INFLUENCE OF SOIL PROFILE PROPERTIES ON RESPIRED CARBON DIOXIDE (CO2) AND METHANE (CH4) GASES BEFORE, DURING, AND AFTER DISTURBANCE BY A RETROGRESSIVE THAW SLUMP ALONG THE SELAWIK RIVER, NW ALASKA. by Amy E. Jensen A thesis submitted in partial fulfillment of the requirements for the degree of Masters of Science in Geology Idaho State University In presenting this thesis in partial fulfillment of the requirements for an advanced degree at Idaho State University, I agree that the Library shall make it freely available for inspection. I further state that permission for copying of my thesis for scholarly purposes may be granted by the Dean of Graduate Studies, Dean of my academic division, or by the University Librarian. It is understood that any copying or publication of this thesis for financial gain shall not be allowed without my written permission. Signature______________________________________ Date__________________________________________ To the Graduate Faculty: The members of the committee appointed to examine the thesis of Amy E. Jensen find it satisfactory and recommend that it be accepted. _________________________________________ Benjamin T. Crosby, Principal Advisor _________________________________________ Kathleen A. Lohse, Second Advisor _________________________________________ Keith Reinhardt, Graduate Faculty Representative iii Acknowledgements Margaret Murnane this is for you! Without your love, devotion, dedication, support and unwavering ability to hold me accountable, I would have never become the person I am today. You give more than a ton, and truly you’re the glue that holds our crazy family together! To the rest of my family, you all are without a doubt both the best and strangest things in my life. Thank you for all your love and support couldn’t have done this without all the laughs, distractions, and encouragement from you all, I love you bunches! Ben Crosby, where do I even begin? Thanks for sharing your person, family, and dance with me you all are good weird, and I’ve enjoyed myself immensely with you all! Alaska, what a life experience, thank you so much for allowing me to work with you on such amazing research in such a gorgeous place! You’ve given a lot of yourself in my pursuit of these ~100 pages and I hope I’ve managed to take most of it in! Ben Abbott, thank you for all your insight and willingness to share your expertise. Without your help and guidance I would have been utterly lost. Kathleen Lohse, you’re the women: an amazing person and scientist! Thank you for all the time and effort you committed to me. Your insight and guidance have not only shaped this project into a story with teeth, grit, and importance, but you’ve also given me great confidence in my ability as a scientist, and for that I will be forever grateful. It’s all about the SOILS! Claudia Mora, thank you so much for all your time and influence! You are an incredible person and scientist! Thank you so much for such an amazing project to work on! You have opened my eyes to how effective science is conducted. Joel Rowland, thank you for the use of your meterological data for chapter 2. Sara Godsey, thank you so much for all the statistical help you provided on this project. Keith Reinhardt, thank you for the willingness to sit on my iv committee! To all my fellow students and friends, BOOM, without you all my headspace would have been an utter mess! This research received financial and logistic support from the Los Alamos National Energy Lab (LANL IGPP Minigrant 166259), the Selawik National Wildlife Refuge (USFWS – CESU 84320-9-J306R) as well as financial support from the NSF’s Arctic System Science (ARCSS) Program (OPP – 0806399) and the NSF Idaho EPSCoR Program in Water Resources in a Changing Climate (EPS 0814387). v Table of Contents List of Figures……………………………………………………………….…………. viii List of Tables……………………………………………………………….………...... ix Abstract……………………………………………………………………….………… x 1 Introduction 1 1.1 Motivation 1 1.1.1 Thermokarst 2 1.1.2 Soil Organic Carbon 3 1.1.3 Soil Properties and Structure 4 1.1.4 Carbon Dioxide Efflux 5 1.1.5 Controls on CO2 Efflux 7 1.1.6 δ13C of Soil Respired CO2 8 1.2 Thesis Objective 10 1.3 Thesis Structure 10 1.4 References 12 2 Soil properties affect variations in carbon dioxide efflux across a retrogressive thaw slump chronosequence in northwest Alaska. 15 2.1 Abstract 15 2.2 Introduction 16 2.3 Field Setting 19 2.4 Study Deisgn: a chronosequence enables a space for time substitution 20 2.5 Methods 22 2.5.1 Meteorology 22 2.5.2 Point measurements of CO2 Efflux, Soil Temperature, Soil Moisture 22 2.5.3 Physical Soil Properties 23 2.5.4 Statistical Analysis 24 2.6 Environmental Conditions over Space and Time 25 2.6.1 Precipitation 25 2.6.2 Air Temperature 25 2.6.3 Soil Temperature 25 2.6.4 Soil Moisture 26 2.6.5 Physical Soil Properties 27 2.7 CO2 Efflux over Space and Time 2.7.1 Controls Affecting CO2 Efflux vi 28 30 2.8 Implications 32 2.9 Conclusion 33 2.10 References 34 2.11 Figures 37 3 Soil matters: Vertical profiles of CO2 and CH4 concentrations and δ13C of CO2 respired from a thaw slump chronosequence reveal that soil properties can control carbon efflux at the surface. 44 3.1 Abstract 44 3.2 Introduction 45 3.3 Field Setting 49 3.4 Thaw slump chronosequence: a space for time substitution 50 3.5 Methods 53 3.5.1 Sampling Locations 53 3.5.2 Soil Analysis 53 3.5.3 Soil Gas Analysis 55 3.5.4 Statistical Analysis 56 3.6 Results 57 3.6.1 Physical Soil Properties 57 3.6.2 Soil Gas CO2 and CH4 Concentrations 59 3.6.3 Stable Isotopic Composition of Soil and Soil Gases 13 3.6.4 Controls on Gas Concentrations and δ C Isotope Values 3.7 4 5 Discussion 60 61 62 3.7.1 Diffusion Limitation 62 3.7.2 Micro-Soil Environments 64 3.8 Implications 66 3.9 Conclusion 68 3.10 Reference 69 3.11 Figures 75 Thesis Summary 79 4.1 Implications 79 4.2 Conclusion 80 Supplemental Material 82 vii List of Figures Chapter 2 Figure 1. Field area location, chronosequence selection………………………….…….36 Figure 2. Day-of-year time series of environmental variables for 2011 and 2012…….. 38 Figure 3. Mean peak growing season soil temperature, moisture and CO2 efflux…….. 39 Figure 4. Soil moisture and temperature controls on CO2 efflux………………....….... 41 Figure 5. Physical soil property controls on CO2 efflux…………...…………………... 42 Chapter 3 Figure 1. Field area location, topographic cross-sections, soil profiles…….………….. 73 Figure 2. Soil profiles physical properties…………………………………..…………. 74 Figure 3. Soil profiles carbon concentration and isotopes…………………………..…. 76 Supplemental Material Figure 1. Soil Profile Photographs................................................................................... 80 viii List of Tables Chapter 2 Table 1. Summary ANOVA value table................................…………….……….…… 37 Table 2. Chronosequence soil and vegetation characteristics…………….……….…… 37 Table 3. Comparisons of CO2 efflux……………………………………………..…….. 40 Chapter 3 Table 1. Comparisons of CO2 efflux and effective diffusivity…….……………….….. 75 Table 2. Controls on CO2, CH4 concentrations, and δ13C of CO2……………………... 75 ix Abstract Warming of the arctic landscape results in permafrost thaw, which causes ground subsidence or thermokarst. On hillslopes, this process is accelerated, altering soil structure, temperature, moisture, as well as the content and quality of soil organic matter. In turn, these changes affect both the rate and mechanism of carbon cycling in permafrost soils. This is a major concern because permafrost soils store nearly half the world’s global carbon. In order to assess the time-evolution of carbon contributions from thermokarst features, we use a three-stage chronosequence of thaw slumps to describe how carbon dioxide (CO2) fluxes from undisturbed, active and stabilized surfaces differ. We then evaluate the fate of carbon within the above three environments, using a soilprofile chronosequence to determine how thermokarst-driven changes in the soil microenvironment affect soil column CO2 and CH4 concentrations as well as the resulting CO2 efflux. The study site, found along the Selawik River in northwest Alaska, contains one of the largest active retrogressive thaw slumps known in North America and had a surface area of ~50,000 m2 in 2012. We designate the undisturbed tundra as the initial condition and an adjacent, bowl-like depression re-vegetated by multiple generations of black spruce trees as a stabilized slump. In this 2-year study, we use peak summer measurements of CO2 efflux across the chronosequence, as well as, soil profile CO2 and CH4 concentrations, soil profile δ13C of both soil respired CO2 and soil organic matter. Physical soil parameters such as temperature, moisture, soil organic carbon %, porosity and water filled pore space at are measured at depths of 3, 5, 15, 30, and 50cm, to determine how carbon emissions are affected by changes within the soil environment resulting from the initiation and x subsequent stabilization of a rapidly evolving thaw slump. CO2 efflux from the active slump is less than half that from either the undisturbed tundra or stabilized slump. While the active slump had the lowest CO2 surface efflux, at depth the CO2 concentrations were 5 orders of magnitude higher than those observed in the other two environments. CH4 concentrations in the active slump were ~3x higher. Although the floor of the active slump is generally 10 to 15°C warmer than the tundra and stabilized slump, we did not observe that soil temperature or moisture exerts a strong control on CO2 efflux. Rather, we found that local physical soil properties such as low porosity, high water filled pore space, and low calculated effective diffusivity in the active slump inhibit CO2 efflux. In contrast to our expectation that the active slump would be primarily aerobic due to landscape position (riverbanks with slopes of 10-25%), observations of soil gleying, heavier δ13C of CO2 (~-15‰), and the production of methane all point to anaerobic soil conditions, suggesting a switch in the metabolic pathway toward methanogenesis. This suggests that though thaw slumps can profoundly alter the biophysical controls on CO2 and CH4 production, the dilution of organic soils by glacial sediment as well as changes in physical soil profile properties in the active feature reduced CO2 efflux below those measured in the undisturbed tundra. As the feature matures and is recolonized as a boreal forest ecosystem, fluxes return toward initial conditions. Catastrophic thermokarst features are likely to increase frequency and extent in a changing climate. Future studies will need to assess whether other thermokarst features with higher organic content substrates respond similarly to these evolving landscape features. xi 1 Introduction 1.1 Motivation Arctic ecosystems are presently experiencing unprecedented climate warming, which dramatically alters topography, soil structure and function, carbon storage, water balance, and carbon emissions. This introduction first examines past and current work on geomorphic changes associated with permafrost thaw and carbon emissions as a result of permafrost degradation. Second, changes in physical soil properties including soil temperature and moisture as well as substrate quality are examined as controls on carbon gas emissions and isotopic values. Third, this chapter discusses how changes in soil properties with depth, such as bulk density, porosity, soil organic matter, soil temperature, and soil moisture may influence carbon-cycling. International research has clearly documented a warming climate in Arctic ecosystems (IPCC, 2007). Since the Little Ice Age, defined as the period between the 16th and 19th centuries, mean temperatures in the Arctic have risen by 3 -5 °C (ACIA, 2004; IPCC, 2007). Within Alaska mean temperature has risen by 1 -3 °C in the last three decades (Hinzman et al., 2005). Results from general circulation models differ somewhat regarding future trends, but models and scenarios selected for the Arctic Climate Impact Assessment (2004) agree that, by 2100, average annual temperatures in the Arctic are expected to increase 3-5°C and winter temperatures may increase by 4-7°C. These models also suggest that rising temperatures will be accompanied by increased precipitation, mostly in the form of rain (IPCC, 2007). 1 1.1.1 Thermokarst A warming climate will have important consequences for arctic ecosystems. One major impact is permafrost thaw and subsequent formation of thermokarst terrain. Permafrost is defined as soil or rock that remains at or below 0°C for 2 or more consecutive years (Jorgenson and Osterkamp, 2005). Found just above the permafrost, the active layer is defined as the uppermost layer of soils (~0.4 – 2m thick) which thaws during the summer and freezes again during the autumn (Jorgenson et al., 2008b). As a consequence of permafrost thaw the land-surface subsides, resulting in surface subsidence (thermokarst) and/or mass wasting (thermal erosion feature) (Jorgenson et al., 2010; Rowland et al., 2010). There are many types of thermokarst features. Formation of these features depends on the amount and type of ground ice as well as the geomorphic surface characteristics. This review focuses on a type of thermal erosional features called retrogressive thaw slumps (Jorgenson et al., 2008b). These features initiate when permafrost thaw extends beyond the base of the active layer, resulting in a thick, supersaturated, soil column typically resting on the top of a weakly cohesive layer of ice. This supersaturated soil detaches and the entire active layer (vegetation, peat, inorganic sediments, etc.) begins to flow downhill. Once the active layer has been stripped off the surface, the exposed permafrost thaws rapidly, forming gullies that focus surface overflow and erosive energy into a small network of channels that thaw and transport sediments downslope. The gullies erode both vertically and headward, generating a distinctive arcuate depression, whose edge is defined by a headwall that delineates the boundary between the thermokarst feature and the stable frozen ground. In a 2 retrogressive thaw slump, new material is supplied by the continued thawing of permafrost and subsequent soil instability in the headwall of the feature (Jorgenson et al., 2008a). Thermokarst features cause fundamental alterations in the physical and ecological processes within arctic ecosystems. These changes include, but are not limited to: mass wasting of soils, re-organization of soil profiles, changes in surface albedo, decreases in soil pore ice, exposure of carbon and nutrient pools contained within frozen soils, increased carbon release to the atmosphere, temperature profiles, soil moisture changes, as well as changes in vegetation, hydrology, and topography (Jorgenson and Osterkamp, 2005). 1.1.2 Soil Organic Carbon Permafrost affected soils and peatlands in the arctic typically function as sinks for soil organic carbon (SOC), due to the slow decomposition rates of litter input, and increased retention/storage rates within the ecosystem (Grosse et al., 2011). Stabilization of soil organic matter is determined by the interaction of cold temperatures, permafrost, saturation, and substrate quality. However, the importance of these factors in the global carbon budget and how they will respond to a changing climate are poorly understood (Hobbie et al., 2000; Tarnocai, 2009). Thawing permafrost and subsequent thermokarst development has caused arctic SOC pools to become more available for microbial decomposition, thus leading to an increase in the production and emission of the greenhouse gases, carbon dioxide (CO2) and methane (CH4) to the atmosphere (Rowland et al., 2010). Many workers have attributed increased decomposition rates to altered soil properties, such as increased temperature and soil moisture, as a result of ecosystem 3 changes due to thermokarst development (Lee et al., 2011; Michaelson and Ping, 2003; Michaelson et al., 2011). Stieglitz et al. (2000) suggested that drier conditions in the arctic would increase aerobic soil decomposition, increasing CO2 efflux, leading to a net ecosystem loss of carbon to the atmosphere. In contrast, cooler and moister conditions result in slower anaerobic decomposition, resulting in overall ecosystem carbon sequestration (Stieglitz et al., 2000). 1.1.3 Soil Properties and Structure At a local scale, it is poorly understood how thermokarst-driven changes in soil properties and structure will affect carbon emissions. Organic soils (peatlands) and cryoturbated permafrost-affected mineral soils have the highest mean soil organic carbon contents: 32.2 – 69.6 kg m-2 (Tarnocai, 2009). Thermal erosion features disturb, and rework arctic soils, increasing the availability of soil organic matter for microbes to decompose, leading to an increase in soil respiration (Schuur et al., 2008). Carbon emission from soil can take the form of either carbon dioxide (CO2) or methane (CH4). Saturated, low-oxygenated environments (anaerobic conditions) are likely to contain microbes that reduce CO2 to CH4, through the processes of methanogenesis, which has 25 times more potential to warm the atmosphere than CO2 (Schuur and Abbott, 2011). Conversely in drier, warmer environments (aerobic conditions), soil respiration results in the release of CO2. Experimental incubations of permafrost soils over a 500 day period at 15°C showed a 3.9-10.0 times greater CO2 release under aerobic rather than anaerobic soil conditions (Lee et al., 2012). Deep permafrost mineral soils have also been shown to release similar amounts of carbon as organic soils for some soil types when compared on 4 a per gram carbon basis (Lee et al., 2012). These findings suggest that permafrost carbon may be very labile, but significant differences exist across soil types. 1.1.4 Carbon Dioxide Efflux Carbon dioxide efflux is primarily a product of heterotrophic respiration within the soil environment. CO2 efflux is a product of microbial processes and passes through soil to the atmosphere following Fick’s law of diffusion. CO2 concentrations vary as a function of soil depth and are dependent on production and consumption rates in the case of anaerobic soils and the diffusive ability of the soil profile (Amundson and Davidson, 1990). Controls on the release of CO2 within the soil profile can be contributed to physical soil properties, soil organic matter content, temperature, and moisture (Amundson and Davidson, 1990). For example, increased soil organic matter quality coupled with increased soil temperature results in higher soil CO2 efflux. Carbon isotope values, which are the ratio of 13C/12C relative to Vienna Pee Dee Belemnit (VPDB) standard, represented as δ13C, also vary as a function of depth, which is a function of soil organic matter decomposition and interactions with atmospheric CO2. The factors controlling δ13C soil profiles are complex but many models suggest that these profiles, in part, are controlled by decomposing organic matter, the difference in 12C and 13C diffusion coefficients, and the rate at which CO2 is produced by biological activity within the soil (Amundson and Davidson, 1990). It has been noted by numerous studies that CO2 concentrations in the soil increase with depth due to atmospheric mixing at the surface to values dependent upon the production rate (Amundson and Davidson, 1990; Amundson et al., 1998; Shanhun et al., 2012). While δ13C values decrease from atmospheric values (-8‰) near the surface to values approaching that of the decomposing 5 organic matter/root respiration with increasing depth (-27‰) (Amundson and Davidson, 1990; Amundson et al., 1998; Shanhun et al., 2012). Rates of CO2 release from thermal erosional features have been estimated by numerous studies using both continuous and random measurements of CO2 efflux. (Lee et al., 2011; Lee et al., 2010; Schuur et al., 2009; Vogel et al., 2008a). Overall, the terrestrial ecosystems of northern regions are a net source of carbon to the atmosphere at 276 Tg C yr-1 (Tarnocai, 2009). Given current warming trends, it is projected that the arctic regions will remain a net source of carbon, and could possibly double carbon released to the atmosphere, to 473 Tg C yr-1 in the next 30 years (Zhuang et al., 2006). At present, the carbon contribution from thermokarst features to the projected increase in carbon release is poorly quantified. Detailed studies of thermokarst carbon cycling and efflux have been conducted with varying results. Lee et al. (2010) found that for thermokarst features, CO2 release to the atmosphere averaged between 177 to 270 g CO2- C m-2 per year over a three year period. These rates were least in the least-disturbed, moist, acidic tundra soils and greatest where thawing of permafrost and thermokarst formation was most pronounced. Over half of the variability in CO2 production for this study was explained by surface subsidence, soil temperature, and site differences. Schuur et al. (2009) examined thermokarst CO2 respiration along a thaw gradient, and found that on an annual basis the extensive thaw site had significantly higher CO2 efflux, with greater total CO2 loss than the minimal thaw site, while the moderate site had intermediate CO2 efflux between the two. Ground subsidence, permafrost thaw and increased microbial activity accounted for the above observed trends. Other research conducted by Vogel et al. (2009) provide 6 contrasting results; moderately thawed sites were a sink for CO2, and minimally thawed sites remained neither a source nor a sink for CO2. The differing results of carbon efflux from thermokarst terrain have complicated researcher’s ability to spatially scale up to extract an overall carbon release from these features. Clearly, more studies are needed to help quantify the overall impact of thermokarst features on total C release from the Arctic. 1.1.5 Controls on CO2 Efflux Soil temperature, moisture, and substrate quality (%SOC) exhibit interactive controls on CO2 flux rates within the arctic ecosystem (Hobbie et al., 2000; Huemmrich et al., 2010; Michaelson and Ping, 2003; Oberbauer et al., 2007). Many studies have shown a positive linear correlation between CO2 efflux and soil temperature (Huemmrich et al., 2010; Oberbauer et al., 2007). Results of an experimental warming study indicated that at -2°C, the CO2 respiration for both the organic and mineral horizons are about the same (Michaelson and Ping, 2003). However when warmed to 4°C, average respiration rates were twice as high in organic soil horizons than those found for mineral horizons (Michaelson and Ping, 2003). Oberbauer et al. (2007) conducted numerous field warming studies around Toolik Lake and Barrow, Alaska. They found that, in general warming increased soil respiration with the largest increase observed at drier sites (Oberbauer et al., 2007). The interaction of soil temperature and moisture has been shown to affect the rates of CO2 efflux. For example Huemmrich et al. (2010) determined that the water table determined whether the ecosystem was a source or sink for carbon, with temperature modifying the strength of the source or sink. Increased moisture can shift the soil 7 environment to anaerobic conditions whereby the majority of carbon in the system may be released as CH4 instead of CO2. Signigicant knowledge gaps exist in the area of how the physical structure of soils relates to carbon efflux in arctic environments. 1.1.6 δ13C of Soil Respired CO2 δ13C of soil CO2 and CH4 allow for an examination of how thermokarst features alter soil profiles by either mixing or compacting soil. Variations in carbon isotope composition (δ13C) between soil organic matter and CO2 efflux enable tracing sources and sinks of respired CO2. However, this approach has rarely been applied in arctic ecosystems. In general, δ13C of soil respired CO2 becomes more negative with depth in soil profiles (Amundson and Davidson, 1990). This trend can be attributed to mixing with atmospheric CO2 at the surface (less negative), and values approaching that of the decomposing organic matter/root respiration (more negative) with increasing soil depth (Flanagan et al., 2005). Variations in the above trend, are a function of ecosystem productivity, amount of organic carbon burial and vegetation type. It is predicted that thermokarst features will re-work soil profiles by unburying older sources of carbon allowing them to be worked on by microbial processes. We hypothesis that typical δ13C soil profiles will not be seen within thermokarst features. Rather these profiles will show the influence of older carbon δ13C values (more negative) closer to the surface due to accelerated mixing by mass wasting. Research on δ13C vertical soil profiles within the arctic ecosystem is sparse, and represents a knowledge gap within overall arctic carbon cycling theory. It has been shown that, in general, SOM at wetter sites has lower δ13C values. This is due to less drought stress on plants that contribute to δ13C values as litterfall (Flanagan et al., 2005). 8 Research in western Canada along a transect from boreal forest to tundra, shows a decrease in δ13C of 0.7-0.9‰ in the upper 30cm of soil (Bird et al., 2002). Recent work in Antarctica and peatland bogs in northern England has investigated the effects of temperature, soil moisture and substrate quality (% SOC) on the flux and carbon isotope content of soil-respired CO2 (Hardie et al., 2011; Shanhun et al., 2012). For these studies, temperature and substrate quality were main drivers of isotopic C compositions within the soil profile. This research noted that increased temperatures increased the fractionation of 13C and that an increase in lignin composition down the soil profile lead to an overall depletion in δ13C. Within the Arctic, δ13C of soil respired CO2 has been used to determine whether the soil environment is aerobic or anaerobic. In general, within a thermokarst aerobic soil conditions occur in well-drained areas, such as slopes and uplands. Conversely, anaerobic soil conditions occur in poorly-drained areas with water-logged soils, such as lowlands or areas of excessive ponding (Lee et al., 2012). Within Arctic environments, aerobic soil conditions tend to produce δ13C of soil respired CO2 values between -23 to -27‰ (Lee et al., 2012). While anaerobic soil conditions tend to produce values that are heavier, ranging from -11 to -23‰ (Lee et al., 2012). Less negative δ13C values observed in anaerobic soils in the Arctic can be contributed to the influence of methanogenesis, whereby 12C is preferentially used as opposed to 13C. Studies on the effects of carbon cycling for both anaerobic and aerobic soil conditions within thermokarst systems have mainly been focused on laboratory incubations of arctic soil, as well as, the forms of carbon released. It is unclear if the above trends will hold true in a field setting. More 9 studies need to focus on the changes in field δ13C profiles as they relate to both aerobic and anaerobic conditions. 1.2 Thesis Objective In this thesis, I use a thaw slump chronosequence composed of active, stabilized and undisturbed surfaces to examine soil CO2 efflux from a large thermokarst failure. In 2011 and 2012, we quantified soil CO2 efflux during peak summer months. I use these data to examine the controls of soil moisture, temperature, as well as, soil physical properties in governing the release of CO2 across the chronosequence. I hypothesize that soil CO2 efflux will be greater in the active slump and stabilized slump features as opposed to the tundra due to deep thaw and mixing of soil organic carbon pools, and increased soil temperature and moisture. We also use soil profiles from the thaw slump chronosequence to examine how changes in the soil environment affect CO2 production across the soil column, as well as the resulting surface CO2 efflux. In 2012 we measured CO2 and CH4 soil concentrations, δ13C of respired soil CO2 . I use these data to examine the controls of porosity, effective diffusivity, soil temperature, moisture, as well as other physical soil properties in governing the production and release of CO2 across the chronosequence. 1.3 Thesis Structure Chapter one provides a general overview of the relevant literature, including what is poorly understood about carbon-cycling within artic soils. The second chapter investigates soil CO2 efflux along a thaw slump chronosequence, as well as the controls of soil temperature, moisture, bulk density and soil organic matter content on surface CO2 efflux. The third chapter investigates how changes in physical soil properties across thaw 10 slump chronosequence affects soil profile carbon-cycling and the resulting CO2 efflux. The fourth chapter serves as a brief discussion of the implications and conclusions of chapters two and three. 11 1.4 References ACIA, 2004, Impacts of a Warming Climate: Arctic Climate Impact Assessment. Alewell, C., R. Giesler, J. Klaminder, J. Leifeld, and M. Rollog, 2011, Stable carbon isotopes as indicators for micro-geomorphic changes in palsa peats: Biogeosciences Discussions, v. 8, p. 527-548. Amundson, R., and E. Davidson, 1990, Carbon dioxide and nitrogenous gases in the soil atmosphere: Journal of Geochemical Exploration, v. 38, p. 13-41. Amundson, R., L. Stern, T. Baisden, and Y. Wang, 1998, The isotopic composition of soil and soil-respired CO< sub> 2</sub>: Geoderma, v. 82, p. 83-114. Bird, M., H. Santruckova, J. Lloyd, and E. Lawson, 2002, The isotopic composition of soil organic carbon on a north-south transect in western Canada: European Journal of Soil Science, v. 53, p. 393-403. Flanagan, L. B., J. R. Ehleringer, and D. E. Pataki, 2005, Stable Isotopes and BiosphereAtmosphere Interactions: Processes and Biological Controls, Elsevier, 310 p. Grosse, G., J. Harden, M. Turetsky, A. D. McGuire, P. Camill, C. Tarnocai, S. Frolking, E. A. G. Schuur, T. Jorgenson, S. Marchenko, V. Romanovsky, K. P. 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Kicklighter, 2006, CO2 and CH4 exchanges between land ecosystems and the atmosphere in northern high latitudes over the 21st century: Geophysical Research Letters, v. 33. 14 2 Soil properties affect variations in carbon dioxide efflux across a retrogressive thaw slump chronosequence in northwest Alaska. 2.1 Abstract Warming of the arctic landscape results in permafrost thaw, which causes ground subsidence or thermokarst. On hillslopes, these features can grow rapidly, altering soil structure and likely temperature, moisture, as well as the content and quality of soil organic matter. In turn, these changes likely affect both the rate and mechanism of carbon cycling in permafrost soils. This is a major concern because permafrost soils store nearly half the world’s global carbon. In order to assess the time-evolution of carbon contributions from features like these, we use a three-stage chronosequence of thaw slumps to describe the differences in carbon dioxide (CO2) fluxes from undisturbed, active and stabilized features. Our study site, found along the Selawik River in northwest Alaska, contains one of the largest active retrogressive thaw slumps known in North America and had a surface area of ~50,000 m2 in 2012. We designate the undisturbed tundra as the initial condition and an adjacent, bowl-like depression revegetated by multiple generations of black spruce trees as the stabilized slump. In this 2-year study, we use peak summer measurements of CO2 efflux across the chronosequence to determine how belowground carbon emissions compare among features of different maturity. Using measurements of soil temperature, soil moisture, soil organic matter, and bulk density, we also evaluate how environmental factors control CO2 emissions within each of the three stages. CO2 efflux from the active slump is less than half that observed in either the undisturbed tundra or stabilized slump. Although the floor of the active slump is generally 10 to 15°C warmer than the tundra and stabilized slump, we did not observe soil temperature or moisture to exert a strong control on CO2. 15 Rather we found local physical soil properties such as soil organic matter and bulk density to be strongly and inversely related among these features (r2=0.97) and could potentially explain ~50% of the variation in CO2 efflux from our system. Because of the low organic matter content in the active slump (1%-3%), as well as bulk densities close to particle density (~2.3g-dry/cm3), there is a substrate quality and diffusivity limitation within the active slump which decreases CO2 efflux. Our findings suggest that though thaw slumps can profoundly alter the biophysical controls on CO2 production, the mixture of low-organic content mineral substrates with peaty soils actually reduces CO2 efflux below initial conditions. As the feature matures and is recolonized as a boreal forest ecosystem, fluxes from this altered stable state return toward initial conditions. In order to assess the significance of catastrophic thermokarst on global carbon budgets, future studies must assess whether CO2 fluxes from features in high organic content substrates are significantly elevated above initial conditions as well as provide higher spatial resolution maps of carbon content in thawing permafrost soils. 2.2 Introduction Permafrost degradation and thermokarst features are dramatically altering carbon cycling across the Artic landscape (Grosse et al., 2011; Rowland et al., 2010; Schuur et al., 2008; Tarnocai, 2009). Although numerous types of thermokarst exist across the Arctic landscape (Jorgenson et al., 2008b), carbon cycling studies primarily measure fluxes from gradual ground subsidence in low relief terrain (Lee et al., 2010; Schuur et al., 2009). At the other end of the spectrum, fluxes from rapid erosional features such as retrogressive thaw slumps have received little attention. The increasing recognition of these catastrophic thermokarst throughout the arctic (Gooseff et al., 2009; Jorgenson et 16 al., 2008b; Lacelle et al., 2010), creates an explicit need to quantify soil carbon dioxide (CO2) emissions and study the governing controls within these features. Warming trends in the arctic and associated landscape changes have received international attention and are projected to increase with future changes in climate (ACIA, 2004; IPCC, 2007; Winton, 2006). Over the past 30 years, temperatures within Alaska have risen by 1-3°C (ACIA, 2004). Results from general circulation models differ somewhat regarding future trends, but models and scenarios selected for the Arctic Climate Impact Assessment (2004) generally agree that average annual temperatures in the arctic will increase a further 3-5°C and winter temperatures may increase by 4-7°C by 2100. Model scenarios also suggest that rising temperatures will be accompanied by increased precipitation, mostly in the form of rain. This warming trend has accelerated widespread permafrost degradation throughout Alaska (Jorgenson et al., 2010; Jorgenson et al., 2006). A direct consequence of this degradation is thermokarst, where thaw leads to ground subsidence (Jorgenson et al., 2010; Rowland et al., 2010). Thermokarst features directly impact soil and hydrologic properties, ecosystem energy balance, increase exposure of soil carbon and nutrient pools due to active layer deepening, as well as changes to vegetation and landscape topography (Jorgenson and Osterkamp, 2005). Thermokarst can broadly be characterized by either gradual thaw or catastrophic failure. Gradual thaw occurs in areas with high soil organic matter content, low relief, and stable topography result in increased water storage associated with active layer deepening (Jorgenson et al., 2008b). In contrast, catastrophic failures occur on hillslopes, where vegetation is typically stripped, exposing bare soil which causes a multitude of cascading effects: increased exposure to incoming solar 17 radiation, decreased available soil organic matter, exposure of buried soil material, increased erosion by surface overflow and rapid fluctuations in soil moisture (Gooseff et al., 2009). Progressive permafrost degradation has the potential to release of vast stores of previously frozen carbon contained within permafrost soils. Through thaw, this carbon becomes available for microbial decomposition, causing the release of greenhouse gases such as CO2 and methane (CH4) to the atmosphere through increased soil respiration (Amundson and Davidson, 1990; Schuur and Abbott, 2011). This transfer of organic carbon from permafrost to the atmosphere could induce a positive feedbacks with global temperatures (Schuur et al., 2008). However, the magnitude and timing of carbon release is poorly constrained due to changes in soil physical properties associated with permafrost thaw, uncertainty in how permafrost will thaw across a heterogeneous landscape, as well as temperature and moisture constraints on the decomposition of previously frozen carbon (Grosse et al., 2011; Hinzman et al., 2005; Schuur and Abbott, 2011; Schuur et al., 2008). Most CO2 efflux studies in the Arctic have been small in spatial scale (< 10m2) and conducted in areas of gradual thaw, where active layer thaw deepens into organic rich substrates and changes the rate of carbon cycling within the ecosystem (Lee et al., 2011; Schuur et al., 2009; Vogel et al., 2009). These studies generally show that CO2 production increases as the thermokarst matures. In recent years, catastrophic thermokarst failures have been increasing in frequency across the Alaskan landscape (Gooseff et al., 2009), yet few studies have examined CO2 efflux from these features as well as the physical and biological controls on these fluxes. 18 Studies have shown that soil temperature, moisture, and substrate quality exhibit interactive controls on CO2 efflux rates within the arctic ecosystem (Huemmrich et al., 2010; Michaelson and Ping, 2003; Oberbauer et al., 2007). In general, increases in soil temperature lead to an increase in CO2 soil respiration, with the largest increase observed under drier conditions (Huemmrich et al., 2010). Increasing soil moisture has the effect of shifting CO2 production from an aerobic process to an anaerobic process, whereby the majority of carbon is released in the form of methane (Anthony, 2009). It is unclear how catastrophic thermokarst will alter soil moisture and temperature controls on soil CO2 efflux and whether these features are sources or sinks of carbon to the atmosphere. Here we use a thaw slump chronosequence to examine soil CO2 efflux from a catastrophic thermokarst failure. In 2011 and 2012, we quantify soil CO2 efflux during peak summer months and examine the influence of soil moisture, temperature, as well as, soil physical properties on the release of CO2 across the chronosequence. We hypothesize that soil CO2 efflux should be higher in the active slump and stabilized slump as opposed to the undisturbed tundra due to deeper thaw and mixing of soil organic carbon pools, and increased soil temperature and moisture. 2.3 Field Setting The Selawik slump field area is located along the upper Selawik River (157°36”43”W, 66°29’54”N) in northwest Alaska (FIGURE 1). This area is composed of an upland tussock shrub tundra community, an active retrogressive thaw slump that initiated in 2004, and a stabilized retrogressive thaw slump that is estimated to be >500 years old. 19 Mean annual precipitation in this area is 256 mm per year and mean annual air temperature is -5.67°C. Soil temperature regime is gelic with a mean soil temperature of 4.67°C and the soil moisture regime is classified as aquic (Schoeneberger et al., 2002). The parent material in this area is a glacial diamict composed of poorly sorted silt, gravel and cobble overlain by fine grained loess (Lanan, 2013). The active layer (the upper portion of the soil column that freezes and thaws each year) varies between the different sites and extends to depths of 0.3 to 0.8 m. Because this field site is remote (~108 km east of Selawik Village) and difficult to access during spring, fall, and winter (helicopter only), no sampling occurred during these seasons. Sampling focused on summer months when we expected to observe the highest CO2 effluxes owing to higher temperatures and biologic productivity. 2.4 Study Deisgn: a chronosequence enables a space for time substitution We used a space for time substitution (thaw slump chronosequence) to examine the evolution of thaw slumps and their subsequent stabilization. Our field site includes three stages of feature evolution: undisturbed tundra, active slump, and stabilized slump (FIGURE 1). Other factors such as climate, slope, parent material, and biota are all held relatively constant (Chapin et al., 2011; Jenny, 1941). Since there are no biotic barriers across this chronosequence, differences in vegetation are a function of time since disturbance. In our chronosequence conceptual model, the final state of our system does return to initial tundra conditions. We postulate that the ending trajectory of the active slump will be similar in nature to the forested stabilized slump feature, due to geomorphic and ecosystem drivers. 20 The tundra environment has not undergone any physical disturbance and represents our arctic landscape reference condition or control. The tundra ~20m north of the Selawik slump headwall (FIGURE 1). Primary vegetation consists of sedge, tussocks (Eriophorum vaginatun, and Carex spp.) with interspersed moss and lichen. Summer active layer thickness ranges from 30 to 60 centimeters. A Gellic Typic Fibristels, which is characterized by a wet, poorly decomposed thick (15-20 cm) peat, that transitions to a mineral soil with permafrost in the upper meter. This soil is also characterized as loamy that is poor to moderately drained (Jorgenson et al., 2009) (TABLE 2). The active slump initiated in 2004 is one of largest known active retrogressive thaw slump in the world. This feature has mobilized more than a half million cubic meters of ice and sediment, and is growing at a rate of ~20 m/year. The slump floor is approximately 50,000 m2, with a headwall measuring 15-18 m tall. The headwall is composed mostly of glacial diamict and loess, with a small (20 cm) upper cap of organic rich peat and tussock community as previously described for the tundra. Because the active slump grows quickly and the vast majority of the eroded material is diamict, the slump floor is largely composed of overlapping mudflows of unsorted silts and gravels with no detectable soil profiles. Three percent of the slump floor is mantled by vegetated rafts (0.05-0.5 m2 each), which are composed of intact pieces of tundra that have fallen off the headwall and been transported with sediment downslope. Frost probing the slump floor revealed no permafrost in the upper meter (TABLE 2). The stabilized slump is directly adjacent and west of the active slump (FIGURE 1) and represents a likely trajectory of our active thaw slump. Following catastrophic failure, this area has since been recolonized by black spruce, alder (Picea mariana and 21 Alnus spp.), and various grasses. Soil profiles have been re-established and are classified as Gellic Typic Aquorthels, which are wet mineral soils over permafrost, which lack cryoturbation. This soil type is characterized as loamy and is poorly to moderately drained (Jorgenson et al., 2009). Summer active layer thicknesses range from 50 to 80 cm (TABLE 2). The feature is thought to be greater than 500 years old based on the presence of numerous generations of black spruce logs found decaying on the surface. The active slump has eroded the eastern flank of the stabilized slump revealing both a texture of the ancient thaw slump deposit and the new soil profiled developed above. 2.5 Methods 2.5.1 Meteorology Continuous air temperature and precipitation were collected in thirty minute intervals from a weather station located approximately 50 m due north of the active slump headwall in the tundra domain (FIGURE 1). Air temperature was collected using a shielded sensor 215 cm above ground. Precipitation was collected using a tippingbucket 242 cm above ground. Data were collected from January to September in 2011, and from June to early August in 2012. Due to the close spatial proximity of our chronosequence to the weather station, we assume precipitation and air temperature data are consistent throughout the study area. 2.5.2 Point measurements of CO2 Efflux, Soil Temperature, Soil Moisture Sampling sites for soil CO2 efflux, soil temperature, and soil moisture were established along our defined chronosequence: six sampling sites within the tundra, eleven sites within the active slump, and nine sites within the stabilized slump (26 total, FIGURE 1). Sites within a given region sample different types of vegetation and 22 disturbance to assess heterogeneity within each category. After sites were established, a 12.7x10.2 cm polyvinyl chloride pipe (soil collar) was driven 8cm into the upper portion of the soil column. The soil was then allowed to stabilize for twenty-four hours prior to any measurements (LI-COR, 2007). In July of 2011, each site was sampled approximately five times in a six-day sampling period. In July and August of 2012, each site was sampled approximately twelve times over an eighteen-day sampling period. Sampling times for each collar were distributed throughout the day and night to average across expected temporal variability in measured parameters. Soil CO2 efflux, soil temperature, and soil moisture were measured using a LiCor8100A analyzer (Lincoln, NE). CO2 efflux was collected using a LiCor-8100-102, 10cm diameter survey chamber attachment, placed on top of the soil collar platforms and set at a 1.5 minute sampling interval. Soil temperature was measured at depths of 5, 10, and 15 cm next to the chamber with a LiCor 8100-203 soil thermistor probe. Volumetric water content (VWC) (volume water/volume soil), hereafter referred to as soil moisture, was measured using a Delta-T ML2x probe (Lincoln, NE) at a depth of 10cm. Post-processing of soil CO2, temperature and soil moisture was conducted using the LI-8100 Data File Viewer (v2.0). Soil volumetric water content was adjusted for high organic content soils using the equation provided in the Li-COR manual (2007). 2.5.3 Physical Soil Properties In 2012, soil bulk density and soil organic matter content were determined for a subset of collars along the chronosequence. Two rectangles of known volume were excised from the soil collar after all flux measurements had been completed. The soil sample was subsequently frozen and transported back to Idaho State University where 23 they were analyzed for soil organic matter (SOM) and bulk density following methods described by Schumacher (2002) and Blake and Hartge (1986), respectively. In brief, SOM was determined by loss-on-ignition by combusting 100 g of dry soil for 24 hours at 500°C and reweighing the remaining mass. Bulk density was determined by drying the soil at 105°C and weighing the dry mass and sieving the soil to retain the fine fraction <2 mm. 2.5.4 Statistical Analysis Repeated CO2, soil temperature and moisture measurements were averaged for each ring location each day within the chronosequence environment. CO2 efflux measurements were log transformed to improve normality and homoscedasticity. Other parameters such as soil moisture and soil temperature were normally distributed and thus did not require transformation. ANOVA and Tukey-Kramer HSD statistical tests for soil CO2 efflux, soil temperature, and soil moisture were used to determine statistical differences within each environment along the chronosequence (TABLE 1). Collars within each environment (tundra, active, and stabilized slump) showed no significant differences within each environment so that data collected within each environment was pooled for both 2011 and 2012. ANOVA tests and Tukey-Kramer HSD were then conducted to determine statistical differences between chronosequence environments for 2011 and 2012. Linear and multiple linear regression models were used to determine environmental controls on CO2 efflux. All statistical analyses were performed in JMP 10 (Cary, NC) software. 24 2.6 Environmental Conditions over Space and Time 2.6.1 Precipitation Both magnitude and intensity of precipitation during the 2012 campaign were higher than 2011. Cumulative precipitation during the 2011 sampling period (FIGURE 2a) was relatively low, totaling 9 mm from two small events. In contrast, the 2012 sampling period was much wetter, including three significant events, the largest of which occurred during the first week of sampling and delivered 20 mm. The second and third events occurred in the latter half of the 2012 campaign each delivered approximately 5 mm. 2.6.2 Air Temperature Air temperature was generally higher in 2011 than during the 2012 sampling period (FIGURE 2b). Average air temperature during the 2011 sampling period was ~16±5.3°C, and showed an overall cooling trend. In contrast, 2012 average air temperature was lower, ~14±3.8°C, and showed a slight warming trend in the first half of the sampling period, followed by a slight cooling trend throughout the latter half of the period. For both 2011 and 2012, periods of precipitation reduced the magnitude of the diel cycle in air temperature. 2.6.3 Soil Temperature Average daily soil temperatures at 15 cm were consistently higher in 2011 for all three chronosequence environments (FIGURE 2c). This mean behavior corresponded with the higher air temperatures and lower precipitation in 2011. Within individual years, similar correlations existed between measurements of air temperature, precipitation and soil temperature. These correlations were most apparent in the active slump. 25 Soil temperatures were significantly different among the environments for both 2011 and 2012 (2011 F2,21=64.07, p<0.0001; 2012 F2,25=78.4, p=0.0001) (FIGURE 3a)(TABLE 1). Post-hoc Tukey tests showed that although there are no significant differences between soil temperatures in the tundra and the stabilized slump, soil temperatures were significantly elevated; 3-4 times higher, in the active slump relative to these two environments (p<0.05). We attribute these differences to the higher thermal conductivity and lower albedo of the dark, bare mineral soil in the active slump. The abundant, multi-story vegetation at both the tundra and stabilized slump insulate the soil and shade against solar radiation, dampening variability in soil temperature. The tundra and stabilized slump also have thinner active layers, placing permafrost closer to the surface. 2.6.4 Soil Moisture Average daily soil moisture for both the 2011 and 2012 seasons were more temporally variable than soil temperatures, with generally higher soil moistures observed in the 2012 season (FIGURE 2d). The tundra had the highest soil moisture, whereas the mineral soil in the active slump has the lowest soil moisture in both years. Average soil moisture differed significantly among chronosequence environments (FIGURE 3b) in both years with the tundra having higher soil moisture than the other two environments (2011 F2,21=7.52, p<0.0039; 2012 F2,25=5.08, p=0.015)(TABLE 1). Posthoc Tukey tests revealed no significant differences between the active and the stabilized slump whereas the tundra was significantly elevated relative to these two environments (p<0.05). We attribute the differences between the tundra and both the active and stabilized slump to differences in topographic setting. The tundra in our study area 26 consists mostly of mosses, lichen and tussock communities on a relatively flat lying slope. These characteristics allow water to have a longer residence time in that environment. In contrast, both the active and stabilized slumps are located on steeper surfaces, sloping 10-25°toward the Selawik River such that water likely drains faster, thus reducing soil moisture. Alternatively, differences in soil organic matter, albedo and bulk density affecting soil water holding capacity could drive differences in moisture contents across environments. 2.6.5 Physical Soil Properties Soil organic matter (SOM) and bulk density differed considerably among the three environments. SOM content ranged from 1-95%. In the active slump, where the parent material for this active depositional surface is dominated by glacial diamict, we observed the lowest SOM content while the stabilized slump contained the highest SOM content (TABLE 2). The tundra’s SOM values ranged between the active and stabilized slumps. Bulk density along the chronosequence was also highly variable (0.1-2.5 gdry/cm3) (TABLE 2). However, a strong inverse exponential correlation existed between soil organic matter and bulk density and corresponded to different chronosequence environments (r2=0.97) (FIGURE 5a). The active slump floor, for example, has the lowest organic matter content because it is composed of sediment remobilized from the thawing headwall, which is dominated by glacial silts and gravels. The thawed materials flow away from the headwall as a thick, viscous slurry and stabilize on the slump floor. Because of the high silt content and low porosity, the active slump samples also had the highest bulk densities. In contrast, the stabilized slump had the highest SOM values and 27 to the lowest bulk density. Though the stabilized slump had the same bulk density material at depth, this environment has been completely re-vegetated and has a mature soil profile with a greater proportion of grasses than the mosses and lichens common in the tundra environment. This results in lower bulk densities and higher SOM values in the stabilized slump. 2.7 CO2 Efflux over Space and Time CO2 efflux was generally greater in 2011 than in 2012 in each of the chronosequence environments. CO2 efflux for both seasons decreased over the sampling period (Figure 2e) corresponding to increases in soil moisture as well as slight increases in soil temperature. This correlation is most evident in the tundra and active slump in 2012. CO2 effluxes were significant different among the chronosequence environments (figure 3c) and differed among years (2011, F3,22=12.69 p<0.0001, 2012 F3,25=27.48, p<0.0001)(TABLE 1). In 2011, fluxes from the tundra and stabilized slump were similar. The fluxes from the active slump were significantly lower (p<0.05) than those from the other two environments. Conversely, in 2012, the CO2 fluxes from the tundra, active slump and stabilized slump were all significantly different from each other. The highest fluxes came from the stabilized slump and lowest from the active slump. Measurements of CO2 efflux along the chronosequence for both 2011 and 2012 were scaled up to estimate total grams of carbon lost to the atmosphere per day during peak growing season (TABLE 2). Total carbon released as CO2 in the tundra for 2011 was greater than in 2012. Numerous studies have determined average carbon release specifically for the tundra environment via CO2 during the growing season (Giblin et al., 28 1991; Poole and Miller, 1982; Raich and Schlesinger, 1992) and our observed values were 1.5 to 2 times higher than these studies report. These differences may be due to a dampening effect of cooler temperatures inhibiting soil CO2 efflux at the more northerly comparison sites. Average carbon released from CO2 in the active slump during peak summer in 2011 was 1.75±0.15 g CO2-C m-2 day-1. In 2012, these fluxes were half that (0.86±0.24 g CO2-C m-2 day-1). These values fall within the lower range of fluxes observed along a chronosequence of minimally thawed to extensively thawed gradual thermokarst sites in Alaska (Lee et al., 2010; Schuur et al., 2009)(TABLE 2). Unlike our system, there has been no significant vegetation stripping, sediment esposure or remobilization. These changes have not altered the structure of the soil column beyond deepening the frost table, allowing more carbon to become functionally available. Compared to our site, their albedo changes were insignificant. Because of these differences, the values that we observed for CO2 efflux in the active slump were closer to sites that had been minimally thawed, but are not directly comparable. Average carbon release from the stabilized slump during peak summer 2011 was 5.14±0.27 g CO2-C m-2 day-1, while in 2012 we observed only 3.24±0.13 g CO2-C m-2 day-1. Again, our estimates (TABLE 3) fell within in the higher range of measured estimates for black spruce forests within Alaska (which we use as a proxy for the stabilized slump) (Raich and Schlesinger, 1992; Schlentner and van Cleve, 1985; Vogel et al., 2008b). Most of the values from other studies were averaged over a full year. Our values represent peak growing season and therefore tended to be skewed to the upper end of existing measurements. 29 2.7.1 Controls Affecting CO2 Efflux 2.7.1.1 Soil Temperature and Moisture Soil temperature and moisture exhibit a surprisingly weak control on soil CO2 efflux across our chronosequence. In 2011, soil moisture exerts a slightly stronger control while in 2012, soil temperature exerts a slightly greater control on CO2 efflux (FIGURE 4). We suggest that during 2011, our system was water-limited, and therefore soil moisture exerted a stronger control on soil CO2 efflux. In 2012, due to the increased precipitation, the system was no longer water limited and soil temperature exerted stronger control on CO2 efflux along our chronosequence. Our weak correlations between either soil temperature or moisture and CO2 efflux along the chronosequence are likely due to limited environmental variation during our sampling campaign. Data were collected only during the peak growing season (~18 hours of sun) when the driving variables did not change much. We believe that if given the ability to collect data during shoulder seasons and winter we would have observed higher correlations between soil temperature and moisture with soil CO2 efflux. Also, although we measured CO2 efflux intermittently during both day and the night, we did not use automated sensors to collect data at regular, high frequency intervals. Because measurements were made at irregular times over days when environmental conditions such as precipitation were also changing, we have less explanatory power. For example, at one collar, one measurement might have been made on a warm, dry night and then next on a cool, dry night. Although we did not find strong correlations between soil CO2 efflux and soil temperature or moisture, the correlations between variables that we did observe were consistent with the observations of other workers (Huemmrich et al., 2010; Michaelson 30 and Ping, 2003; Natali et al., 2011; Oberbauer et al., 2007; Peterson and Billings, 1975). For example, it has been shown that increased soil temperature, increases soil CO2 efflux with the greatest increases observed in sites in drier ecosystems. In general, soil CO2 efflux increased with increasing soil temperature, and decreased with increasing soil moisture (Michaelson and Ping, 2003; Oberbauer et al., 2007). 2.7.1.2 Physical Soil Properties In contrast to our weak correlations for soil moisture and temperature, we found a strong inverse correlation between bulk density and soil CO2 efflux (R2= 0.50) (FIGURE 5b). Along the chronosequence, the tundra and stabilized slump have some of the lowest bulk densities and highest average soil CO2 effluxes (TABLE 2&3). In contrast, the active slump has some of the highest bulk densities and lowest soil CO2 effluxes (FIGURE 5b). Indeed, soil bulk density values in the active slump approached typical particle density values of 2.65 g cm-3. These findings suggest that higher bulk densities may provide a diffusion limitation inherent in the soil profiles along the chronosequence and possibly inhibiting gas from rising to the surface (Davidson and Trumbore, 1995). In contrast, we found a strong positive correlation between soil organic matter and soil CO2 efflux (R2=0.51) (FIGURE 5c). The tundra and stabilized slump had some of the highest organic matter contents and some of the highest soil CO2 efflux. In contrast, the active slump had the lowest soil organic matter content and the lowest soil CO2 efflux possibly suggesting an organic substrate limitation to respiration. These results suggest that physical soil properties, such as bulk density and soil organic matter, act as stronger local control on CO2 efflux than environmental factors such as soil temperature and moisture. Though we cannot differentiate whether SOM or bulk density are more 31 influential in controlling CO2 efflux because of the correlation between SOM and bulk density (FIGURE 5a), these observations suggest fruitful avenues for future studies. 2.8 Implications In a warming world, the prevalence of large, rapidly evolving, thermal erosional features like the Selawik slump are predicted to increase in frequency (Gooseff et al., 2009; Lacelle et al., 2010; Rowland et al., 2010). However, no published studies to our knowledge have examined soil CO2 emissions, as well as the governing controls on these fluxes, within these catastrophic thaw slumps. This study contributes to our knowledge of how these retrogressive thaw slumps may initially function and give rise to changes in soil physical properties that either limit or enhance soil CO2 efflux and how these geomorphic thaw slumps may evolve over time. Findings from this study indicates that quantifying the initial substrate quantity, used as a proxy for carbon availability, as well as the material’s diffusivity will likely be of great importance to understanding CO2 efflux in these rapidly changing environments. The Arctic is composed of a heterogeneous landscape where substrate soil organic matter ranges from 1-3% as seen at the active Selawik slump, to 90-100% as seen in yedoma soils of northern Alaska and Siberia (Kanevskiy et al., 2011) and the stabilized slump in our study. Initial substrate appears to play a large role in driving differences in CO2 efflux from a given environment, with lower fluxes from the active slump compared to the tundra and stabilized slump, suggesting a critical need to quantify soil carbon and other soil properties in these environments. Our research also suggests that geomorphic controls governing the initiation and development of thaw slumps influences overall CO2 efflux. Our findings show that 32 thermokarst features such as retrogressive thaw slumps ultimately result in compaction of the soil structure increasing soil bulk density and decreasing porosity. These soil structural changes appear to reduce the release rate of soil CO2 due to diffusivity limitations and merit further study. 2.9 Conclusion We examined CO2 efflux along a thaw slump chronosequence from one of the largest known retrogressive thaw slumps. To our knowledge, this is the first study to publish CO2 efflux, and their possible controls in a thermokarst feature of this type and magnitude. In contrast to our initial expectations that the active slump would have higher soil CO2 effluxes, we found that soil CO2 effluxes in the active thaw slump were significantly lower, approximately half that measured in the tundra and stabilized slump for 2011 and 2012. 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Zimov, 2008, Vulnerability of Permafrost Carbon to Climate Change: Implications for the Global Carbon Cycle: BioScience, v. 58, p. 701-714. Schuur, E. A. G., J. G. Vogel, K. G. Crummer, H. Lee, J. O. Sickman, and T. E. Osterkamp, 2009, The effect of permafrost thaw on old carbon release and net carbon exchange from tundra: Nature, v. 459, p. 556-559. Tarnocai, C., 2009, Soil organic carbon pools in the northern circumpolar permafrost region: Global Biogeochemical Cycles, v. 23, p. 1-11. Vogel, J., E. Schuur, C. Trucco, and H. Lee, 2009, Response of CO2 Exchange in a Tussock Tundra Ecosystem to Permafrost Thaw and Thermokarst Development Journal of Geophysical Research, v. 114, p. G04018. Vogel, J. G., B. P. Bond-Lamberty, E. A. G. Schuur, S. T. Gower, M. C. Mack, K. E. B. O'Connell, D. W. Valentine, and R. W. Ruess, 2008, Carbon allocation in boreal black spruce forests across regions varying in soil temperature and precipitation: Global Change Biology, v. 14, p. 1503-1516. Winton, M., 2006, Amplified Arctic climate change: What does surface albedo feedback have to do with it?: Geophysical Research Letters, v. 33, p. L03701. 36 2.11 Figures Figure 1. Map view of the Selawik slump. Each environment is symbolized as follows: black squares denote tundra, black triangles denote active slump, and black circles denote stabilized slump. Stippled pattern in the stabilized slump is made by Black Spruce shadows. The boundary for each chronosequence is outlined. The Selawik River flows east to west at the base of the image. The inlay map in the bottom right corner shows the location of the field area in Alaska. Weather station location is denoted by a black circle with white ring. 37 Table 1. Summary ANOVA value table. 2011 Soil Temperature 2012 Soil Temperature 2011 Soil Moisture 2012 Soil Moisture 2011 CO2 Efflux 2012 CO2 Efflux N Value F Value P Value Degrees Freedom 21 25 21 25 22 25 64.07 78.4 7.52 5.08 12.69 27.48 <0.0001 0.0001 <0.0039 0.015 <0.0001 <0.0001 2 2 2 2 3 3 Table 2. Soil and vegetation characteristics for each chronosequence environment. Active slump has some of the highest bulk densities, lowest soil organic matter %, with no detectable soil profile. Vegetation Tundra Active Slump Stabilized Slump Shrub, Sedge, Tussock, Moss, Lichen None. Bare mineral diamict, 3% - vegetated tundra rafts Black spruce, alder, grasses Soil Type Soil Organic Matter (%) Bulk Density (cm3/cm3) July Active Layer Thickness (cm) Gellic typic fibristel 25 - 90 0.06 - 0.8 30 - 60 No soil profile, bare mineral diamict 1-8 1.3 - 2.2 >100 Gellic typic aquorthel 85 - 95 0.1 – 0.3 50 - 80 38 Figure 2. Day-of-the-year time series of environmental variables for 2011 and 2012 field seasons (grey shading). (a) cumulative precipitation (mm), (b) air temperature (°C), (c) soil temperature at 15cm depth (°C), (d) soil moisture (cm3/cm3), (e) soil CO2 efflux (g CO2-C/m2/day). For figures a and b, light grey and black lines represent continuous weather station data from 2011 and 2012, respectively. For figures c-e, daily means are shown as black squares for tundra, black triangles for the active slump, and white circles for the stabilized slump. 39 Figure 3. Average mean peak growing season (a) temperature (°C), (b) soil moisture (cm3/cm3), (c) soil CO2 efflux (g CO2-C/m2/day), in both 2011 (light grey) and 2012 (dark grey) for the chronosequence environments: tundra, active slump, stabilized slump. Bars represent the mean of all measurements and error bars represent one standard error. Lettering above each bar represents the results for significant differences within year and across environments using a Tukey-Kramer HSD. Columns with similar letters are not significantly different. 40 Table 3. Average daily values of CO2 efflux (g CO2-C/m2/day) in 2011 and 2012 for each chronosequence environment. Also included for comparison are CO2 efflux from relatively similar environments. 2011 CO2 efflux (g-CO2-C/m2/day) Tundra Active Slump Stabilized Slump 2012 CO2 efflux (g-CO2-C/m2/day) Comparable CO2 efflux (g-CO2-C/m2/day) 3.32±0.027 1.89±0.16 0.46 to 1.71,2,3 1.75±0.15 0.86±0.23 0.72 to 2.644,5 5.14±0.27 3.24±0.13 0.264 to 5.896,7,8 1 Giblin et al., 1991, 2 Poole and Miller, 1982, 3 Raich and Schlesinger, 1992, 4 Lee et al., 2010, 5 Schuur et al., 2009, 6 Raich and Schlesinger, 1992, 7 Schlentner and van Cleve, 1985, 8 Vogel et al., 2008. 41 Figure 4. Soil temperature (°C) and soil moisture (cm3/cm3) controls on CO2 efflux (g CO2-C/m2/day) in 2011 and 2012, along the chronosequence: tundra, active slump, stabilized slump. For all graphs, regressions of soil moisture with CO2 efflux are represented by black lines. Regressions of soil temperature with CO2 efflux are represented by grey lines. r2 and p values for each soil temperature regression (grey) and soil moisture regression (black) are in the bottom left corner of each graph. 42 Figure 5. (a) Correlation between soil organic matter (%) and bulk density (g-dry/cm3), exponential fit. (b) Negative correlation between bulk density (g-dry/cm3) and CO2 efflux (g CO2-C/m2/day). (c) Positive correlation between soil organic matter (%) and CO2 efflux (g CO2-C/m2/day). For all graphs, chronosequence is represented as follows: black squares are tundra, grey triangles are active slump, white circles are stabilized slump. 43 3 Soil matters: Vertical profiles of CO2 and CH4 concentrations and δ13C of CO2 respired from a thaw slump chronosequence reveal that soil properties can control carbon efflux at the surface. 3.1 Abstract Arctic landscapes are experiencing unprecedented warming resulting in permafrost thaw, which causes ground subsidence or thermokarst. On hillslopes, these features result in erosion, altering physical soil structure and properties such as temperature and moisture. This raises concerns because permafrost soils store nearly half the world’s global carbon. In order to evaluate the time evolution of carbon released from thaw slumps, we evaluated a soil-profile chronosequence at the Selawik slump in northwest Alaska, including measurements from undisturbed tundra, the active slump and a stabilized, revegetated slump. We use these three environments to assess how thermokarst-driven changes affect soil column CO2 and CH4 production and the resulting surface efflux. Our previous measurements at this site determined that CO2 efflux from the active slump was half that from the tundra or stabilized slump. This current study aims to resolve whether this difference can be explained by soil diffusivity or the quantity and quality of the soil organic matter in the soil profile. Toward these ends, we measured soil profile CO2 and CH4 concentrations, δ13C of both soil respired CO2 and soil organic matter, as well as physical soil parameters such as soil organic carbon %, porosity and water filled pore space at depths of 3, 5, 15, 30, and 50 cm. These data constrain how belowground carbon emissions are affected by changes within the soil environment resulting from the initiation and subsequent stabilization of a rapidly evolving thaw slump. Though the active slump had the lowest CO2 surface efflux, we were surprised to find that the CO2 concentrations at depth were 5 orders of 44 magnitude higher than those observed in the other two environments. CH4 concentrations in the active slump were ~3x higher. The low porosity, high water filled pore space, and low calculated effective diffusivity in the active slump soil profile all indicate that these soil properties limit carbon fluxes at the surface. Observations of soil gleying, heavier δ13C of CO2 (~-15 ‰), and elevated methane concentrations all point to anaerobic soil conditions in these environments. This suggests that thaw slumps switch the metabolic pathway toward methanogenesis. Though thermal erosion features like thaw slumps are predicted to become more prevalent on the landscape, their soil properties may ultimately inhibit them from becoming hot-spots of carbon efflux. Our observations suggest that rapidly evolving thaw slumps with high topographic relief profoundly alter the local environmental conditions and biophysical controls on carbon cycling but do not appear to produce a rapid ‘flush’ of carbon to the atmosphere. 3.2 Introduction Permafrost soils in the arctic store approximately 1600 Pg of carbon as soil organic matter which constitutes ~50 % of global terrestrial carbon (Schuur et al., 2008; Tarnocai, 2009; Zimov et al., 2006). These landscapes are undergoing dramatic geomorphic transformations due to increased warming associated with climate change that have important consequences for soil carbon cycling (ACIA, 2004; IPCC, 2007; Serreze et al., 2000). Over the past 30 years, mean temperatures within Alaska, for example, have risen by 1-3 °C (ACIA, 2004). By 2050, temperatures are projected to increase by 3-5 °C during the summer, and 4-7 °C during winter (ACIA, 2004). This warming may also be accompanied by increased precipitation in the form of rain. 45 Within Alaska, permafrost soils have experienced a 1-4 °C rise in temperature over the past 30 years, which has caused widespread permafrost degradation (Osterkamp and Romanovsky, 1999; Osterkamp, 2005). A direct result of permafrost degradation has been thermokarst formation, whereby thaw leads to ground subsidence (Hinzman et al., 2005; Jorgenson et al., 2010; Jorgenson et al., 2008b; Rowland et al., 2010). Thermokarst features directly impact soil and hydrologic properties, physically changing soil profiles and soil microenvironments, ecosystem energy balance, increase exposure of soil carbon and nutrient pools due to active layer deepening, as well as changes to vegetation and landscape topography (Jorgenson and Osterkamp, 2005; Rowland et al., 2010). In particular, thermokarst features occurring on hillslopes can strip vegetation and expose frozen soils to incoming solar radiation and warm air temperatures. On sloping surfaces, thawed material is transported away by mass movements or surface overflow, leading to continued thaw and feature growth. Rapidly evolving thermokarst currently composes only 2-4 % of the landscape but are expected to increase in spatial extent, magnitude and frequency with warming climate (Gooseff et al., 2009). Despite these trends, few studies have examined how altered physical soil properties in thermal erosion features could affect the delivery of carbon to the atmosphere. Permafrost degradation has the potential to expose vast stores of frozen soil carbon to microbial decomposition. This would result in the release of greenhouse gases to the atmosphere, such as carbon dioxide (CO2) and methane (CH4) (Amundson and Davidson, 1990; Schuur and Abbott, 2011). Most CO2 efflux studies within the arctic have focused on slowly evolving thermokarst features on relatively low relief terrain with relatively small spatial extents. In these studies, CO2 efflux increases with thermokarst maturity 46 (Lee et al., 2010; Schuur et al., 2009; Vogel et al., 2009). % SOC, soil temperature and moisture have been shown to be the strongest controls on efflux (Lee et al., 2011; Schuur et al., 2009; Vogel et al., 2009). In general, increases in soil temperature result in increases in CO2 soil respiration (Hobbie et al., 2000; Huemmrich et al., 2010; Michaelson and Ping, 2003), while increases in soil moisture can shift CO2 production from an aerobic process to an anaerobic process, whereby the majority of carbon is released in the form of methane through methanogenesis (Anthony, 2009; Huemmrich et al., 2010; Lee et al., 2012; Michaelson and Ping, 2003; Oberbauer et al., 2007). Rapidly evolving thermokarst create both aerobic and anaerobic soil conditions in relatively small spatial scales (>1 m), which effects carbon cycling within these systems (Lee et al., 2012). CO2 and CH4 concentration within the soil profile are governed by both rate of production, gas conversions, and the soil diffusivity which is a function of porosity (amount of air-filled pore space within material) and soil moisture (Amundson and Davidson, 1990). In general, CO2 concentrations in soil profiles affected by permafrost thaw, are shown to decrease with depth, while CH4 concentrations increase with depth (Michaelson et al., 2011) Depth to water-table, landscape position, soil moisture, and temperature as well as vegetation composition have been shown to have interactive controls on carbon production within these systems (Lee et al., 2012; Michaelson et al., 2011; Olefeldt et al., 2013). Furthermore, stable isotope studies suggest that the δ13C of soil respired CO2 in arctic environments ranges from -28 to -11 ‰ (Alewell et al., 2011; Hesterberg and Siegenthaler, 1991) with aerobic soil conditions tending to produce δ13C of soil respired CO2 values between -23 to -27 ‰ (Lee et al., 2012) and anaerobic soil conditions 47 producing values that are heavier, ranging from -11 to -23 ‰ (Lee et al., 2012), due to the preferential use of 12C over 13C during methanogenesis . Studies on the effects of carbon cycling for both anaerobic and aerobic soil conditions within thermokarst systems have mainly focused on the forms of carbon released as well as the production rate under varying temperature and moisture conditions from laboratory soil incubations (Huemmrich et al., 2010; Lee et al., 2012). No studies have focused on gas characteristics in soil profiles on rapidly evolving thermokarst features. Previous work by Jensen et al., (in review) showed that, when compared to both the undisturbed tundra and an adjacent stabilized thaw slump, the lowest soil CO2 efflux was from the surface of the active thaw slump. Soil moisture and temperature were found to be weak controls on these fluxes. Rather, findings from this previous study suggested that changes in physical soil properties such as initial substrate quality and/or the material’s diffusivity likely play a key role in governing CO2 efflux in these rapidly changing environments (Amundson and Davidson, 1990; Davidson and Trumbore, 1995). In this effort, we use soil profiles across a thaw slump chronosequence to examine how changes in soil characteristics affect the concentration and isotopic character of CO2 and CH4 . We use these data to examine the influence of porosity, effective diffusivity, soil temperature, moisture, as well as other physical soil properties on the production and release of carbon across the chronosequence. We hypothesize that lower soil CO2 efflux in the active slump compared to the tundra and stabilized slump can be explained by changes in physical soil properties associated with the initiation and geomorphic evolution of thermal erosion features. 48 3.3 Field Setting The Selawik slump field area is located in the upper Selawik River basin (157°36”43”W, 66°29’54”N) in northwest Alaska (FIGURE 1a). This field area is located ~108 km east of Selawik Village, and is only accessible by helicopter. The field site contains a thaw slump chronosequence composed of the undisturbed upland tussock shrub tundra, an active retrogressive thaw slump, and a stabilized retrogressive thaw slump. The active slump, which initiated in 2004, is the largest known retrogressive thaw slump in Alaska. The active slump floor is approximately 50,000 m2, with a headwall measuring 15-18 m tall, which erodes headward into a tundra upland at a rate of ~10 m/yr. Mean annual air temperature at the Kotzebue airport weather station is -5.67 °C, averaged over 30 years. Our field site is further inland and is expected to be warmer in the summer and colder in the winter with a similar annual mean. The soil temperature regime is gelic, with a mean soil temperature of -4.67 °C. Mean annual precipitation for this area is 256 mm per year. The soil moisture regime is classified as aquic (Schoeneberger et al., 2002). The parent material is a glacial diamict composed of poorly sorted cobble, gravel and silt (Lanan, 2013). Factors such as climate, slope, parent material, and biota are relatively consistent across the chronosequence (Chapin et al., 2011; Jenny, 1941; Jenny and Amundson, 1997). Since there are no biotic barriers across this chronosequence, differences in vegetation are a function of time since disturbance. Due to the difficulty in accessing this area, sampling was targeted during the summer months, when we expected to observe the highest CO2 production and efflux, as well as, the greatest variability in environmental conditions. 49 3.4 Thaw slump chronosequence: a space for time substitution In order to assess the temporal evolution of a thaw slump, we utilize a space for time substitution and observe three contemporary surfaces that range in feature maturity from undisturbed tundra to active slump, and finally stabilized slump (FIGURE 1a). In this chronosequence, the final state of our system does not represent a return to tundra conditions but rather in a trajectory toward a re-vegetated, forested surface due to oneway geomorphic and ecosystem drivers. The tundra environment has not undergone any physical disturbance and represents our arctic landscape “reference” condition or control. The tundra is ~20m north of the Selawik slump headwall (FIGURE 1a). Typical soil profiles for this area (FIGURE 1I) consist of an organic layer (0-18 cm), a cryoturbated A horizon (19-23 cm), and a mottled B horizon (23-55 cm). Summer active layer depths for this area range from 30-60 cm (FIGURE 1II). The O horizon in the tundra is composed of three distinct units all in various states of decomposition: Oi, Oe, Oa. The Oi horizon (0-4 cm) is the least decomposed containing moss, and lichen. The Oe horizon (4-9 cm) shows evidence of primary decomposition. This horizon is mainly composed of sedge and tussock (Eriophorum vaginatun, and Carex spp.) root systems. The Oa horizon (9-18 cm) is the most decomposed, which consists of peat, humus and lignin. Soil color within the O horizon ranges from brown to light brown (10YR 3/4 dry, 10YR 3/2 moist) (FIGURE 1II) (SPP 1). The A horizon represents a transition from organic to mineral soils. Horizon A (19-23 cm) is characterized by cryoturbation, consisting of decomposed material from above being worked into the upper portion of the A horizon due to freezing and thawing (FIGURE 1I). Soil colors are grey (2.5Y 6/3-7/2 dry, and 5GY 5/1 moist) (FIGURE 1II) 50 (SPP 1). Horizon B (23-55 cm) is composed of silts and clays which, show evidence of gleying and redoximorphic soil features (FIGURE 1I). Gleying within the B horizon is characterized by soil colors ranging from grey (2.5Y 6/2-7/2 dry, and 5GY 4/1-5/1 moist) (FIGURE 1II) (SPP 1). Our observed soil profiles are consistent with those defined by Jorgenson (2009) for the Selawik area. Cross section 1-1’ in Figure 1b, shows the transition from the control tundra to the active slump floor. The headwall is composed mostly of glacial diamict and ice, with a small (20 cm) upper cap of organic rich peat and tussock community (the tundra environment). As a consequence, the vast majority of the material eroding into the active slump is glacial diamict from the headwall, which is transported downslope through mudflows and rill erosion on the floor of the active slump. ~60 % of the slump floor is covered with these slurries of water, fine sediment, cobbles and gravels. These materials are sufficiently saturated to support flow. There are no detectable soil profiles within the active slump. Instead, the profile (0-50 cm) is composed of unconsolidated pebbles, gravels, cobbles, silts, and clays with sparse interspersed peat material (FIGURE 1III). There was no detectable active layer in the upper meter. All active slump soil profiles showed strong evidence of gleying, with soil colors from dark grey to grey (2.5Y 5/2-6/1 dry, and N 3/ - 5GY 4/1 moist) (FIGURE 1IV) (SPP 1), due to water saturation. The stabilized slump is directly adjacent to and west of the active slump (FIGURE 1a). This feature is >500 years old based on the presence of numerous generations of black spruce logs found decaying on the surface. We use this feature to represent the likely trajectory of our active thaw slump. Cross section 2-2’ (FIGURE 1c) shows the landscape transition from tundra to stabilized slump. Unlike the transition from 51 tundra to active slump, this transition is denoted by a gently sloping hillside that transitions into a slight depression downslope. Typical soil profiles within this area consist of an O horizon (0-9 cm), an A horizon (9-13 cm), and a B horizon (13-60 cm), which contains material similar to the active slump at the base (FIGURE 1V). The O horizon consists of both an Oi and an Oe horizon, and is less decomposed than the O horizon in the tundra. The Oi horizon consists of grass, moss and lichen, which transitions into an Oe horizon that is mainly composed black spruce, and alder (Picea mariana and Alnus spp.) root systems, with primary decomposed material (FIGURE 1V). Soil colors range from 10YR 3/4-6 dry, and 10YR 3/1 moist (FIGURE 1VI) (SPP 1). The A horizon (9-13 cm) is denoted by a transition from organic to mineral material within the soil profile. Within this horizon, cryoturbation is present with material from the Oe horizon being cycled into the upper portion of the A horizon through freeze thaw action. Soil color ranges from light brown to brown (2.5Y 5/2-6/2 dry, and 5GY 4/1-N 4/0 moist) (FIGURE 1VI) (SPP 1). Horizon B (13-60 cm) is composed of silts and clays which, show evidence of gleying and redoximorphic soil features (FIGURE 1V). Gleying throughout the B horizon is characterized by soil colors ranging from light grey to grey (2.5Y 6/2-3 dry, and 5G 4/1-N 4/0 moist) (FIGURE 1VI) (SPP 1). Within the B horizon there is also a layer of unconsolidated gravels and cobbles (35-50 cm) at the base. We consider this material to be similar in composition and origin that observed on the floor of the active slump (FIGURE 1V). 52 3.5 Methods 3.5.1 Sampling Locations Sampling sites were established along our chronosequence for the collection of both soil physical properties as well as soil gases. At each of these sites, soil gases from various depths were collected first, then soil pits were dug to 60cm. Three sites were established in both the tundra and the stabilized slump. In the active slump, 4 sites where established, with one site, SL12-07 dominated by organic peat. This profile is anomalous as it represents only ~4% of the area of the slump floor. Each of these sites represents slightly different environment, vegetation composition as well as landscape position within the stabilized slump. 3.5.2 Soil Analysis Soil temperature and soil moisture were taken at depths of 3, 5, 15, 30, and 50 cm at each soil pit using a LiCor-8100A analyzer (Lincoln, NE). Soil temperature was measured using a LiCor 8100-203 soil thermistor probe attachment. Volumetric water content (VWC, volume water/volume soil), hereafter referred to as soil moisture, was measured using a Kelta-T ML2x probe (Lincoln, NE). Post-processing of soil temperature and moisture was conducted using the LI-8100 Data File Viewer (v2.0). Soil volumetric water content was adjusted for high organic content soils using the equation provided in the (LI-COR, 2007). Total soil cores of known volume were taken at each soil pit at depths of 3, 5, 15, 30, and 50 cm. These 50 samples were subsequently frozen and transported back to Idaho State University and analyzed for bulk density and gravimetric water content (GWC) following methods described by (Schumacher, 2002), and (Black, 1965), respectively. In 53 brief, bulk density was determined by drying the soil at 105°C and weighing the dry mass and sieving the soil to retain the fine fraction <2 mm. GWC was determined by drying 20 g of soil for 24 hours at 105 °C and reweighing the remaining mass. Porosity and water filled pore space (WFPS) are factors thought to be limiting to diffusivity (Firestone et al., 1989). We calculated the above parameters using measured bulk density and GWC. Porosity was calculated using the equation, % porosity = (1-(bulk density/particle density)*100). We assumed a constant particle density of 2.65 g/cm3. WFPS was calculated using the equation, WFPS (%) = (gravimetric water content x soil bulk density/1-(soil bulk density/particle density))*100 (Firestone et al., 1989; Hall and Matson, 2003). Soil samples were also analyzed for % soil organic carbon (SOC) and δ13C of soil organic carbon. Soil samples were prepared for analysis by drying 100 g of soil for 24 hours at 60 °C and then grinding it to a fine powder. Samples for carbon elemental concentrations and stable isotope ratios were analyzed at the Idaho State University’s Interdisciplinary Laboratory for Elemental and Isotopic Analysis (ILEIA) using a Costech ECS 4010 elemental analyzer interfaced to a Thermo Delta V Advantage continuous flow isotope ratio mass spectrometer. All stable isotopic data are reported in standard delta notation (δ13C) relative to the Vienna PeeDee Belemnite (VPDB) reference standard. Analytical precision, calculated from analysis of standards distributed throughout each run, was ≤ ± 0.2‰ for carbon isotopes, and < ± 0.5% of the sample value for %SOC. Effective diffusivity (DEFF)(m2 s-1) was calculated for all three chronosequence environments using the Fick’s first law transformed to calculate DEFF = -Jc x ∂c/∂x)-1 54 (Preuss et al., 2012), where Jc (µmols m-2 s-1) values are our previous measurements of CO2 efflux across the same chronosequence (Jensen et al., in review). We also differenced CO2 concentrations (∂c) (mol m-3) from depths of 0.03 and 0.50 (∂x)(m) to determine effective diffusivity. We assume that there are no net additions or losses of CO2 along this path. 3.5.3 Soil Gas Analysis Soil gas sampling equipment “dogbones” were used to collect soil gas samples from each site location at depths of 3, 5, 15, 30, and 50 cm. A dogbone is composed of a 1/4” stainless steel cylinder cut to lengths of 10, 10, 25, 40, or 60 cm. Inserted into the 1/4” cylinder was a 1/8” stainless steel rod, that was 3 cm longer. The dogbone was then pushed into the ground so that the tip of the cylinder is at the designated depth. The inner 1/8” stainless steel rod is then removed and a 10 cm section of flexible tubing connects the hollow steel to a three-way stopcock. The stopcock was then left open for 24 hours allowing free exchange to the atmosphere, re-establishing equilibrium with the soil environment. After 24 hours, the stopcock was closed, allowing for soil gases to fill the dogbone over a period of ~24 hours. Accumulated soil gas samples (5-8 ml) were then extracted from the dogbones using a syringe fitted with a stainless steel needle, and evacuated into glass exetainers (Labco Limited, United Kingdom). These samples were analyzed for concentration of both CO2 and CH4, as well as, δ13C of soil respired CO2, at Los Alamos National Energy Lab (LANL), Los Alamos, NM, USA. Delta 13C of soil respired CO2 values were measured using a GV Instruments Isoprime continuous flow isotope ratio mass spectrometer (GV Instruments, Manchester, UK) coupled to a TraceGas peripheral instrument. Briefly, 15 to 1500 uL of gas was sent 55 through an injection port and CO2 was cryogenically separated from other gases prior to introduction to the mass spectrometer. Reported results are the average of 2 duplicates. δ13C of CO2 results are reported relative to VPDB, and were calibrated off NOAA Climate Monitoring and Diagnositics Laboratory “gold” standards for CO2 concentration and isotope ratios. CO2 concentrations were measured using a GV Instruments Isoprime continuous flow isotope ratio mass spectrometer (GV Instruments, Manchester, UK) coupled to a multiflow peripheral instrument. CO2 concentration was proportionate to mass spectrometer response and calibrated using CO2/air standards of known concentration. High concentration samples were diluted 1:12 prior to analysis. Precision on 8 replicates of air within a sealed glove box was 3 ppm. CH4 concentrations were measured using an Agilent 6890A GC equipped with a packed column (Restek RT-Msieve 5A) and flame ionization detector (FID). Carrier helium flow was 1.5 mL/min, with the GC oven at 50 °C. Reported results are the average of two 200 uL injections. Concentrations were proportionate to FID response and calibrated off methane/helium standards prepared in-house. 3.5.4 Statistical Analysis Multiple linear regression and step-wise linear regression models were used to determine environmental controls on concentration of both CO2 and CH4 as well as, δ13C of soil respired CO2. Concentrations of both CO2 and CH4 were log transformed to improve normality and homoscedasticity. Other parameters such as soil moisture, temperature, porosity, and % SOC were normally distributed and thus did not require any transformation. All statistical analyses were performed in JMP 10 (Cary, NC) software. 56 3.6 Results 3.6.1 Physical Soil Properties Soil moisture in the three different chronosequence environments were relatively similar (0.3 to 0.6 cm3/cm3) (FIGURE 2a,g,m); the lowest values were in the active slump where there as little variation down the soil profile. Both the tundra and the stabilized slump at 3 cm had soil moistures equivalent to the active slump, however when transitioning through the organic layer, soil moisture doubles compared to the active slump and stays relatively constant through the mineral horizon down the soil profile (FIGURE 2a,g,m). Soil temperatures within the active slump were 3x higher than both the tundra and stabilized slump (15 to 20 °C) (FIGURE 2h). This trend was consistent down profile with the active slump displaying the least variation in temperature with depth. In contrast, both the tundra and stabilized slump decreased in temperature (~3 °C) with depth (FIGURE 2b,n) as you approach the frost table. Soil organic carbon % (SOC) showed greatest variation in the organic layers of both the tundra and the stabilized slump (FIGURE 2c,o) where values ranged from 5-40 % SOC. However, % SOC was dramatically reduced to ~3 %, when transitioning into the mineral layers in the above two environments. The active slump, which had no organic layer, had the lowest % SOC (~1-2 %) with little variation with depth (FIGURE 2i). In general, the mineral horizons of all three chronosequence environments, showed similar low trends in % SOC, as well as, little variation with soil profile depth. The highest measured bulk densities were found in the active slump (0.9-2.3 gdry/cm3), with the greatest values in the upper 10 cm. Values decreased 1.5x at 15 cm 57 and remainded relatively constant in the lower portion of the profile (FIGURE 2j). In contrast, both the tundra and stabilized slump had the lowest bulk densities (~0.2-0.4 gdry/cm3) near the surface and increased slightly with depth to values of ~0.6 g-dry/cm3 (FIGURE 2d,p). Calculated porosity has an opposite patterns compared to bulk density in all chronosequence environments. The active slump had the lowest porosity at surface (0.10.3, values are dimensionless), and doubled down profile to a depth of 15cm (FIGURE 2k). In contrast both the tundra and stabilized slump had the highest porosity (~0.8-0.9) at vegetated surface and decreased slightly to a depth of 15cm (FIGURE 2e,q). The tundra, active slump and stabilized slump showed similar porosities in their mineral horizons (~0.8) starting at 15 cm and continuing down the soil profile (FIGURE 2e,k,q). The organic horizon within the tundra showed the most variability in calculated water filled pore space (WFPS) with values ranging from (1-99 %); however, after 15 cm, the variability decreased, with most values ~25 % WFPS throughout the mineral horizon to depth (15-50 cm)( FIGURE 2f). In contrast, the stabilized slump had low variability in the upper organic layer with the lowest calculated WFPS (~15-25 %) in the upper 15 cm (FIGURE 2r). However, below 15 cm the mineral horizon within the stabilized slump showed the highest variability between sites (~1-50 %). The active slump showed no site variability and had the highest WFPS near the surface (~97 %) and drastically decreased to 10 % from 15 to 50 cm (FIGURE 2l). 58 3.6.1.1 Calculated Effective Diffusivity All environments had different calculated effective diffusivities (DEFF). Higher values indicate more connectivity between soil gases and the surface. The stabilized slump had the highest DEFF, 138 m2 day-1. In contrast, the active slump had the lowest DEFF, and was approximately four orders of magnitude lower than the stabilized slump (TABLE 1). The DEFF in the tundra was both two orders of magnitude less than the active slump and two orders more than the stabilized slump (TABLE 1). 3.6.2 Soil Gas CO2 and CH4 Concentrations We observed similar trends in CO2 and CH4 concentrations across the chronosequence soil profiles. CO2 concentrations were 2 orders of magnitude more than CH4 concentrations. CO2 concentrations in the active slump were the highest, showed the most variability throughout the soil profile among sites, and showed a general trend of increasing CO2 concentrations with depth: ~600 ppm at surface and ~10,000 ppm at depth (FIGURE 3e). In contrast, both the tundra and stabilized slump had less severe gradients in CO2 concentration (~600 ppm at surface to ~3000 ppm at depth, FIGURE 3a,i). Atmospheric CO2 concentrations for the study area were determined to be ~400 ppm. CH4 concentrations were surprisingly high within the active slump, 3x higher than either the tundra or stabilized slump, and showed the most variability with depth (FIGURE 3f). These concentrations increased with depth: ~6 ppm at surface and ~10 to 1200 ppm at depth (FIGURE 3f). In contrast, both the tundra and stabilized slump had similar CH4 concentrations (~6-30 ppm), and were consistent throughout the soil profile 59 (FIGURE 3b,j). Atmospheric CH4 concentrations for the study area were determined to be ~3 ppm. 3.6.3 Stable Isotopic Composition of Soil and Soil Gases The δ13C of soil organic matter (SOM) was similar across all soil profile chronosequence environments (-29 to -25 ‰), with the active slump being slightly heavier in composition. There was little variation in the values with depth across the chronosequence, except in the stabilized slump, which showed a slight increase in δ13C of SOM with depth. The δ13C of soil CO2 gas was variable across the chronosequence during both 2011 and 2012. In 2011, δ13C in the upper 15 cm, for all environments, ranged from -20 to -15 ‰. The stabilized slump was the only environment to become lighter (more negative) with similar value to the δ13C of soil organic matter at depth. In contrast, both the tundra and active slump δ13C of soil CO2 was extremely variable throughout the soil profile between sites. Among sites for both the tundra and active slump, we observed a shift from becoming both lighter and heavier with depth. For both the tundra and the active slump, the difference between δ13C of SOM and δ13C of soil CO2 gas was ~-10 ‰. In 2012, we observed no typical δ13C of soil CO2 gas profiles. Instead all environments were heavier than -22 ‰, with average values ~18 ‰ (FIGURE 3d,h,l). We observed the most variability both with depth and between sites in the active slump (FIGURE 3h). In general, the tundra and the active slump showed a slight trend of heavy to light δ13C within the upper 30cm (FIGURE 3d,h) whereas the stabilized slump was similar through all depths (FIGURE 3l). 60 3.6.4 Controls on Gas Concentrations and δ 13C Isotope Values Soil temperature and moisture were strong controls on CO2 concentration within the tundra and stabilized slump (r2=0.45, r2=0.49, respectively) (TABLE 2). CO2 concentrations within the tundra were controlled by soil temperature (p=0.04), whereas concentrations within the stabilized slump showed an interactive effect between soil temperature and moisture (p=0.04). In contrast, porosity (p=0.02) was the strongest control on CO2 concentrations within the active slump, with soil moisture (p=0.03) and temperature (p=0.05) exhibiting a weaker control (r2=0.61) (TABLE 2). Soil temperature and the δ13C of soil organic matter (SOM) exhibited strong controls on CH4 concentration across the soil profile chronosequence (table 2). Within the tundra environment, δ13C of SOM was the only control (r2=0.49) (p=0.03). In contrast, within the active slump, the control switched to soil temperature (r2=0.42) (p=0.003). Within the stabilized slump both soil temperature (p=0.03) and δ13C of SOM (p=0.008) had a strong control on CH4 concentrations within the soil profile (r2=0.50) (TABLE 2). Both CO2 and CH4 concentrations, as well as, the environmental variables of soil moisture and temperature exerted control on δ13C of soil CO2 gas. The only variable that exerted control in the tundra environment (r2=0.51) was CO2 concentration (p=0.006). Within the stabilized slump, the strongest control was also CO2 concentration (r2=0.87, p<0.0001), although soil temperature (p=0.03) was also controlling δ13C of CO2 gas (TABLE 2). In contrast, CH4 concentration (p=0.002) and soil moisture (p=0.004) (TABLE 2) were the main controls on the δ13C values of soil CO2 gas in the active slump (r2=0.72) (TABLE 2). 61 3.7 Discussion 3.7.1 Diffusion Limitation Findings from our study showed the highest CO2 and CH4 concentrations occur at depth in the active slump. This was seemingly in contrast with our previous work where we measured the lowest soil CO2 efflux from the active slump. Following analysis of soil properties, we found that low porosity, high water filled pore space (WFPS), and low calculated effective diffusivity all suggest that our low efflux measurements were a consequence of gas trapping rather than low production rates. Though we did not make measurements of methane flux, low diffusivity would limit the rate of these fluxes as well. In contrast to the relatively depth-invariant porosity in the tundra and stabilized slump, porosities in the upper 20 cm of active slump profiles decreased from ~0.8 to 0.4 (FIGURE 2), which we suggest limits gas diffusion and elevates both CO2 and CH4 concentrations at depth (FIGURE 3). Multiple linear regression also confirmed porosity as the strongest control on CO2 concentrations within the active slump. The active slump floor is composed of sediment remobilized from the thawing headwall, which is dominated by glacial silts and gravels. The thawed materials flow away from the headwall as a thick, viscous slurry and stabilize upon reaching lower slopes. Our findings suggest that the fine, silty sediment that rises to the top of these flows acts to reduce air-filled pore space within the upper 20 cm, decreasing porosity and “capping” the slump floor resulting in a build-up of CO2 and CH4 gases at depth. Gas concentration profiles in thawing or eroding permafrost are limited, but have been shown to both increase and decrease with depth depending on location (Michaelson et al., 2011). While there is no published work relating greenhouse gas concentrations 62 within active thaw slumps to physical soil properties, work conducted in temperate and tropical environments have shown increased CO2 concentrations at depth corresponding to either higher production rates, which correspond to organic horizons within soil profiles, or decreases in a material’s effective diffusivity (Davidson and Trumbore, 1995; Fierer et al., 2005; Scanlon et al., 2000). The active slump contains no organic horizon, evident by extremely low soil organic carbon (FIGURE 2), suggesting that rather than observing increased gas production rates; we are observing the effects of lower diffusivity in the active slump. Drastic increases (~95 %) in water filled pore space (WFPS) were also observed in the upper 20 cm of the active slump (FIGURE 2). Soils are typically considered aeration-limited when soil WFPS starts to exceed 60 % (Linn and Doran, 1984). These high values (FIGURE 2) suggest anaerobic conditions are present in the slump. This conclusion reinforced by the fact that most of the area of the slump floor (~65 %) is so saturated that it impassable (quicksand-like conditions). The combination of reduced pore volume within the top 20 cm of the active slump and the shift from air filled to water filled pore space increases gas entrapment due to slower diffusions rates of CO2 in water as opposed to air. Other studies have shown that increases in water filled pore volume slow gas diffusivity in a material, as well as, increasing gas trapping at depth (Davidson and Trumbore, 1995; Millington and Shearer, 1971; Nazaroff, 1992; Risk et al., 2008). Finally, calculated effective diffusivity across the chronosequence supported the patterns of lower CO2 efflux from the active slump compared to the other two environments. We found that the lowest CO2 efflux occurred within the active slump for both 2011 and 2012, corresponding to the lowest calculated effective diffusivity (TABLE 63 1). In contrast, the stabilized slump’s effective diffusivity was five orders of magnitude greater than the active slump, corresponding to the highest mean CO2 efflux in both 2011 and 2012. Although the stabilized slump has the same material as the active slump at depth, this environment has been completely re-vegetated with black spruce and a more diffusive soil profile has been re-established. Research relating soil moisture to CO2 and CH4 production within retrogressive thaw slumps is limited, but collectively, our findings suggest that the retrogressive thaw slump dramatically alters the soil physical environment and strongly influences the production and fate of the CO2 and CH4 through the interactive controls of diffusivity and moisture. Consistent with our findings, the few other studies that have evaluated increasing soil moisture conditions on CO2 indicate decreases in CO2 efflux and shifts carbon production to methanogenesis (Alewell et al., 2011; Lee et al., 2012; Michaelson et al., 2011; Oberbauer et al., 2007; Walter et al., 2008). We expand on this idea below. 3.7.2 Micro-Soil Environments In contrast to our initial expectation that soil profiles within the active slump would have more aerobic activity due to increased availability carbon after thaw and slumping, we found that the majority of soil profiles across the chronosequence to be anaerobic in nature as indicated by (1) the abundance of methane, (2) gleying and redoximorphic features, and (3) significant fractionation of carbon, leading to lighter δ13C values in CO2 gas. Collectively, we interpret the results to suggest that conditions in the active thaw slumps may shift carbon cycling, at least in the short term, towards anaerobic metabolic pathways such as methanogenesis owing to the drastically altered soil environment conditions. 64 Methane concentrations were 3-5 orders of magnitude higher in the active slump and increased with depth, when compared to the tundra or stabilized slump. Indeed, methane concentrations within the active slump were consistent (mean 97 ppm) with those reported from Alaskan lakes undergoing permafrost degradation, and other waterlogged tundra environments (5-1000 ppm) (Michaelson et al., 2011; Thebrath et al., 1993; Torn and Chapin, 1993; von Fischer et al., 2010; Walter et al., 2008). Saturation existed within the active slump in 2012, as indicated by the ~95 % water filled pore space in the upper part of the soil column in the more well drained areas and the fact that 60 % of the slump was too saturated to walk on. Anaerobic soil conditions, as evidenced by gleying and redoximorphic features, were also observed throughout the soil profile in the active slump and in the lower portions of the soil profile for both the tundra and stabilized slump. This assertion is supported by dark grey to grey gleyed soil colors (5GY 4/1-5/2, N 4/0-3/0). Gleying was observed in all the soil profiles across the chronosequence. Gleying appeared to be the strongest in the active slump, where the entire profile was dominated by dark grey soil colors of 2.5Y 6/1 dry, and 5GY 4/1 – N 4/0 moist (FIGURE SP1). In contrast the mineral horizons in the tundra and stabilized slump where extremely mottled with patchy dark grey colors 2.5Y 6/2 dry, and 5GY 4/1-3 moist (FIGURE SP1)driven by fluctuations in water-table position (Simonson and Boersma, 1972). Within the arctic, it has been shown that the gleying and redoximorphic features we observed across our chronosequence are primarily due to anaerobic soil conditions (Jorgenson et al., 2009; Melke and Chodorowski, 2006; Sjögersten et al., 2006). 65 Finally, the δ13C values of soil CO2 was, across the sites, on average -15 ‰, which is 2-3x heavier than our theoretically predicted value of ~-22.6 ‰ (based on -4.4‰ fractionation) if CO2 was derived from SOC (Amundson et al., 1998; Cerling et al., 1991), suggesting that metabolic pathways were shifting from aerobic to anaerobic ones. Our expectations were that the δ13C of soil respired CO2 would increase toward the surface, starting with values close to the δ13C of soil organic matter (-27 ‰) and equilibrating with the atmosphere (-8 ‰) (Amundson et al., 1998; Cerling et al., 1991). However, this pattern was only observed in the warmer and dryer 2011 and only in the stabilized slump (FIGURE 3). Rather than observing a fractionation effect of the SOM pool, our values of δ13C of CO2 appear to reflect fractionation associated with anaerobic soil conditions and the processes of methanogenesis over a shorter time period thereby resulting in heavier δ13C-CO2 values. Arctic soil lab incubations under both aerobic and anaerobic soil conditions, as well as, field work on littoral lakes in Alaska, support this conclusion showing that heavy δ13C values of CO2 (-15 ‰) are formed under anaerobic soil conditions and can be influenced by methanogenesis (Bates et al., 2011; Lee et al., 2012; Thebrath et al., 1993). Similar patterns of δ13C of CO2 becoming heavier with depth as seen in our soil profiles (FIGURE 3) have been observed across the arctic in waterlogged soils, and these patterns have also been correlated to increases in methane production within the soil profile (Alewell et al., 2011; Krull and Retallack, 2000; Zaccone et al., 2008). 3.8 Implications No studies to our knowledge have examined changes in physical soil characteristics and micro-environment shifts that occur as a result of large, rapidly evolving, thermal- 66 erosional feature development. Although thermokarst features are predicted to increase in frequency, (Gooseff et al., 2009; Lacelle et al., 2010; Rowland et al., 2010) our results from a low % SOC substrate slump indicate that changes to the physical soil structure may prevent features like ours from functioning as hotspots of CO2 efflux to the atmosphere during their active phase as previously thought. Our study determined that quantifying a material’s diffusivity limitations are key to controlling the efflux of CO2 and possibly CH4 to the atmosphere from retrogressive thaw slumps. Although CO2 efflux from active features is below the initial tundra efflux, with subsequent feature stabilization and rebuilding of the soil profile, our research indicates that these features will become greater source of CO2 efflux to the environment. Geomorphic controls governing the initiation and development of thaw slumps influence overall CO2 efflux. Our findings show that thermokarst features on hillslopes, such as thaw slumps, may be expected to have well-drained aerobic soil conditions but material properties may dictate largely anaerobic conditions. This ultimately affects carbon cycling by shifting decomposition pathways to methanogensis, resulting in possible greater CH4 emissions than previously considered. These shifts in soil conditions could lead to underestimation of these features carbon fluxes and warrant further study. Thermokarst CO2 efflux studies primarily rely on surface efflux measurements, which may not represent production occurring at depth. Quantifying physical soil profile properties, as well as, soil micro-environment shifts over small spatial scales, will become important predictors of the effects of rapidly evolving thermo-erosional features on the global carbon cycle. Until we focus on not only the surface but also soil profile 67 changes, our ability to accurately spatially upscale these features effects on the global carbon cycle will be limited. 3.9 Conclusion We use a soil profile thaw slump chronosequence to examine how changes in the soil environment due to rapidly evolving thermokarst features, affect soil column CO2 production as well as the resulting soil CO2 efflux. 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In b and c, boxes labeled A, B, C represent the rough positions of representative soil profiles shown in I, III, and V respectively. These schematic soil profiles from the tundra, active slump, and stabilized slump are paired with photographs (II, IV, and VI) of soil profiles from the Selawik slump. 75 Figure 2. Soil depth profiles of physical soil properties across the chronosequence: tundra (a-f), active slump (g-l), and stabilized slump (m-r). Representative soil profiles for each chronosequence are shown on the far left and correspond to representative profiles in figure 1-I, III, V. The horizontal grey line in the tundra and stabilized slump plots, marks the approximate transition from organic to mineral horizons. 76 Table 1. Calculated effective diffusivity and average daily CO2 efflux (g CO2-C/m2/day) in 2011 and 2012 for each chronosequence environment: tundra, active slump, stabilized slump. Active slump has the lowest effective diffusivity corresponding to the lowest CO2 efflux for both 2011 and 2012. Environment Effective Diffusivity (m2/day) Tundra Active Slump Stabilized Slump 2011 CO2 efflux (g-CO2-C/m2/day) 5.24 0.012 3.32±0.0271 1.75±0.151 2012 CO2 efflux (g-CO2-C/m2/day) 138 5.14±0.271 3.24±0.131 1.89±0.161 0.86±0.231 1 Jensen et al., (in review) Table 2. Controls on CO2 and CH4 concentrations and δ13C of soil CO2 gas. Porosity exhibited the strongest control on CO2 concentrations in the active slump. CO2 Concentration (ppm) CH4 Concentration (ppm) δ 13C of soil CO2 gas (‰) Tundra R2 = 0.45 Soil Temperature (p=0.039) R2 = 0.49 δ 13C of SOM (p=0.029) R2 = 0.51 CO2 Concentration (p=0.0056) Active Slump R2 = 0.61 Porosity (p=0.017) Soil Moisture (p=0.025) Soil Temperature x Porosity (p=0.048) R2 = 0.49 Soil Temperature x Soil Moisture (p=0.041) R2 = 0.42 Soil Temperature (p=0.0028) R2 = 0.72 CH4 Concentration (p=0.0015) Soil Moisture (p=0.0037) R2 = 0.50 Soil Temperature (p=0.026) δ 13C of SOM (p=0.0076) R2 = 0.87 CO2 concentration (p<0.0001) Soil Temperature (p=0.029) Stabilized Slump 77 Figure 3. Soil depth profiles of CO2 and CH4 concentrations, as well as, δ13C of soil organic matter (SOM) and δ13C-CO2 across the chronosequence: tundra (a-d), active slump (e-h), stabilized slump (i-l). Representative soil profiles for each chronosequence are shown in the first column. Note that 2012 CO2 and CH4 gas concentrations are on log axes. Comparison of both δ13C of SOM (solid lines) and δ13C of CO2 (dashed lines) in 2011 and 2012 show that soil gases are considerably lighter than the soil material that they are derived from. For all plots within the tundra and stabilized slump, the grey horizontal line represents the transition from organic to mineral horizons. 78 4 Thesis Summary 4.1 Implications This study is the first to examine how retrogressive thaw slumps give rise to changes in soil physical properties that either limit or enhance soil CO2 efflux and how these characteristics evolve over time. In a warming world, rapidly evolving, thermal erosional features like the Selawik slump are predicted to increase in frequency (Gooseff et al., 2009; Lacelle et al., 2010; Rowland et al., 2010), and therefore warrant further study. Our findings indicate that quantifying the initial substrate quantity, used as a proxy for carbon availability, as well as the displaced material’s diffusivity will be of great importance to understanding CO2 efflux in these rapidly changing environments. The arctic is a heterogeneous landscape where soil organic matter (SOM) ranges from 1-3% as seen at the active Selawik slump, to 90-100% as seen in the stabilized slump and yedoma soils of northern Alaska and Siberia (Kanevskiy et al., 2011). Higher carbon fluxes are observed in environments with higher SOM (our tundra and stabilized slump), suggesting a critical need to quantify soil carbon and other soil properties in these environments. On the floor of the active slump, materiel diffusivity also appears to play an important role in controlling the efflux of CO2 and possibly CH4 to the atmosphere. Although we observed CO2 concentrations at depth in the active slump to be 3x greater than that of the tundra or stabilized slump, the surface efflux was ~2x lower than in the tundra or stabilized slump in both 2011 and 2012. Low porosity, high water filled pore space and calculations of effective diffusivity across the chronosequence all suggest that the soil profile changes occurring due to the initiation of rapidly evolving thermokarst 79 dampen the release of CO2 gas to the atmosphere. However, with subsequent stabilization and development of a soil profile, the active Selawik slump may become a greater source of CO2 efflux to the environment than the initial tundra environment. Quantifying the evolution of physical soil properties of thaw slumps will become important in determining their long-term effect on the global carbon cycle. Our research also suggests that geomorphic controls governing the initiation and development of thaw slumps influences overall CO2 efflux. Thermokarst features such as retrogressive thaw slumps which occur on hillslopes might be expected to be welldrained with aerobic soil conditions but we found largely anaerobic soil environments. This ultimately affects carbon cycling by decreasing decomposition rate, which may ultimately lead to slower soil C emissions. Due to the heterogeneous soil microenvironments that occur within these features at relatively small spatial scales, our ability to project the effect of thaw slumps on the global carbon cycle remains limited. 4.2 Conclusion We examined CO2 efflux along a thaw slump chronosequence from one of the largest known retrogressive thaw slumps. To our knowledge, this is the only study to measure CO2 efflux, and possible controls in a thermokarst feature of this type and magnitude. In contrast to our initial expectations that the active slump would have higher soil CO2 effluxes, we found that soil CO2 effluxes in the active thaw slump were approximately half that measured in the tundra and stabilized slump for 2011 and 2012. While some studies have shown a strong correlation with soil temperature and moisture controlling CO2 efflux, our research suggests that physical soil properties such as bulk 80 density and soil organic matter also influence CO2 efflux. Further study of these local controls will improve our understanding of carbon-cycling within these features. We use a soil profile thaw slump chronosequence to examine how changes in the soil environment due to rapidly evolving thermokarst features, affect soil column CO2 production as well as the resulting soil CO2 efflux. To our knowledge, this is the only study to examine changes in physical soil characteristics and the resulting effect on CO2 efflux. Within the active slump, consolidated slump floor material limit gas diffusion, inhibiting CO2 surface efflux and impounding CO2 at depth. We also determined that the majority of our chronosequence exists under anaerobic soil conditions, despite high surface slopes. 81 5 Supplemental Material Figure 1. Photographs of each soil profile within the thaw slump chronosequence. Note the absence of a dark, upper organic horizon in the active slump. The wooden pegs delineate the depths where soil and gas were sampled: 3, 5, 15, 30, and 50cm. Because photographs were taken looking down into the pits, the length scale becomes compressed with depth. 82
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