Nitrous oxide emissions from agricultural soils challenge climate sustainability in the US Corn Belt.

Agricultural landscapes are the largest source of anthropogenic nitrous oxide (N2O) emissions, but their specific sources and magnitudes remain contested. In the US Corn Belt, a globally important N2O source, in-field soil emissions were reportedly too small to account for N2O measured in the regional atmosphere, and disproportionately high N2O emissions from intermittent streams have been invoked to explain the discrepancy. We collected 3 y of high-frequency (4-h) measurements across a topographic gradient, including a very poorly drained (intermittently flooded) depression and adjacent upland soils. Mean annual N2O emissions from this corn-soybean rotation (7.8 kg of N2O-N ha-1⋅y-1) were similar to a previous regional top-down estimate, regardless of landscape position. Synthesizing other Corn Belt studies, we found mean emissions of 5.6 kg of N2O-N ha-1⋅y-1 from soils with similar drainage to our transect (moderately well-drained to very poorly drained), which collectively comprise 60% of corn-soybean-cultivated soils. In contrast, strictly well-drained soils averaged only 2.3 kg of N2O-N ha-1⋅y-1 Our results imply that in-field N2O emissions from soils with moderately to severely impaired drainage are similar to regional mean values and that N2O emissions from well-drained soils are not representative of the broader Corn Belt. On the basis of carbon dioxide equivalents, the warming effect of direct N2O emissions from our transect was twofold greater than optimistic soil carbon gains achievable from agricultural practice changes. Despite the recent focus on soil carbon sequestration, addressing N2O emissions from wet Corn Belt soils may have greater leverage in achieving climate sustainability.

Resolving the influence of lignin on soil organic matter decomposition with mechanistic models and continental-scale data.

Confidence in model estimates of soil CO2 flux depends on assumptions regarding fundamental mechanisms that control the decomposition of litter and soil organic carbon (SOC). Multiple hypotheses have been proposed to explain the role of lignin, an abundant and complex biopolymer that may limit decomposition. We tested competing mechanisms using data-model fusion with modified versions of the CN-SIM model and a 571-day laboratory incubation dataset where decomposition of litter, lignin, and SOC was measured across 80 soil samples from the National Ecological Observatory Network. We found that lignin decomposition consistently decreased over time in 65 samples, whereas in the other 15 samples, lignin decomposition subsequently increased. These "lagged-peak" samples can be predicted by low soil pH, high extractable Mn, and fungal community composition as measured by ITS PC2 (the second principal component of an ordination of fungal ITS amplicon sequences). The highest-performing model incorporated soil biogeochemical factors and daily dynamics of substrate availability (labile bulk litter:lignin) that jointly represented two hypotheses (C substrate limitation and co-metabolism) previously thought to influence lignin decomposition. In contrast, models representing either hypothesis alone were biased and underestimated cumulative decomposition. Our findings reconcile competing hypotheses of lignin decomposition and suggest the need to precisely represent the role of lignin and consider soil metal and fungal characteristics to accurately estimate decomposition in Earth-system models.

High carbon losses from oxygen-limited soils challenge biogeochemical theory and model assumptions.

Oxygen (O2 ) limitation contributes to persistence of large carbon (C) stocks in saturated soils. However, many soils experience spatiotemporal O2  fluctuations impacted by climate and land-use change, and O2 -mediated climate feedbacks from soil greenhouse gas emissions remain poorly constrained. Current theory and models posit that anoxia uniformly suppresses carbon (C) decomposition. Here we show that periodic anoxia may sustain or even stimulate decomposition over weeks to months in two disparate soils by increasing turnover and/or size of fast-cycling C pools relative to static oxic conditions, and by sustaining decomposition of reduced organic molecules. Cumulative C losses did not decrease consistently as cumulative O2 exposure decreased. After >1 year, soils anoxic for 75% of the time had similar C losses as the oxic control but nearly threefold greater climate impact on a CO2 -equivalent basis (20-year timescale) due to high methane (CH4 ) emission. A mechanistic model incorporating current theory closely reproduced oxic control results but systematically underestimated C losses under O2  fluctuations. Using a model-experiment integration (ModEx) approach, we found that models were improved by varying microbial maintenance respiration and the fraction of CH4 production in total C mineralization as a function of O2 availability. Consistent with thermodynamic expectations, the calibrated models predicted lower microbial C-use efficiency with increasing anoxic duration in one soil; in the other soil, dynamic organo-mineral interactions implied by our empirical data but not represented in the model may have obscured this relationship. In both soils, the updated model was better able to capture transient spikes in C mineralization that occurred following anoxic-oxic transitions, where decomposition from the fluctuating-O2 treatments greatly exceeded the control. Overall, our data-model comparison indicates that incorporating emergent biogeochemical properties of soil O2 variability will be critical for effectively modeling C-climate feedbacks in humid ecosystems.

Trade-offs in soil carbon protection mechanisms under aerobic and anaerobic conditions.

Oxygen (O2 ) limitation is generally understood to suppress oil carbon (C) decomposition and is a key mechanism impacting terrestrial C stocks under global change. Yet, O2 limitation may differentially impact kinetic or thermodynamic versus physicochemical C protection mechanisms, challenging our understanding of how soil C may respond to climate-mediated changes in O2 dynamics. Although O2 limitation may suppress decomposition of new litter C inputs, release of physicochemically protected C due to iron (Fe) reduction could potentially sustain soil C losses. To test this trade-off, we incubated two disparate upland soils that experience periodic O2 limitation-a tropical rainforest Oxisol and a temperate cropland Mollisol-with added litter under either aerobic (control) or anaerobic conditions for 1 year. Anoxia suppressed total C loss by 27% in the Oxisol and by 41% in the Mollisol relative to the control, mainly due to the decrease in litter-C decomposition. However, anoxia sustained or even increased decomposition of native soil-C (11.0% vs. 12.4% in the control for the Oxisol and 12.5% vs. 5.3% in the control for the Mollisol, in terms of initial soil C mass), and it stimulated losses of metal- or mineral-associated C. Solid-state 13 C nuclear magnetic resonance spectroscopy demonstrated that anaerobic conditions decreased protein-derived C but increased lignin- and carbohydrate-C relative to the control. Our results indicate a trade-off between physicochemical and kinetic/thermodynamic C protection mechanisms under anaerobic conditions, whereby decreased decomposition of litter C was compensated by more extensive loss of mineral-associated soil C in both soils. This challenges the common assumption that anoxia inherently protects soil C and illustrates the vulnerability of mineral-associated C under anaerobic events characteristic of a warmer and wetter future climate.

Interactive global change factors mitigate soil aggregation and carbon change in a semi-arid grassland.

The ongoing global change is multi-faceted, but the interactive effects of multiple drivers on the persistence of soil carbon (C) are poorly understood. We examined the effects of warming, reactive nitrogen (N) inputs (12 g N m-2  year-1 ) and altered precipitation (+ or - 30% ambient) on soil aggregates and mineral-associated C in a 4 year manipulation experiment with a semi-arid grassland on China's Loess Plateau. Our results showed that in the absence of N inputs, precipitation additions significantly enhanced soil aggregation and promoted the coupling between aggregation and both soil fungal biomass and exchangeable Mg2+ . However, N inputs negated the promotional effects of increased precipitation, mainly through suppressing fungal growth and altering soil pH and clay-Mg2+ -OC bridging. Warming increased C content in the mineral-associated fraction, likely by increasing inputs of root-derived C, and reducing turnover of existing mineral-associated C due to suppression of fungal growth and soil respiration. Together, our results provide new insights into the potential mechanisms through which multiple global change factors control soil C persistence in arid and semi-arid grasslands. These findings suggest that the interactive effects among global change factors should be incorporated to predict the soil C dynamics under future global change scenarios.

From pools to flow: The PROMISE framework for new insights on soil carbon cycling in a changing world.

Soils represent the largest terrestrial reservoir of organic carbon, and the balance between soil organic carbon (SOC) formation and loss will drive powerful carbon-climate feedbacks over the coming century. To date, efforts to predict SOC dynamics have rested on pool-based models, which assume classes of SOC with internally homogenous physicochemical properties. However, emerging evidence suggests that soil carbon turnover is not dominantly controlled by the chemistry of carbon inputs, but rather by restrictions on microbial access to organic matter in the spatially heterogeneous soil environment. The dynamic processes that control the physicochemical protection of carbon translate poorly to pool-based SOC models; as a result, we are challenged to mechanistically predict how environmental change will impact movement of carbon between soils and the atmosphere. Here, we propose a novel conceptual framework to explore controls on belowground carbon cycling: Probabilistic Representation of Organic Matter Interactions within the Soil Environment (PROMISE). In contrast to traditional model frameworks, PROMISE does not attempt to define carbon pools united by common thermodynamic or functional attributes. Rather, the PROMISE concept considers how SOC cycling rates are governed by the stochastic processes that influence the proximity between microbial decomposers and organic matter, with emphasis on their physical location in the soil matrix. We illustrate the applications of this framework with a new biogeochemical simulation model that traces the fate of individual carbon atoms as they interact with their environment, undergoing biochemical transformations and moving through the soil pore space. We also discuss how the PROMISE framework reshapes dialogue around issues related to SOC management in a changing world. We intend the PROMISE framework to spur the development of new hypotheses, analytical tools, and model structures across disciplines that will illuminate mechanistic controls on the flow of carbon between plant, soil, and atmospheric pools.

Enrichment of Lignin-Derived Carbon in Mineral-Associated Soil Organic Matter.

A modern paradigm of soil organic matter proposes that persistent carbon (C) derives primarily from microbial residues interacting with minerals, challenging older ideas that lignin moieties contribute to soil C because of inherent recalcitrance. We proposed that aspects of these old and new paradigms can be partially reconciled by considering interactions between lignin decomposition products and redox-sensitive iron (Fe) minerals. An Fe-rich tropical soil (with C4 litter and either 13C-labeled or unlabeled lignin) was pretreated with different durations of anaerobiosis (0-12 days) and incubated aerobically for 317 days. Only 5.7 ± 0.2% of lignin 13C was mineralized to CO2 versus 51.2 ± 0.4% of litter C. More added lignin-derived C (48.2 ± 0.9%) than bulk litter-derived C (30.6 ± 0.7%) was retained in mineral-associated organic matter (MAOM; density >1.8 g cm-3), and 12.2 ± 0.3% of lignin-derived C vs 6.4 ± 0.1% of litter C accrued in clay-sized (<2 µm) MAOM. Longer anaerobic pretreatments increased added lignin-derived C associated with Fe, according to extractions and nanoscale secondary ion mass spectrometry (NanoSIMS). Microbial residues are important, but lignin-derived C may also contribute disproportionately to MAOM relative to bulk litter-derived C, especially following redox-sensitive biogeochemical interactions.

Reconciling multiple impacts of nitrogen enrichment on soil carbon: plant, microbial and geochemical controls.

Impacts of reactive nitrogen (N) inputs on ecosystem carbon (C) dynamics are highly variable, and the underlying mechanisms remain unclear. Here, we proposed a new conceptual framework that integrates plant, microbial and geochemical mechanisms to reconcile diverse and contrasting impacts of N on soil C. This framework was tested using long-term N enrichment and acid addition experiments in a Mongolian steppe grassland. Distinct mechanisms could explain effects of N on particulate and mineral-associated soil C pools, potentially explaining discrepancies among previous N addition studies. While plant production predominated particulate C changes, N-induced soil acidification strongly affected mineral-associated C through decreased microbial growth and pH-sensitive associations between iron and aluminium minerals and C. Our findings suggest that effects of N-induced acidification on microbial respiration and geochemical properties should be included in Earth system models that predict ecosystem C budgets under future N deposition/input scenarios.

An optical method for carbon dioxide isotopes and mole fractions in small gas samples: Tracing microbial respiration from soil, litter, and lignin.

RATIONALE: Carbon dioxide isotope (δ13 C value) measurements enable quantification of the sources of soil microbial respiration, thus informing ecosystem C dynamics. Tunable diode lasers (TDLs) can precisely measure CO2 isotopes at low cost and high throughput, but are seldom used for small samples (≤5 mL). We developed a TDL method for CO2 mole fraction ([CO2 ]) and δ13 C analysis of soil microcosms. METHODS: Peaks in infrared absorbance following constant volume sample injection to a carrier were used to independently measure [12 CO2 ] and [13 CO2 ] for subsequent calculation of δ13 C values. Using parallel soil incubations receiving differing C substrates, we partitioned respiration from three sources using mixing models: native soil organic matter (SOM), added litter, and synthetic lignin containing a 13 C label at Cß of the propyl side chain. RESULTS: Once-daily TDL calibration enabled accurate quantification of δ13 C values and [CO2 ] compared with isotope ratio mass spectrometry (IRMS), with long-term external precision of 0.17 and 0.31‰ for 5 and 1 mL samples, respectively, and linear response between 400 and 5000 µmol mol-1 CO2 . Production of CO2 from native soil C, added litter, and lignin Cß varied over four orders of magnitude. Multiple-pool first-order decay models fitted to data (R2  > 0.98) indicated substantially slower turnover for lignin Cß (17 years) than for the dominant pool of litter (1.3 years) and primed soil C (3.9 years). CONCLUSIONS: Our TDL method provides a flexible, precise, and high-throughput (60 samples h-1 ) alternative to IRMS for small samples. This enables the use of C isotopes in increasingly sophisticated experiments to test biogeochemical controversies, such as the fate of lignins in soil.

Persistent Urban Influence on Surface Water Quality via Impacted Groundwater.

Growing urban environments stress hydrologic systems and impact downstream water quality. We examined a third-order catchment that transitions from an undisturbed mountain environment into urban Salt Lake City, Utah. We performed synoptic surveys during a range of seasonal baseflow conditions and utilized multiple lines of evidence to identify mechanisms by which urbanization impacts water quality. Surface water chemistry did not change appreciably until several kilometers into the urban environment, where concentrations of solutes such as chloride and nitrate increase quickly in a gaining reach. Groundwater springs discharging in this gaining system demonstrate the role of contaminated baseflow from an aquifer in driving stream chemistry. Hydrometric and hydrochemical observations were used to estimate that the aquifer contains approximately 18% water sourced from the urban area. The carbon and nitrogen dynamics indicated the urban aquifer also serves as a biogeochemical reactor. The evidence of surface water-groundwater exchange on a spatial scale of kilometers and time scale of months to years suggests a need to evolve the hydrologic model of anthropogenic impacts to urban water quality to include exchange with the subsurface. This has implications on the space and time scales of water quality mitigation efforts.

Stream Nitrogen Inputs Reflect Groundwater Across a Snowmelt-Dominated Montane to Urban Watershed.

Snowmelt dominates the hydrograph of many temperate montane streams, yet little work has characterized how streamwater sources and nitrogen (N) dynamics vary across wildland to urban land use gradients in these watersheds. Across a third-order catchment in Salt Lake City, Utah, we asked where and when groundwater vs shallow surface water inputs controlled stream discharge and N dynamics. Stream water isotopes (δ(2)H and δ(18)O) reflected a consistent snowmelt water source during baseflow. Near-chemostatic relationships between conservative ions and discharge implied that groundwater dominated discharge year-round across the montane and urban sites, challenging the conceptual emphasis on direct stormwater inputs to urban streams. Stream and groundwater NO3(-) concentrations remained consistently low during snowmelt and baseflow in most montane and urban stream reaches, indicating effective subsurface N retention or denitrification and minimal impact of fertilizer or deposition N sources. Rather, NO3(-) concentrations increased 50-fold following urban groundwater inputs, showing that subsurface flow paths potentially impact nutrient loading more than surficial land use. Isotopic composition of H2O and NO3(-) suggested that snowmelt-derived urban groundwater intercepted NO3(-) from leaking sewers. Sewer maintenance could potentially mitigate hotspots of stream N inputs at mountain/valley transitions, which have been largely overlooked in semiarid urban ecosystems.

Scale-dependent linkages between nitrate isotopes and denitrification in surface soils: implications for isotope measurements and models.

Natural abundance nitrate (NO3 (-)) isotopes represent a powerful tool for assessing denitrification, yet the scale and context dependence of relationships between isotopes and denitrification have received little attention, especially in surface soils. We measured the NO3 (-) isotope compositions in soil extractions and lysimeter water from a semi-arid meadow and lawn during snowmelt, along with the denitrification potential, bulk O2, and a proxy for anaerobic microsites. Denitrification potential varied by three orders of magnitude and the slope of δ(18)O/δ(15)N in soil-extracted NO3 (-) from all samples measured 1.04 ± 0.12 (R (2) = 0.64, p < 0.0001), consistent with fractionation from denitrification. However, δ(15)N of extracted NO3 (-) was often lower than bulk soil δ(15)N (by up to 24 ‰), indicative of fractionation during nitrification that was partially overprinted by denitrification. Mean NO3 (-) isotopes in lysimeter water differed from soil extractions by up to 19 ‰ in δ(18)O and 12 ‰ in δ(15)N, indicating distinct biogeochemical processing in relatively mobile water versus soil microsites. This implies that NO3 (-) isotopes in streams, which are predominantly fed by mobile water, do not fully reflect terrestrial soil N cycling. Relationships between potential denitrification and δ(15)N of extracted NO3 (-) showed a strong threshold effect culminating in a null relationship at high denitrification rates. Our observations of (1) competing fractionation from nitrification and denitrification in redox-heterogeneous surface soils, (2) large NO3 (-) isotopic differences between relatively immobile and mobile water pools, (3) and the spatial dependence of δ(18)O/δ(15)N relationships suggest caution in using NO3 (-) isotopes to infer site or watershed-scale patterns in denitrification.

Lignin decomposition is sustained under fluctuating redox conditions in humid tropical forest soils.

Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia is thought to suppress lignin decomposition, yet potential effects of oxygen (O2 ) variability in surface soils have not been explored. Here, we tested the impact of redox fluctuations on lignin breakdown in humid tropical forest soils during ten-week laboratory incubations. We used synthetic lignins labeled with 13 C in either of two positions (aromatic methoxyl or propyl side chain Cß ) to provide highly sensitive and specific measures of lignin mineralization seldom employed in soils. Four-day redox fluctuations increased the percent contribution of methoxyl C to soil respiration relative to static aerobic conditions, and cumulative methoxyl-C mineralization was statistically equivalent under static aerobic and fluctuating redox conditions despite lower soil respiration in the latter treatment. Contributions of the less labile lignin Cß to soil respiration were equivalent in the static aerobic and fluctuating redox treatments during periods of O2 exposure, and tended to decline during periods of O2 limitation, resulting in lower cumulative Cß mineralization in the fluctuating treatment relative to the static aerobic treatment. However, cumulative mineralization of both the Cß - and methoxyl-labeled lignins nearly doubled in the fluctuating treatment relative to the static aerobic treatment when total lignin mineralization was normalized to total O2 exposure. Oxygen fluctuations are thought to be suboptimal for canonical lignin-degrading microorganisms. However, O2 fluctuations drove substantial Fe reduction and oxidation, and reactive oxygen species generated during abiotic Fe oxidation might explain the elevated contribution of lignin to C mineralization. Iron redox cycling provides a potential mechanism for lignin depletion in soil organic matter. Couplings between soil moisture, redox fluctuations, and lignin breakdown provide a potential link between climate variability and the biochemical composition of soil organic matter.

Mechanisms underlying episodic nitrate and phosphorus leaching from poorly drained agricultural soils.

Poorly drained depressions within tile-drained croplands can have disproportionate environmental and agronomic impacts, but mechanisms controlling nutrient leaching remain poorly understood. We monitored nitrate and soluble reactive phosphorus (SRP) leaching using zero-tension soil lysimeters across a depression to upland gradient over 2 years in a corn-soybean (Zea mays L.-Glycine max [L.] Merr.) field in Iowa. We also measured stable isotopes (δ15N and δ18O) of nitrate to examine its sources and transformations. SRP concentrations peaked during winter and early spring after phosphorus (P) fertilization (mean = 3 mg P L-1), with highest values in the depression, and SRP was relatively stable thereafter (mean = 0.3 mg P L-1) irrespective of periods of high soil moisture that led to widespread iron (Fe) reduction across the field. During a near-average precipitation year, nitrate stable isotopes indicated direct leaching of fertilizer nitrate within days of application, followed by nitrification of fertilizer ammonium and several weeks of denitrification in depressional soils. Nevertheless, nitrate concentrations remained high (mean = 28 mg N L-1) in the depression despite strong isotopic evidence for denitrification (>48% N removal). During a wet year, nitrate concentrations were lower in the depression than upland and nitrate isotopes were highly variable, consistent with nearly complete nitrate removal by denitrification in the depression and significant denitrification in upland soils. We conclude that poorly drained depressional soils can potentially decrease nitrate leaching via denitrification under sustained wet conditions, but they inconsistently denitrify and are vulnerable to high nitrate and SRP losses when soils are not saturated, especially following fertilization.

Insights on agricultural nitrate leaching from soil block mesocosms.

Quantifying nitrate leaching in agricultural fields is often complicated by inability to capture all water draining through a specific area. We designed and tested undisturbed soil monoliths (termed "soil block mesocosms") to achieve complete collection of drainage. Each mesocosm measures 1.5 m × 1.5 m × 1.2 m and is enclosed by steel on the sides and bottom with a single outlet to collect drainage. We compared measurements from replicate mesocosms planted to corn (Zea mays L.) with a nearby field experiment with tile-drained plots ("drainage plots"), and with drainage from nearby watersheds from 2020 through 2022 under drought conditions. Annual mesocosm drainage volumes were 6.5-24.6 cm greater than from the drainage plots, likely because the mesocosms were isolated from the subsoil and could not store groundwater below the drain depth, whereas the drainage plots accumulated infiltration as groundwater. Thus, we obtained consistent nitrate leaching measurements from the mesocosms even when some drainage plots yielded no water. Despite drainage volume differences, mean flow-weighted nitrate concentrations were similar between mesocosms and drainage plots in 2 of 3 years. Mesocosm annual drainage volume was 8.7 cm lower to 16.7 cm higher than watershed drainage, likely due to lagged influences of groundwater. Corn yields were lower in mesocosms than drainage plots in 2020, but with irrigation, yields were similar in subsequent years. Mean 2020 surface soil moisture and temperature were similar between the mesocosms and nearby fields. Based on these comparisons, the mesocosms provide a robust method to measure nitrate leaching with lower variability than field plots.

Poorly drained depressions can be hotspots of nutrient leaching from agricultural soils.

Much of the US Corn Belt has been drained with subsurface tile to improve crop production, yet poorly drained depressions often still flood intermittently, suppressing crop growth. Impacts of depressions on field-scale nutrient leaching are unclear. Poor drainage might promote denitrification and physicochemical retention of phosphorus (P), but ample availability of water and nutrients might exacerbate nutrient leaching from cropped depressions. We monitored nitrate, ammonium, and reactive P leaching across multiple depression-to-upland transects in north-central Iowa, using resin lysimeters buried and retrieved on an annual basis. Crops included conventional corn/soybean (Zea mays/Glycine max) rotations measured at fields with and without a winter rye (Secale cereale) cover crop, as well as juvenile miscanthus (Miscanthus × giganteus), a perennial grass. Leaching of nitrogen (N) and P was greater in depressions than in uplands for most transects and years. The median difference in nutrient leaching between paired depressions and uplands was 56 kg N ha-1 year-1 for nitrate (p = 0.0008), 0.6 kg N ha-1 year-1 for ammonium (p = 0.03), and 2.4 kg P ha-1 year-1 for reactive P (p = 0.006). Transects managed with a cover crop or miscanthus tended to have a smaller median difference in nitrate (but not ammonium or P) leaching between depressions and uplands. Cropped depressions may be disproportionate sources of N and P to downstream waters despite their generally poor drainage characteristics, and targeted management with cover crops or perennials might partially mitigate these impacts for N, but not necessarily for P.

Extreme low-flow conditions in a dual-chamber denitrification bioreactor contribute to pollution swapping with low landscape-scale impact.

Denitrification bioreactors are an effective edge-of-field conservation practice for nitrate (NO3) reduction from subsurface drainage. However, these systems may produce other pollutants and greenhouse gases during NO3 removal. Here a dual-chamber woodchip bioreactor system experiencing extreme low-flow conditions was monitored for its spatiotemporal NO3 and total organic carbon dynamics in the drainage water. Near complete removal of NO3 was observed in both bioreactor chambers in the first two years of monitoring (2019-2020) and in the third year of monitoring in chamber A, with significant (p < 0.01) reduction of the NO3-N each year in both chambers with 8.6-11.4 mg NO3-N L-1 removed on average. Based on the NO3 removal observed, spatial monitoring of sulfate (SO4), dissolved methane (CH4), and dissolved nitrous oxide (N2O) gases was added in the third year of monitoring (2021). In 2021, chambers A and B had median hydraulic residence times (HRTs) of 64 h and 39 h, respectively, due to varying elevations of the chambers, with drought conditions making the differences more pronounced. In 2021, significant production of dissolved CH4 was observed at rates of 0.54 g CH4-C m-3 d-1 and 0.07 g CH4-C m-3 d-1 in chambers A and B, respectively. In chamber A, significant removal (p < 0.01) of SO4 (0.23 g SO4 m-3 d-1) and dissolved N2O (0.21 mg N2O-N m-2 d-1) were observed, whereas chamber B produced N2O (0.36 mg N2O-N m-2 d-1). Considering the carbon dioxide equivalents (CO2e) on an annual basis, chamber A had loads (~12,000 kg CO2e ha-1 y-1) greater than comparable poorly drained agricultural soils; however, the landscape-scale impact was small (<1 % change in CO2e) when expressed over the drainage area treated by the bioreactor. Under low-flow conditions, pollution swapping in woodchip bioreactors can be reduced at HRTs <50 h and NO3 concentrations >2 mg N L-1.

Contrasting geochemical and fungal controls on decomposition of lignin and soil carbon at continental scale.

Lignin is an abundant and complex plant polymer that may limit litter decomposition, yet lignin is sometimes a minor constituent of soil organic carbon (SOC). Accounting for diversity in soil characteristics might reconcile this apparent contradiction. Tracking decomposition of a lignin/litter mixture and SOC across different North American mineral soils using lab and field incubations, here we show that cumulative lignin decomposition varies 18-fold among soils and is strongly correlated with bulk litter decomposition, but not SOC decomposition. Climate legacy predicts decomposition in the lab, and impacts of nitrogen availability are minor compared with geochemical and microbial properties. Lignin decomposition increases with some metals and fungal taxa, whereas SOC decomposition decreases with metals and is weakly related with fungi. Decoupling of lignin and SOC decomposition and their contrasting biogeochemical drivers indicate that lignin is not necessarily a bottleneck for SOC decomposition and can explain variable contributions of lignin to SOC among ecosystems.