Peatland pools are tightly coupled to the contemporary carbon cycle.

Peatlands are globally important stores of soil carbon (C) formed over millennial timescales but are at risk of destabilization by human and climate disturbance. Pools are ubiquitous features of many peatlands and can contain very high concentrations of C mobilized in dissolved and particulate organic form and as the greenhouses gases carbon dioxide (CO2 ) and methane (CH4 ). The radiocarbon content (14 C) of these aquatic C forms tells us whether pool C is generated by contemporary primary production or from destabilized C released from deep peat layers where it was previously stored for millennia. We present novel 14 C and stable C (δ13 C) isotope data from 97 aquatic samples across six peatland pool locations in the United Kingdom with a focus on dissolved and particulate organic C and dissolved CO2 . Our observations cover two distinct pool types: natural peatland pools and those formed by ditch blocking efforts to rewet peatlands (restoration pools). The pools were dominated by contemporary C, with the majority of C (~50%-75%) in all forms being younger than 300 years old. Both pool types readily transform and decompose organic C in the water column and emit CO2 to the atmosphere, though mixing with the atmosphere and subsequent CO2 emissions was more evident in natural pools. Our results show little evidence of destabilization of deep, old C in natural or restoration pools, despite the presence of substantial millennial-aged C in the surrounding peat. One possible exception is CH4 ebullition (bubbling), with our observations showing that millennial-aged C can be emitted from peatland pools via this pathway. Our results suggest that restoration pools formed by ditch blocking are effective at preventing the release of deep, old C from rewetted peatlands via aquatic export.

Aquatic export of young dissolved and gaseous carbon from a pristine boreal fen: Implications for peat carbon stock stability.

The stability of northern peatland's carbon (C) store under changing climate is of major concern for the global C cycle. The aquatic export of C from boreal peatlands is recognized as both a critical pathway for the remobilization of peat C stocks as well as a major component of the net ecosystem C balance (NECB). Here, we present a full year characterization of radiocarbon content (14 C) of dissolved organic carbon (DOC), carbon dioxide (CO2 ), and methane (CH4 ) exported from a boreal peatland catchment coupled with 14 C characterization of the catchment's peat profile of the same C species. The age of aquatic C in runoff varied little throughout the year and appeared to be sustained by recently fixed C from the atmosphere (<60 years), despite stream DOC, CO2 , and CH4 primarily being sourced from deep peat horizons (2-4 m) near the mire's outlet. In fact, the 14 C content of DOC, CO2 , and CH4 across the entire peat profile was considerably enriched with postbomb C compared with the solid peat material. Overall, our results demonstrate little to no mobilization of ancient C stocks from this boreal peatland and a relatively large resilience of the source of aquatic C export to forecasted hydroclimatic changes.

Ancient dissolved methane in inland waters revealed by a new collection method at low field concentrations for radiocarbon (14C) analysis.

Methane (CH4) is a powerful greenhouse gas that plays a prominent role in the terrestrial carbon (C) cycle, and is released to the atmosphere from freshwater systems in numerous biomes globally. Radiocarbon (14C) analysis can indicate both the age and source of CH4 in natural environments. In contrast to CH4 present in bubbles released from aquatic sediments (ebullition), dissolved CH4 in lakes and streams can be present in low concentrations compared to carbon dioxide (CO2), and therefore obtaining sufficient aquatic CH4 for radiocarbon (14C) analysis remains a major technical challenge. Previous studies have shown that freshwater CH4, in both dissolved and ebullitive form, can be significantly older than other forms of aquatic C, and it is therefore important to characterise this part of the terrestrial C balance. This study presents a novel method to capture sufficient amounts of dissolved CH4 for 14C analysis in freshwater environments by circulating water across a hydrophobic, gas-permeable membrane and collecting the CH4 in a large headspace volume. The results of laboratory and field tests show that reliable dissolved δ13CH4 and 14CH4 samples can be readily collected over short time periods (∼4-24 h), at relatively low cost and from a variety of surface water types. The initial results further support previous findings that dissolved CH4 may be significantly older than other forms of aquatic C, and is currently unaccounted for in many terrestrial C balances and models. This method is suitable for use in remote locations, and could potentially be used to detect the leakage of unique 14CH4 signatures from point sources into waterways, e.g. coal seam gas and landfill gas.

Regional variation in the biogeochemical and physical characteristics of natural peatland pools.

Natural open-water pools are a common feature of northern peatlands and are known to be an important source of atmospheric methane (CH4). Pool environmental variables, particularly water chemistry, vegetation community and physical characteristics, have the potential to exert strong controls on carbon cycling in pools. A total of 66 peatland pools were studied across three regions of the UK (northern Scotland, south-west Scotland, and Northern Ireland). We found that within-region variability of pool water chemistry was low; however, for many pool variables measured there were significant differences between regions. PCA analysis showed that pools in SW Scotland were strongly associated with greater vegetative cover and shallower water depth which is likely to increase dissolved organic carbon (DOC) mineralisation rates, whereas pools in N Scotland were more open and deeper. Pool water DOC, particulate organic carbon and dissolved CH4 concentrations were significantly different between regions. Pools in Northern Ireland had the highest concentrations of DOC (mean=14.5 mg L(-1)) and CH4 (mean=20.6 µg C L(-1)). Chloride and sulphate concentrations were significantly higher in the pools in N Scotland (mean values 26.3 and 2.40 mg L(-1), respectively) than elsewhere, due to a stronger marine influence. The ratio of UV absorbance at 465 nm to absorbance at 665 nm for pools in Northern Ireland indicated that DOC was sourced from poorly humified peat, potentially increasing the bioavailability and mineralisation of organic carbon in pools compared to the pools elsewhere. This study, which specifically aims to address a lack of basic biogeochemical knowledge about pool water chemistry, clearly shows that peatland pools are highly regionally variable. This is likely to be a reflection of significant regional-scale differences in peatland C cycling.

Biogeochemistry of "pristine" freshwater stream and lake systems in the western Canadian Arctic.

Climate change poses a substantial threat to the stability of the Arctic terrestrial carbon (C) pool as warmer air temperatures thaw permafrost and deepen the seasonally-thawed active layer of soils and sediments. Enhanced water flow through this layer may accelerate the transport of C and major cations and anions to streams and lakes. These act as important conduits and reactors for dissolved C within the terrestrial C cycle. It is important for studies to consider these processes in small headwater catchments, which have been identified as hotspots of rapid mineralisation of C sourced from ancient permafrost thaw. In order to better understand the role of inland waters in terrestrial C cycling we characterised the biogeochemistry of the freshwater systems in a c. 14 km2 study area in the western Canadian Arctic. Sampling took place during the snow-free seasons of 2013 and 2014 for major inorganic solutes, dissolved organic and inorganic C (DOC and DIC, respectively), carbon dioxide (CO2) and methane (CH4) concentrations from three water type groups: lakes, polygonal pools and streams. These groups displayed differing biogeochemical signatures, indicative of contrasting biogeochemical controls. However, none of the groups showed strong signals of enhanced permafrost thaw during the study seasons. The mean annual air temperature in the region has increased by more than 2.5 °C since 1970, and continued warming will likely affect the aquatic biogeochemistry. This study provides important baseline data for comparison with future studies in a warming Arctic.

Annual variability in the radiocarbon age and source of dissolved CO2 in a peatland stream.

Radiocarbon dating has the capacity to significantly improve our understanding of the aquatic carbon cycle. In this study we used a new passive sampler to measure the radiocarbon ((14)C) and stable carbon (δ(13)C) isotopic composition of dissolved CO(2) for the first time in a peatland stream throughout a complete year (May 2010-June 2011). The in-stream sampling system collected time-integrated samples of CO(2) continuously over approximately 1 month periods. The rate of CO(2) trapping was proportional to independently measured streamwater CO(2) concentrations, demonstrating that passive samplers can be used to estimate the time-averaged dissolved CO(2) concentration of streamwater. While there was little variation and no clear trend in δ(13)CO(2) values (suggesting a consistent CO(2) source), we found a clear temporal pattern in the (14)C concentration of dissolved CO(2). The (14)C age of CO(2) varied from 707±35 to 1210±39 years BP, with the youngest CO(2) in the autumn and oldest in spring/early summer. Mean stream discharge and (14)C content of dissolved CO(2) were positively correlated. We suggest that the observed pattern in the (14)C content of dissolved CO(2) reflects changes in its origin, with older carbon derived from deeper parts of the peat profile contributing proportionally more gaseous carbon during periods of low stream flow.

Stream water hydrochemistry as an indicator of carbon flow paths in Finnish peatland catchments during a spring snowmelt event.

Extreme hydrological events are known to contribute significantly to total annual carbon export, the largest of which in Arctic and boreal catchments is spring snowmelt. Whilst previous work has quantified the export of carbon during snowmelt, the source of the carbon remains unclear. Here we use cation hydrochemistry to trace the primary flowpaths which govern the export of carbon during the snowmelt period; specifically we aim to examine the importance of snowpack meltwater to catchment carbon export. The study was carried out in two forested peatland (drained and undrained) catchments in Eastern Finland. Both catchments were characterised by base-poor stream water chemistry, with cation concentrations generally decreasing in response to increasing discharge. Streamflow during the snowmelt period was best described as a mixture of three sources: pre-event water, snowpack meltwater and a third dilute component we attribute to the upper snow layer which was chemically similar to recent precipitation. Over the study period, pre-event water contributed 32% and 43% of the total stream runoff in Välipuro (undrained) and Suopuro (drained), respectively. The results also suggest a greater near-surface throughflow component in Suopuro, the drained catchment, prior to snowmelt. CO(2) and DOC concentrations correlated positively with cation concentrations in both catchments indicating a common, peat/groundwater flowpath. CH(4) concentrations were significantly higher in the drained catchment and appeared to be transported in near-surface throughflow. Meltwater from the snowpack represented an important source of stream water CO(2) in both catchments, contributing up to 49% of total downstream CO(2) export during the study period. We conclude that the snowpack represents a potentially important, and often overlooked, transient carbon store in boreal snow-covered catchments.