Recent increases in annual, seasonal, and extreme methane fluxes driven by changes in climate and vegetation in boreal and temperate wetland ecosystems.

Climate warming is expected to increase global methane (CH4 ) emissions from wetland ecosystems. Although in situ eddy covariance (EC) measurements at ecosystem scales can potentially detect CH4 flux changes, most EC systems have only a few years of data collected, so temporal trends in CH4 remain uncertain. Here, we use established drivers to hindcast changes in CH4 fluxes (FCH4 ) since the early 1980s. We trained a machine learning (ML) model on CH4 flux measurements from 22 [methane-producing sites] in wetland, upland, and lake sites of the FLUXNET-CH4 database with at least two full years of measurements across temperate and boreal biomes. The gradient boosting decision tree ML model then hindcasted daily FCH4 over 1981-2018 using meteorological reanalysis data. We found that, mainly driven by rising temperature, half of the sites (n = 11) showed significant increases in annual, seasonal, and extreme FCH4 , with increases in FCH4 of ca. 10% or higher found in the fall from 1981-1989 to 2010-2018. The annual trends were driven by increases during summer and fall, particularly at high-CH4 -emitting fen sites dominated by aerenchymatous plants. We also found that the distribution of days of extremely high FCH4 (defined according to the 95th percentile of the daily FCH4 values over a reference period) have become more frequent during the last four decades and currently account for 10-40% of the total seasonal fluxes. The share of extreme FCH4 days in the total seasonal fluxes was greatest in winter for boreal/taiga sites and in spring for temperate sites, which highlights the increasing importance of the non-growing seasons in annual budgets. Our results shed light on the effects of climate warming on wetlands, which appears to be extending the CH4 emission seasons and boosting extreme emissions.

Modeled production, oxidation, and transport processes of wetland methane emissions in temperate, boreal, and Arctic regions.

Wetlands are the largest natural source of methane (CH4 ) to the atmosphere. The eddy covariance method provides robust measurements of net ecosystem exchange of CH4 , but interpreting its spatiotemporal variations is challenging due to the co-occurrence of CH4 production, oxidation, and transport dynamics. Here, we estimate these three processes using a data-model fusion approach across 25 wetlands in temperate, boreal, and Arctic regions. Our data-constrained model-iPEACE-reasonably reproduced CH4 emissions at 19 of the 25 sites with normalized root mean square error of 0.59, correlation coefficient of 0.82, and normalized standard deviation of 0.87. Among the three processes, CH4 production appeared to be the most important process, followed by oxidation in explaining inter-site variations in CH4 emissions. Based on a sensitivity analysis, CH4 emissions were generally more sensitive to decreased water table than to increased gross primary productivity or soil temperature. For periods with leaf area index (LAI) of ≥20% of its annual peak, plant-mediated transport appeared to be the major pathway for CH4 transport. Contributions from ebullition and diffusion were relatively high during low LAI (<20%) periods. The lag time between CH4 production and CH4 emissions tended to be short in fen sites (3 ± 2 days) and long in bog sites (13 ± 10 days). Based on a principal component analysis, we found that parameters for CH4 production, plant-mediated transport, and diffusion through water explained 77% of the variance in the parameters across the 19 sites, highlighting the importance of these parameters for predicting wetland CH4 emissions across biomes. These processes and associated parameters for CH4 emissions among and within the wetlands provide useful insights for interpreting observed net CH4 fluxes, estimating sensitivities to biophysical variables, and modeling global CH4 fluxes.

Observational constraints reduce model spread but not uncertainty in global wetland methane emission estimates.

The recent rise in atmospheric methane (CH4 ) concentrations accelerates climate change and offsets mitigation efforts. Although wetlands are the largest natural CH4 source, estimates of global wetland CH4 emissions vary widely among approaches taken by bottom-up (BU) process-based biogeochemical models and top-down (TD) atmospheric inversion methods. Here, we integrate in situ measurements, multi-model ensembles, and a machine learning upscaling product into the International Land Model Benchmarking system to examine the relationship between wetland CH4 emission estimates and model performance. We find that using better-performing models identified by observational constraints reduces the spread of wetland CH4 emission estimates by 62% and 39% for BU- and TD-based approaches, respectively. However, global BU and TD CH4 emission estimate discrepancies increased by about 15% (from 31 to 36 TgCH4 year-1 ) when the top 20% models were used, although we consider this result moderately uncertain given the unevenly distributed global observations. Our analyses demonstrate that model performance ranking is subject to benchmark selection due to large inter-site variability, highlighting the importance of expanding coverage of benchmark sites to diverse environmental conditions. We encourage future development of wetland CH4 models to move beyond static benchmarking and focus on evaluating site-specific and ecosystem-specific variabilities inferred from observations.

Methane Bubble Size Distributions, Flux, and Dissolution in a Freshwater Lake.

The majority of methane produced in many anoxic sediments is released via ebullition. These bubbles are subject to dissolution as they rise, and dissolution rates are strongly influenced by bubble size. Current understanding of natural methane bubble size distributions is limited by the difficulty in measuring bubble sizes over wide spatial or temporal scales. Our custom optical bubble size sensors recorded bubble sizes and release timing at 8 locations in Upper Mystic Lake, MA continuously for 3 months. Bubble size distributions were spatially heterogeneous even over relatively small areas experiencing similar flux, suggesting that localized sediment conditions are important to controlling bubble size. There was no change in bubble size distributions over the 3 month sampling period, but mean bubble size was positively correlated with daily ebullition flux. Bubble data was used to verify the performance of a widely used bubble dissolution model, and the model was then used to estimate that bubble dissolution accounts for approximately 10% of methane accumulated in the hypolimnion during summer stratification, and at most 15% of the diffusive air-water-methane flux from the epilimnion.

Substantial hysteresis in emergent temperature sensitivity of global wetland CH4 emissions.

Wetland methane (CH4) emissions ([Formula: see text]) are important in global carbon budgets and climate change assessments. Currently, [Formula: see text] projections rely on prescribed static temperature sensitivity that varies among biogeochemical models. Meta-analyses have proposed a consistent [Formula: see text] temperature dependence across spatial scales for use in models; however, site-level studies demonstrate that [Formula: see text] are often controlled by factors beyond temperature. Here, we evaluate the relationship between [Formula: see text] and temperature using observations from the FLUXNET-CH4 database. Measurements collected across the globe show substantial seasonal hysteresis between [Formula: see text] and temperature, suggesting larger [Formula: see text] sensitivity to temperature later in the frost-free season (about 77% of site-years). Results derived from a machine-learning model and several regression models highlight the importance of representing the large spatial and temporal variability within site-years and ecosystem types. Mechanistic advancements in biogeochemical model parameterization and detailed measurements in factors modulating CH4 production are thus needed to improve global CH4 budget assessments.

Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters.

Atrazine leaching from biochar-amended soils.

The herbicide atrazine is used extensively throughout the United States, and is a widespread groundwater and surface water contaminant. Biochar has been shown to strongly sorb organic compounds and could be used to reduce atrazine leaching. We used lab and field experiments to determine biochar impacts on atrazine leaching under increasingly heterogeneous soil conditions. Application of pine chip biochar (commercially pyrolyzed between 300 and 550 °C) reduced cumulative atrazine leaching by 52% in homogenized (packed) soil columns (p=0.0298). Biochar additions in undisturbed soil columns did not significantly (p>0.05) reduce atrazine leaching. Mean peak groundwater atrazine concentrations were 53% lower in a field experiment after additions of 10 t ha(-1) acidified biochar (p=0.0056) relative to no biochar additions. Equivalent peat applications by dry mass had no effect on atrazine leaching. Plots receiving a peat-biochar mixture showed no reduction, suggesting that the peat organic matter may compete with atrazine for biochar sorption sites. Several individual measurement values outside the 99% confidence interval in perched groundwater concentrations indicate that macropore structure could contribute to rare, large leaching events that are not effectively reduced by biochar. We conclude that biochar application has the potential to decrease peak atrazine leaching, but heterogeneous soil conditions, especially preferential flow paths, may reduce this impact. Long-term atrazine leaching reductions are also uncertain.