure makes the method suitable for time-limited sampling campaigns and sampling in cold climate.

Twelve-year interannual and seasonal variability of stream carbon export from a boreal peatland catchment

Understanding stream carbon export dynamics is needed to accurately predict how the carbon balance of peatland catchments will respond to climatic and environmental change. We used a 12year record ...

Decoupling of carbon dioxide and dissolved organic carbon in boreal headwater streams

Streams and rivers emit large quantities of carbon dioxide (CO2) to the atmosphere. The sources of this CO2 are in-stream mineralization of organic carbon (OC) and CO2 input via groundwater inflow but their relative importance is largely unknown. In this study, we quantified the role of in-stream OC mineralization as a source of CO2 in a number of nested boreal headwater streams. The results showed that mineralization of stream OC contributed 3% of CO2 supersaturation at timescales comparable to the estimated water travel times in the streams (<24 hours). Mass balances showed that downstream losses of OC were ≤3% in low order streams whereas up to 16% of the OC was lost in the largest (4th order) streams. In contrast, 85% of the CO2 was lost along the stream network (longest total stream length = 17 km). Under the assumption that in-stream OC mineralization was the main source of stream CO2, higher rates of OC mineralization (6% of OC) than those reported across the literature (≤0.7% of OC) would be required to sustain observed CO2 supersaturation. Further, model results indicated that groundwater inflows were sufficient to sustain observed stream CO2 concentrations. We hence conclude that in-stream OC mineralization was a minor source of CO2 in these boreal headwater systems and that the main source of stream CO2 was inflowing groundwater transporting CO2 originating from soil respiration.

Spatio-temporal patterns of stream methane and carbon dioxide emissions in a hemiboreal catchment in Southwest Sweden

Global stream and river greenhouse gas emissions seem to be as large as the oceanic C uptake. However, stream and river emissions are uncertain until both spatial and temporal variability have been quantified. Here we investigated in detail the stream CH4 and CO2 emissions within a hemiboreal catchment in Southwest Sweden primarily covered by coniferous forest. Gas transfer velocities (k600), CH4 and CO2 concentrations were measured with multiple methods. Our data supported modelling approaches accounting for various stream slopes, water velocities and discharge. The results revealed large but partially predictable spatio-temporal variabilities in k600, dissolved gas concentrations, and emissions. The variability in CO2 emission was best explained by the variability in k, while dissolved CH4 concentrations explained most of the variability in CH4 emission, having implications for future measurements. There were disproportionately large emissions from high slope stream reaches including waterfalls, and from high discharge events. In the catchment, stream reaches with low slope and time periods of moderate discharge dominated (90% of area and 69% of time). Measurements in these stream areas and time periods only accounted for <36% of the total estimated emissions. Hence, not accounting for local or episodic high emissions can lead to substantially underestimated emissions.

Multiple sources and sinks of dissolved inorganic carbon across Swedish streams, refocusing the lens of stable C isotopes

It is well established that stream dissolved inorganic carbon (DIC) fluxes play a central role in the global C cycle, yet the sources of stream DIC remain to a large extent unresolved. Here, we explore large-scale patterns in δ13C-DIC from streams across Sweden to separate and further quantify the sources and sinks of stream DIC. We found that stream DIC is governed by a variety of sources and sinks including biogenic and geogenic sources, CO2 evasion, as well as in-stream processes. Although soil respiration was the main source of DIC across all streams, a geogenic DIC influence was identified in the northernmost region. All streams were affected by various degrees of atmospheric CO2 evasion, but residual variance in δ13C-DIC also indicated a significant influence of in-stream metabolism and anaerobic processes. Due to those multiple sources and sinks, we emphasize that simply quantifying aquatic DIC fluxes will not be sufficient to characterise their role in the global C cycle.