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Black carbon (BC) is a significant component of the global carbon cycle both in terrestrial and aquatic systems. Dissolved black carbon (DBC) is a significant portion of the total dissolved organic carbon (DOC) pool and represents a major flux of recalcitrant carbon to the coastal and deep oceans. Dissolved black carbon can originate from multiple sources related to its relative biogeochemical reactivity with the dynamics of highly recalcitrant DBC integral to long-term sequestration. Thus, understanding how the more recalcitrant fractions of DBC varies in diverse catchments is critical and currently underexplored. We used hydrogen pyrolysis to isolate the fraction of DBC with aromatic clusters above 7 rings, representing the more stable components. Here we report the dynamics of DBCHyPy over a hydrological year in a temperate catchment, with a long history of coal mining extraction. Quarterly measurements of DBC were undertaken from two main channel and four tributary sites. Hydrogen pyrolysis derived DBC comprised a significant percentage of the total DOC flux (3.2% to 28.3%) and included significant spatial variability. Unlike other studies examining more reactive DBC fractions, bulk DOC concentrations and DBCHyPy were poorly correlated when considered over an annual scale. Rather, DBCHyPy was correlated with indicators of groundwater such as dissolved inorganic carbon and conductivity. Data suggest a consistent source of DBCHyPy not subject to the same mobilisation drivers as DOC, which shows substantial seasonality. Rather, our data shows a potentially consistent supply of stable DBC originating from the coal mining-influenced groundwater. Petrogenic sources of DBC have been poorly constrained to date, the data presented here suggests in some catchments it may be significant and yield catchment scale DOC-DBC decoupling. The dynamics of DBC have implications for carbon fluxes, pollution transport and water quality/treatment requirements. These preliminary findings suggest potentially complex drivers in spatially heterogeneous catchments, contrasting with previous work finding tight DOC-DBC mobilisation dynamics. [ABSTRACT FROM AUTHOR]

Carbon cycles in coastal waters are highly sensitive to human activities and play important roles in global carbon budgets. CO2 sink–source behavior is regulated by spatiotemporal variations in net biological productivity, but the contribution of macrophyte habitats including macroalgae aquaculture to atmospheric CO2 removal has not been well quantified. We investigated the variations in the carbonate system and dissolved organic carbon (DOC) in human-impacted macrophyte habitats and analyzed the biogeochemical drivers for the variations of these processes. Cultivated macroalgal metabolism (photosynthesis, respiration, calcification, and DOC release) was quantified by in situ field-bag experiments. Cultivated macroalgae took up dissolved inorganic carbon (DIC) (16.2–439 mmol-C m−2 day−1) and released DOC (1.2–146 mmol-C m−2 day−1). We estimated that seagrass beds and macroalgae farming contributed 0.8 and 0.4 mmol-C m−2 day−1 of the in situ total CO2 removal (5.7 and 6.7 mmol-C m−2 day−1, respectively) during their growing period in a semi-enclosed embayment but efficient water exchange (i.e., short residence time) in an open coastal area precluded detection of the contribution of macrophyte habitats to the CO2 removal. Although hydrological processes, biological metabolism, and organic carbon storage processes would contribute to the net CO2 sink–source behavior, our analyses distinguished the contribution of macrophytes from other factors. Our findings imply that macroalgae farming, in addition to restoring and creating macrophyte habitats, has potential for atmospheric CO2 removal. [ABSTRACT FROM AUTHOR]

This study has proposed that organic matter transfer and transformation into and through a peatland is dominated by preferential loss of carbohydrates and the retention of lignin-like molecules. Here we used elemental analysis and thermogravimetric analysis to analyse the biomass, litter, peat soil profile, particulate organic matter, and dissolved organic matter fluxes sampled from a continental raised bog in comparison a maritime blanket bog. The macromolecular composition and thermodynamic analysis showed that in the raised bog there had been little or no transformation of the organic matter and the accumulation was rapid with comparatively little transformation with only 13% loss of cellulose by 1 m depth compared to 92% removal of cellulosic material in the blanket bog. The lack of transformation is reflected in a difference in long term carbon accumulation rates between raised and blanket bog sites. We propose that raised bogs, with their lack of a stream outfall, have high stable water tables that mean the pore water become thermodynamically closed and reactions cease higher in the peat profile than in a blanket bog where sloping sites mean a frequent flushing of pore water and discharge of water leading to fluctuating water tables, flushing of reaction products and pore spaces remaining open. [ABSTRACT FROM AUTHOR]

The effects of tree pollen on precipitation chemistry are not fully understood and this can lead to misinterpretations of element deposition in European forests. We investigated the relationship between forest throughfall (TF) element fluxes and the Seasonal Pollen Integral (SPIn) using linear mixed-effects modelling (LME). TF was measured in 1990–2018 during the main pollen season (MPS, arbitrary two months) in 61 managed, mostly pure, even-aged Fagus, Quercus, Pinus, and Picea stands which are part of the ICP Forests Level II network. The SPIn for the dominant tree genus was observed at 56 aerobiological monitoring stations in nearby cities. The net contribution of pollen was estimated as the TF flux in the MPS minus the fluxes in the preceding and succeeding months. In stands of Fagus and Picea, two genera that do not form large amounts of flowers every year, TF fluxes of potassium (K+), ammonium-nitrogen (NH4+-N), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) showed a positive relationship with SPIn. However- for Fagus- a negative relationship was found between TF nitrate-nitrogen (NO3−-N) fluxes and SPIn. For Quercus and Pinus, two genera producing many flowers each year, SPIn displayed limited variability and no clear association with TF element fluxes. Overall, pollen contributed on average 4.1–10.6% of the annual TF fluxes of K+ > DOC > DON > NH4+-N with the highest contribution in Quercus > Fagus > Pinus > Picea stands. Tree pollen appears to affect TF inorganic nitrogen fluxes both qualitatively and quantitatively, acting as a source of NH4+-N and a sink of NO3−-N. Pollen appears to play a more complex role in nutrient cycling than previously thought. [ABSTRACT FROM AUTHOR]

Recent studies suggest aluminum (Al) likely plays a role in the ocean carbon cycle by altering the biological carbon fixation and carbon decomposition of marine diatoms. However, it remains speculative whether Al has similar effects on other ecologically important phytoplankton groups such as the globally important nitrogen-fixing cyanobacterium, Trichodesmium. Here we report the influence of Al on carbon fixation and decomposition in non-axenic cultures of Trichodesmium erythraeum IMS101 (CCMP 1985). By using radiocarbon, and adding oceanic relevant amounts of dissolved Al (yielding concentrations of 40 and 200 nM) along with non-Al-amended controls, we investigated the changes in particulate organic carbon (POC) of Trichodesmium (> 2 μm, Trichodesmium POC), and free-living bacteria (0.2–2 μm, bacterial POC), and dissolved organic carbon (< 0.2 μm, DOC) over a 116-day growth period. The results showed that the rates of increase of POC in the declining growth phase of T. erythraeum were significantly higher (by 11–14%) in the Al-enriched treatments than in the control, and this Al-enhanced carbon fixation is consistent with previous observations on marine diatoms. On the other hand, unlike diatoms, the POC from T. erythraeum decomposed faster in the Al-enriched treatments during the first decay phase when bacterial POC and DOC increased along with the decomposition of Trichodesmium POC. Further addition of the same amounts of Al (again calculated to increase the Al concentration by 40 and 200 nM) was performed on day 71. This treatment was designed to mimic Al supply from sediment after the settling of Trichodesmium colonies to the ocean bottom. Following this second addition, the decomposition rate of both Trichodesmium POC and DOC slowed down by 20–27% and 31–62%, respectively, during the second decay phase, when DOC and bacterial POC decreased. The study suggests that Al fertilization in the surface ocean via dust deposition may increase the net carbon fixation and associated nitrogen fixation by Trichodesmium, and thus the supply of new nitrogen to the euphotic zone, whereas Al from sediment may decrease the decomposition rate of decaying Trichodesmium settled to the ocean bottom. [ABSTRACT FROM AUTHOR]

The dissolved organic carbon (DOC) export from land to ocean via rivers is a significant term in the global C cycle, and has been modified in many areas by human activity. DOC exports from large global rivers are fairly well quantified, but those from smaller river systems, including those draining oceanic regions, are generally under-represented in global syntheses. Given that these regions typically have high runoff and high peat cover, they may exert a disproportionate influence on the global land–ocean DOC export. Here we describe a comprehensive new assessment of the annual riverine DOC export to estuaries across the island of Great Britain (GB), which spans the latitude range 50–60° N with strong spatial gradients of topography, soils, rainfall, land use and population density. DOC yields (export per unit area) were positively related to and best predicted by rainfall, peat extent and forest cover, but relatively insensitive to population density or agricultural development. Based on an empirical relationship with land use and rainfall we estimate that the DOC export from the GB land area to the freshwater-seawater interface was 1.15 Tg C year−1 in 2017. The average yield for GB rivers is 5.04 g C m−2 year−1, higher than most of the world's major rivers, including those of the humid tropics and Arctic, supporting the conclusion that under-representation of smaller river systems draining peat-rich areas could lead to under-estimation of the global land–ocean DOC export. The main anthropogenic factor influencing the spatial distribution of GB DOC exports appears to be upland conifer plantation forestry, which is estimated to have raised the overall DOC export by 0.168 Tg C year−1. This is equivalent to 15% of the estimated current rate of net CO2 uptake by British forests. With the UK and many other countries seeking to expand plantation forest cover for climate change mitigation, this 'leak in the ecosystem' should be incorporated in future assessments of the CO2 sequestration potential of forest planting strategies. [ABSTRACT FROM AUTHOR]

Climate change is melting glaciers and altering watershed biogeochemistry across the globe, particularly in regions dominated by mountain glaciers, such as southeast Alaska. Glacier dominated watersheds exhibit distinct dissolved organic matter (DOM) characteristics compared to forested and vegetated watersheds. However, there is a paucity of information on how stream DOM composition changes as glaciers retreat and terrestrial ecosystem succession ensues. Importantly, it is unclear over what timescales these transformations occur. Here, we used bulk, isotopic and ultrahigh resolution molecular-level techniques to assess how streamwater DOM composition evolves in response to glacier retreat and subsequent terrestrial ecosystem succession. For this, water samples were collected from eleven streams across a chronosequence spanning a temporal gradient 0 to ~ 1400 years since glacier retreat in coastal, southeast Alaska. During the first ~ 200 years since glacier retreat, stream DOM showed marked and consistent changes in bulk, isotopic, and molecular-level composition. In particular, there was a decreased relative abundance (RA) of ancient, energy-rich (e.g., elevated aliphatic contribution), low aromaticity (e.g., low SUVA254 and AImod) DOM and an increased RA of soil and vegetation derived aromatic DOM (e.g., more depleted δ13C, elevated condensed aromatic and polyphenolic contribution) that had a modern radiocarbon age. After ~ 200 years of ecosystem development, DOM composition was comparable to that observed for other temperate and arctic forested watersheds without permafrost influence. These results underscore the timelines on which glacier retreat may have substantial impacts on watershed biogeochemistry and coastal ecosystems that receive DOM from these rapidly changing landscapes. [ABSTRACT FROM AUTHOR]

Dissolved organic matter (DOM) is a heterogeneous mixture of organic compounds that is produced through both microbial degradation and abiotic leaching of solid phase organic matter, and by a wide range of metabolic processes in algae and higher plants. DOM is ubiquitous throughout the hydrologic cycle and plays an important role in watershed management for drinking water supply as well as many aspects of aquatic ecology and geochemistry. Due to its wide-ranging effects in natural waters and analytical challenges, the focal research questions regarding DOM have varied since the 1920s. A standard catchment-scale model has emerged to describe the environmental controls on DOM concentrations. Modest concentrations of DOM are found in atmospheric deposition, large increases occur in throughfall and shallow soil flow paths, and variable concentrations in surface waters occur largely as a result of the extent to which hydrologic flow paths encounter deeper mineral soils, wetlands or shallow organic-rich riparian soils. Both production and consumption of DOM occur in surface waters but appear to frequently balance, resulting in relatively constant concentrations with distance downstream in most streams and rivers. Across biomes the concentration and composition of DOM in flowing waters is driven largely by soil processes or direct inputs to channels, but high levels can be found in streams and rivers from the tropics to the poles. Seven central challenges and opportunities in the study of DOM should frame ongoing research. These include maintaining or establishing long-term records of changes in concentrations and fluxes over time, capitalizing on the use of sensors to describe short-term DOM dynamics in aquatic systems, integrating the full carbon cycle into understanding of watershed and aquatic DOM dynamics, understanding the role of DOM in evasion of greenhouse gases from inland waters, unraveling the enigma of dissolved organic nitrogen, documenting gross versus net DOM fluxes, and moving beyond an emphasis on functional ecological significance to understanding the evolutionary significance of DOM in a wide range of environments. [ABSTRACT FROM AUTHOR]

Landcover changes have altered the natural carbon cycle; however, most landcover studies focus on either forest conversion to agriculture or urban, rarely both. We present differences in dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) molecular composition within Upper Mississippi River Basin low order streams and rivers draining one of three dominant landcovers (forest, agriculture, and urban). Streams draining forest and urban landcovers have greater DOC concentrations, likely driven by differences in carbon sourcing, microbial processing, and soil disturbance. Using Fourier transform-ion cyclotron resonance mass spectrometry, 24% of assigned molecular formulae are common across all landcovers. Relative abundances of N-,S- heteroatomic formulae (CHON, CHOS, CHONS) are higher for agricultural and urban streams, with agricultural stream DOM having more N-containing formulae compared to urban stream DOM, which has more S-containing formulae. Higher N-,S- heteroatomic formulae abundance, along with enrichment in aliphatic, N-aliphatic, and highly unsaturated and phenolic (low O/C) compound categories within agricultural and urban stream DOM are likely to result from increased anthropogenic inputs, autochthonous production, and microbial processing associated with agricultural and urban impacts. Reduced N-,S- heteroatomic formulae abundances in forested stream DOM, along with enrichments in condensed aromatics, polyphenolics, and highly unsaturated phenolic (high O/C) compound categories, likely reflect greater contributions from surrounding organic-rich forest soil and vegetation. Overall, landcover change from forested to agriculture lowers DOC concentrations and changes from forested to agriculture or urban increases autochthonous, and presumably more biolabile, DOM contributions with ramifications for stream biogeochemical cycling. [ABSTRACT FROM AUTHOR]

How sea level rise (SLR) alters carbon (C) dynamics in tidal salt marsh soils is unresolved. Changes in hydrodynamics could influence organo-mineral associations, influencing dissolved organic carbon (DOC) fluxes. As SLR increases the duration of inundation, we hypothesize that lateral DOC export will increase due to reductive dissolution of C-bearing iron (Fe) oxides, destabilizing soil C stocks and influencing greenhouse gas emissions. To test this, soil cores (0–8 cm depth) were collected from the high marsh of a temperate salt marsh that currently experiences changes in water level and soil redox oscillation due to spring-neap tides. Mesocosms experimentally simulated SLR by continuously inundating high marsh soils and were compared to mesocosms with Control conditions, where the water level oscillated on a spring-neap cycle. Porewater DOC, lateral DOC, and porewater reduced Fe (Fe2+) concentrations were significantly higher in SLR treatments (1.7 ± 0.5 mM, 0.63 ± 0.14 mM, and 0.15 ± 0.11 mM, respectively) than Control treatments (1.2 ± 0.35 mM, 0.56 ± 0.15 mM, and 0.08 ± 01 mM, respectively Solid phase analysis with Fe extended X-ray absorption fine-structure spectroscopy further revealed that SLR led to > 3 times less Fe oxide-C coprecipitates than Control conditions In addition, the overall global warming potential (GWP) decreased under SLR due to suppressed CO2 emissions. Our data suggest that SLR may increase lateral C export of current C stocks by dissolving C-bearing Fe oxides but decrease the overall GWP from emissions of soil trace gases. These findings have implications for understanding the fate of SOC dynamics under future SLR scenarios. [ABSTRACT FROM AUTHOR]

Nitrogen (N) inputs to developed coastlines are linked with multiple ecosystem and socio-economic impacts worldwide such as algal blooms, habitat/resource deterioration, and hypoxia. This study investigated the microbial and biogeochemical processes associated with recurrent, seasonal bottom-water hypoxia in an urban estuary, western Long Island Sound (WLIS), that receives high N inputs. A 2-year (2020–2021) field study spanned two hypoxia events and entailed surface and bottom depth water sampling for dissolved nutrients as inorganic N (DIN; ammonia-N and nitrite + nitrate (N + N)), organic N, orthophosphate, organic carbon (DOC), as well as chlorophyll a and bacterial abundances. Physical water quality data were obtained from concurrent conductivity, temperature, and depth casts. Results showed that dissolved organic matter was highest at the most-hypoxic locations, DOC was negatively and significantly correlated with bottom-water dissolved oxygen (Pearson's r = −0.53, p = 0.05), and ammonia-N was the dominant DIN form pre-hypoxia before declining throughout hypoxia. N + N concentrations showed the reverse, being minimal pre-hypoxia then increasing during and following hypoxia, indicating that ammonia oxidation likely contributed to the switch in dominant DIN forms and is a key pathway in WLIS water column nitrification. Similarly, at the most hypoxic sampling site, bottom depth bacteria concentrations ranged ~ 1.8 × 104–1.1 × 105 cells ml−1 pre-hypoxia, declined throughout hypoxia, and were positively and significantly correlated (Pearson's r = 0.57; p = 0.03) with ammonia-N, confirming that hypoxia influences N-cycling within LIS. These findings provide novel insight to feedbacks between major biogeochemical (N and C) cycles and hypoxia in urban estuaries. [ABSTRACT FROM AUTHOR]

Uranium contamination of groundwater remains a pressing problem at many former uranium mining and milling operations, such as the Rifle, Integrated Field Research Challenge (IFRC) site. Biostimulation of the subsurface with an organic carbon source such as acetate, followed by the microbially-induced reductive precipitation of uranium has been proposed as an effective remediation strategy. While uranium bioreduction has been studied in several field experiments, the transformation and fate of injected carbon remains poorly understood. This study evaluated the impact of added organic carbon on the long-term biogeochemical attenuation of uranium in the subsurface of a former mill tailings site. Fluorescence and ultraviolet–visible absorbance analyses were used together with dissolved organic carbon (DOC) measurements to track organic carbon dynamics during and post-biostimulation of the 2011 Rifle IFRC experiment. An electron mass balance was performed on well CD01 to account for any unidentified carbon sinks. Measured DOC values increased to 1.76 mM-C during biostimulation, and to 3.18 mM-C post-biostimulation over background DOC values of 0.3–0.4 mM-C. Elevated DOC levels persisted for 90 days after acetate injections ceased. The electron mass balance revealed that assumed electron acceptors would not account for the total amount of acetate consumed. Excitation–emission matrices showed an increase in signals associated with soluble microbial products, during biostimulation, which disappeared post-biostimulation despite an increase in total DOC. Specific ultraviolet absorbance analyses, indicated that DOC present post-biostimulation is less aromatic in nature, compared to background DOC. Our results suggest that microbes convert injected acetate into a form of solid phase organic matter that may be available to sustain iron reduction post-stimulation.

Water pollution disrupts the ecological integrity of urbanized river systems, but its impacts on riverine metabolic processes and carbon fluxes are poorly studied in developing countries. Three seasonal field surveys were combined with two high-resolution measurements and an in situ incubation experiment to investigate the effects of untreated wastewater on organic matter biodegradation and the partial pressure of CO2 (pCO2) along the Mekong–Tonle Sap network around Phnom Penh. High-resolution measurements during the dry-season survey exhibited large downstream increases in pCO2 along the Mekong reaches receiving Tonle Sap inflows carrying urban sewage, contrasting with little spatial variation during a monsoon survey when the Mekong floodwater reversed the Tonle Sap flow. The monsoonal and dry-season surveys revealed flooding-induced homogenization and large spatial divergences in dissolved organic carbon (DOC) concentration and its δ13C and Δ14C between the Tonle Sap and connected Mekong reaches. During the 3-day incubation of Mekong waters, alone or mixed with sewage, a large initial nocturnal increase in pCO2 in sewage-supplemented river water exceeded the subsequent daytime CO2 uptake by phytoplankton photosynthesis varying with light exposure. This, combined with the preferential consumption of labile DOC components displaying protein-like fluorescence, implies sewage-enhanced biodegradation of riverine organic matter. These results suggest that neglecting wastewater-enhanced CO2 production in urbanized river basins during long dry periods can result in a significant underestimation of riverine CO2 emissions. [ABSTRACT FROM AUTHOR]

Heterotrophic bacteria typically take up directly dissolved organic matter due to the small molecular size, although both particulate and dissolved organic matter have labile (easily consumed) compounds. Tropical coastal waters are important ecosystems because of their high productivity. However, few studies have determined bacterial cycling (i.e. carbon uptake by bacteria and allocation for bacterial biomass and respiration) of dissolved organic carbon in coastal tropical waters, and none has determined bacterial cycling of total and dissolved organic carbon simultaneously. In this study we followed bacterial biomass and production, and organic carbon changes over short-term (12 days) dark incubations with (total organic carbon, TOC) and without particulate organic carbon additions (dissolved organic carbon, DOC). The study was performed at three sites along the middle stretch of the Great Barrier Reef (GBR) during the dry and wet seasons. Our results show that the bacterial growth efficiency is low (0.1–11.5%) compared to other coastal tropical systems, and there were no differences in the carbon cycling between organic matter sources, seasons or locations. Nonetheless, more carbon was consumed in the TOC compared to the DOC incubations, although the proportion allocated to biomass and respiration was similar. This suggests that having more bioavailable substrate in the particulate form did not benefit bacteria. Overall, our study indicates that when comparing the obtained respiration rates with previously measured primary production rates, the GBR is a heterotrophic system. More detailed studies are required to fully explore the mechanisms used by bacteria to cycle TOC and DOC in tropical coastal waters. [ABSTRACT FROM AUTHOR]

Wildfires cause direct and indirect CO2 emissions due to combustion and post-fire decomposition. Approximately half of temperate forest carbon (C) is stored in soil, so post-fire soil C cycling likely impacts forest C sink strength. Soil C sink strength is partly determined by soil microbial anabolism versus catabolism, which dictates the amount of C respired versus stored in microbial biomass. Fires affect soil C availability and composition, changes that could alter carbon use efficiency (CUE) and microbial biomass production, potentially influencing C sink recovery. Wildfire intensity is forecast to increase in forests of the western United States, and understanding the impacts of fire intensity on microbial anabolism is necessary for predicting fire-climate feedbacks. Our objective was to determine the influence of soil heating intensity and pyrogenic organic matter (PyOM) on microbial anabolism. We simulated the effects of fire intensity by heating soils to 100 or 200 °C for 30 min in a muffle furnace, and we amended the soils with charred or uncharred organic matter. Higher intensity soil heating (200 °C) led to lower microbial biomass carbon (MBC) accumulation, greater C respiration, and lower CUE proxies compared to unheated soils. Conversely, lower intensity heating (100 °C) yielded MBC accumulation and estimated CUE that was similar to unheated soils. Soils amended with PyOM exhibited similar MBC accumulation compared to uncharred organic matter, but lower CO2 emissions. These results indicate that high intensity soil heating decreases soil C-sink strength over the short-term by decreasing the amount of microbial anabolism relative to catabolism. [ABSTRACT FROM AUTHOR]

Mercury is a global pollutant of critical concern but its movement through terrestrial upland systems is poorly understood. We investigated whether forest harvesting practices and varying hydrological conditions resulted in different subsurface transport pathways, fluxes and proportions of recent vs. ambient mercury in runoff. In a multiyear field experiment, we measured subsurface lateral mercury fluxes at three adjacent hillslope plots, including one that was not harvested, one where all biomass was removed after harvest, and one where residual biomass was left after harvest. Two different enriched stable mercury isotopes (Hg tracer) were added to the hillslope plots (one pre-harvest and one post-harvest) to help differentiate between recently deposited mercury and ambient mercury in soils, as well as to identify changes between years. More Hg tracer was recovered in runoff post-harvest (16.2–54.0 μg) than pre-harvest (3.7–11.8 μg) from both harvested hillslopes, but differences between harvested hillslopes were not significant. The movement of Hg tracer was governed by periods of near surface preferential flow that was enhanced by forest harvesting. Runoff Hg tracer concentrations were significantly and inversely related to both event runoff magnitude (R2 = 0.85) and runoff ratio (R2 = 0.81). Insignificant relationships between Hg tracer concentrations and both DOC and precipitation pH suggest that for recently deposited mercury, the overarching controls on mobilization were hydrological rather than biogeochemical. The dependence of mercury mobilization on the routing of precipitation to different subsurface flow pathways suggests an important interaction between climate and the age of mercury pools for mercury transport from terrestrial landscapes. [ABSTRACT FROM AUTHOR]

The biogeochemical cycles of carbon (C) and nitrogen (N) are inextricably linked for a range of reactions. For coupled reactions such as denitrification to occur, however, solutes must be found together in space and time. Using the framework of concentration-discharge (c-Q) relationships, we examine the frequency of synchronous C and N export (i.e. identical c-Q behavior) across a river network using > 5 years of high-frequency sensor data. We demonstrate that across space and time the export of C and N to a river network is asynchronous 57% of the time. The probability of simultaneous export in largely forested watersheds demonstrates little temporal structure, while in more human-impacted watersheds, we observe the highest frequency of asynchronous c-Q behavior. We discuss the implications of synchronous c-Q behavior for solute flux estimation models and develop a theoretical framework for predicting where within a landscape we expect the probability of coupled C and N reactions to be greatest. By simultaneously comparing the variability in C and N c-Q relationships we develop an integrated framework for predicting synchronous export of solutes. [ABSTRACT FROM AUTHOR]

We report a data set of dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition (stable carbon isotope signatures, absorption and fluorescence properties) obtained from samples collected in Lake Victoria, a large lake in East Africa. Samples were collected in 2018–2019 along a bathymetric gradient (bays to open waters), during three contrasting seasons: long rainy, short rainy and dry, which corresponded to distinctly water column mixing regimes, respectively, stratified, semi-stratified and mixed regimes. Eight DOM components from parallel factor analysis (PARAFAC) were identified based on three-dimensional excitation–emission matrices (EEMs), which were aggregated into three main groups of components (microbial humic-like, terrestrial humic-like, protein-like). Spatially, the more productive bays were characterized by higher DOM concentration than deeper more offshore waters (fluorescence intensity and DOC were ~ 80% and ~ 30% higher in bays, respectively). Seasonally, the DOM pool shifted from protein-like components during the mixed regime to microbial humic-like components during the semi-stratified regime and to terrestrial humic-like components during the stratified regime. This indicates that pulses of autochthonous DOM derived from phytoplankton occurred when the lake was mixing, which increased the availability of dissolved inorganic nutrients. Subsequently, this freshly produced autochthonous DOM was microbially processed during the following semi-stratified regime. In the open waters, during the stratified regime, only terrestrial refractory DOM components remained because the labile and fresh stock of DOM created during the preceding mixed season was consumed. In the bays, the high terrestrial refractory DOM during the stratified regime may be additionally due to the allochthonous DOM input from the runoff. At the scale of the whole lake, the background refractory DOM probably comes mainly from precipitation and followed by river inputs. [ABSTRACT FROM AUTHOR]

Dissolved organic carbon (DOC) derived from plant litter plays an important role in the ecosystem carbon balance and soil biogeochemistry. However, in boreal coniferous forests no integrated understanding exists of how understory vegetation contributes to litter leaching of DOC, nitrogen (N) and phosphorus (P) with different bioavailability at the forest stand level. We characterized water extractable leachates from fresh and decayed litter of dominant canopy and understory sources in a boreal coniferous forest, in order to explore the contribution of understory vegetation as a source of both total and bioavailable forms of DOC, N and P. Recently produced litter from deciduous species (including Vaccinium myrtillus) yielded the highest amounts of DOC. However, this leaching potential decreased exponentially with mass loss through litter decay. The DOC lability generally showed little interspecific variation, although wood derived DOC was more recalcitrant. Lability decreased progressively with litter aging. Water extractable nutrients increased proportionally with DOC, and roughly a quarter (N) or half (P) had directly bioavailable inorganic forms. Scaled to annual litterfall at the forest stand, understory vegetation contributed ~ 80% of the water extractable DOC and nutrients from fresh litter, with > 60% coming from Vaccinium myrtillus alone. However, as litter decomposes, the data suggest a lower leaching potential is maintained with a larger contribution from needle, wood and moss litter. Our study shows that understory vegetation, especially V. myrtillus, is a key driver of litter DOC and nutrient leaching in boreal coniferous forests. [ABSTRACT FROM AUTHOR]

Dissolved organic carbon (DOC) flux is an important mechanism to convey soil carbon (C) from aboveground organic debris (litter) to deeper soil horizons and can influence the formation of stable soil organic C compounds. The magnitude of this flux depends on both infiltration and DOC production rates which are functions of the climatic, soil, topographic and ecological characteristics of a region. Aboveground litter quantity and quality was manipulated for 20 years in an old-growth Douglas fir forest under six treatments to study relationships among litter inputs, DOC production and flux, and soil C dynamics. DOC concentrations were measured at two depths using tension lysimeters, and a hydrologic model was created to quantify water and DOC flux through the soil profile. DOC concentrations ranged from 3.0–8.0 and 1.5–2.5 mg C/L among treatments at 30 and 100 cm below the soil surface, respectively. Aboveground detrital inputs did not have a consistent positive effect on soil solution DOC; the addition of coarse woody debris increased soil solution DOC by 58% 30 cm belowground, while doubling the mass of aboveground leaf litter decreased DOC concentrations by 30%. We suggest that high-quality leaf litter accelerated microbial processing, resulting in a "priming" effect that led to the lower concentrations. Annual DOC flux into groundwater was small (2.7–3.7 g C/m2/year) and accounts for < 0.1% of estimated litter C at the site. Therefore, direct DOC loss from surface litter to groundwater is relatively negligible to the soil C budget. However, DOC flux into the soil surface was much greater (73–210 g C/m2/year), equivalent to 1.4–2.4% of aboveground litter C. Therefore, DOC transport is an important source of C to shallow soil horizons. [ABSTRACT FROM AUTHOR]

Humid tropical forests contain some of the largest soil carbon (C) stocks on Earth, yet there is uncertainty about how carbon dioxide (CO2) fluxes will respond to climate change in this biome. The magnitude of change in soil respiration over seasonal wetting and drying cycles can provide insight to how CO2 fluxes might respond to precipitation changes. We measured soil respiration in 15 distinct forests across rainfall and soil fertility gradients in lowland Panama to assess spatial variation in seasonal patterns. We predicted that seasonal changes in soil respiration would be related to soil moisture, and that the ratio of wet to dry season CO2 fluxes across landscape gradients would be regulated by soil organic C and nutrient availability. We found that soil respiration during the dry season was relatively stable across the rainfall gradient, averaging 4.3 ± 0.3 µmol CO2 m−2 s−1. In contrast, wet season respiration varied markedly, ranging among sites from a decline of 19% to an increase of 360% in comparison to dry season values. Soil moisture, air temperature, and rainfall were the best predictors of instantaneous soil respiration (R2 = 0.18). Meanwhile, ratios of wet to dry season CO2 fluxes were best predicted by site-scale resin-extractable phosphorus (P; R2 = 0.48). That is, soil respiration in P-rich sites increased more during the wet season relative to respiration in P-poor sites. Also, sites with Wet:Dry season CO2 flux ratios < 1 were all poor in soil P, defined as resin P concentrations < 2 mg P kg−1. Although soil organic C was not related to instantaneous soil respiration rates, forest floor biomass accumulation during the dry season was positively correlated with soil respiration during the wet season (R2 = 0.26), indicating the contribution of microbial decomposition to wet season soil respiration. Overall, nutrient availability regulated soil respiration responses to increased moisture during the wet season, while low soil moisture uniformly suppressed soil respiration across sites during the dry season. Phosphorus availability might therefore regulate feedbacks to climate change among humid tropical forests. [ABSTRACT FROM AUTHOR]

Dissolved organic carbon (DOC) in large river networks is an important carbon pool in the global biogeochemical cycle. DOC compositions vary spatially at global and regional scales, which influences DOC degradation and subsequent in-stream removal in river networks. The Changjiang River Network (CRN) is the third largest river system worldwide and plays an important role in DOC transformation and transportation. However, the relationships between DOC composition and degradation, as well as the quantification of in-stream removal, remain poorly understood. In this study, we chose the CRN to study spatial patterns of DOC fluorescence, as proxies for chemical composition, and degradation. Laboratory degradation experiments were conducted to explore DOC degradability and mechanisms of photodegradation and microbial respiration. We found that DOC fluorescence properties and degradation showed significant spatial differences in the lower reaches of the CRN. DOC with higher proportions of humic acid-like materials showed higher photodegradability. In degradation experiments, the total DOC loss was 49.1–66.0% over about the first 6 to 7 days. Microbial respiration removed 33.0–47.3% of total DOC, while photodegradation removed 9.0–35.3%. The relative contributions of photodegradation and microbial respiration to DOC degradation varied with different DOC fluorescence properties. The experimental values of DOC decay rate constants were 0.217–0.250 d−1. Our study improves understanding of DOC degradability, linking to its composition and providing a reference for estimating DOC in-stream removal in large river networks. [ABSTRACT FROM AUTHOR]

Widespread increases in iron (Fe) concentrations are contributing to ongoing browning of northern freshwaters, but the driver/s behind the trends are not known. Fe mobilization in soils is known to be controlled by redox conditions, pH, and DOC availability for complexation. Moreover, high sulfate concentrations have been suggested to constrain Fe in transition from soil to water, and declining sulfate deposition to have the opposite effect. We studied the effect of these Fe mobilization barriers in a microcosm experiment, applying high (peak S deposition) and low (present day) sulfate treatments and oxic versus anoxic conditions to boreal (O horizon) soil slurries. We hypothesized that anoxic conditions would favor Fe release. On the contrary we expected high sulfate concentrations to suppress Fe mobility, through FeS formation or by lowering pH and thereby DOC concentrations. Anoxia had positive effects on both Fe and DOC concentrations in solution. Contrasting with our hypothesis, Fe concentrations were enhanced at high sulfate concentrations, i.e. increasing acidity in high sulfate treatments appeared to promote Fe mobilization. Establishment of the basidiomycete fungus Jaapia ochroleuca in the oxic treatments 44 days into the experiment had a major impact on Fe mobilization by increasing total Fe concentrations in solution. Thus, anoxia and acidity, along with fungi mediated mobilization, were important in controlling Fe release from soil to the aqueous phase. While Fe is often assumed to precipitate as Fe(oxy)hydroxides in the transition from anoxic to oxic water in the riparian zone, Fe from anoxic treatments remained in solution after introduction of oxygen. Our results do not support reduced atmospheric S deposition as a driver behind increasing Fe concentrations in boreal freshwaters, but confirm the importance of reducing conditions—which may be enhanced by higher soil temperature and moisture—for mobilization of Fe across the terrestrial-aquatic interphase. [ABSTRACT FROM AUTHOR]

Despite being a crucial component of nutrient cycling and soil carbon (C) dynamics in forest ecosystems, there is too little information from past studies to discern whether dissolved organic carbon (DOC) exchanges with soil organic carbon or passes unaltered through soils. In this study, we added 13C-labelled litter-derived DOC into different depth soil columns in a 180-day incubation experiment to determine the fate of DOC in soils, and to monitor the changes in DOC composition when it percolates through the soil. The results showed that δ13C values increased in soil microbes, which indicated that some litter-derived DOC was immobilized by soil microbial communities. Approximately 76% of litter-derived DOC was retained in the soil (60% in topsoil and 16% in midsoil). Meanwhile, 18%, 4%, and 3% of litter-derived DOC were mineralized into CO2 in topsoil, midsoil and subsoil respectively. Only 0.04% of litter-derived DOC leached from the soil column (0–60 cm). These results indicated that DOC was mainly retained on soil, and a small portion was mineralized by microorganisms, with minimal leaching. The composition of water soluble soil organic carbon (WSOC) and leachate DOC (LDOC) were similar between the control and treatment. This indicated that the composition of WSOC and LDOC was more similar to soil C than the added DOC, which supports the previously hypothesized dynamic exchange model. These findings provide new insight by showing that most litter-derived DOC is sequestered in forest soils. [ABSTRACT FROM AUTHOR]

Conversion of native vegetation to agriculture may change the carbon cycle by reducing carbon soil storage capacity and increasing CO2 emissions. We aimed to comparatively assess the impact of land use change on labile pools and dynamics of soil organic carbon (SOC) in two land uses (Urochloa pastures and Eucalyptus forestry) relative to the native reference ecosystem (Brazilian woodland savanna, the cerradão), as a function of soil depth and season. For three replicated study sites, each of them including a control area of the native vegetation (Cerrado) and two land uses (Pasture, Eucalyptus), we sampled soil from 0 to 2 m depth in both dry and wet seasons. We quantified dissolved organic carbon (DOC) and microbial biomass carbon (MBC), estimated the microbial quotient (MBC/SOC) and DOC/SOC ratio, and evaluated C dynamics by assessing soil basal respiration and the metabolic quotient (qCO2). Compared with Cerrado, DOC, MBC and MBC/SOC decreased in both Pasture and Eucalyptus. Differences between land uses vanished below 30 cm soil depth. Seasonality affected most analyzed variables, with lower values for DOC, DOC/SOC and qCO2, and slightly higher values for MBC and MBC/SOC in the wet season. In the dry season qCO2 increased in the Eucalyptus topsoil as compared to Cerrado, suggesting higher stress in the microbial community and/or lower decomposition efficiency in Eucalyptus. Overall, our results show that cerradão conversion to pastures and Eucalyptus plantations negatively affects labile pools and dynamics of SOC, with the effects surpassing a strong spatial and seasonal variability in the soil response to land conversion. [ABSTRACT FROM AUTHOR]

While much research over the past 30 years has focused on the deleterious effects of excess N on forests and associated aquatic ecosystems, recent declines in atmospheric N deposition and unexplained declines in N export from these ecosystems have raised new concerns about N oligotrophication, limitations of forest productivity, and the capacity for forests to respond dynamically to disturbance and environmental change. Here we show multiple data streams from long-term ecological research at the Hubbard Brook Experimental Forest in New Hampshire, USA suggesting that N oligotrophication in forest soils is driven by increased carbon flow from the atmosphere through soils that stimulates microbial immobilization of N and decreases available N for plants. Decreased available N in soils can result in increased N resorption by trees, which reduces litterfall N input to soils, further limiting available N supply and leading to further declines in soil N availability. Moreover, N oligotrophication has been likely exacerbated by changes in climate that increase the length of the growing season and decrease production of available N by mineralization during both winter and spring. These results suggest a need to re-evaluate the nature and extent of N cycling in temperate forests and assess how changing conditions will influence forest ecosystem response to multiple, dynamic stresses of global environmental change. [ABSTRACT FROM AUTHOR]

Export of dissolved organic carbon (DOC) from forested catchments is governed by competing processes of production, decomposition, sorption and flushing. To examine the sources of DOC, carbon isotopes (14C and13C) were analyzed in DOC from surface waters, groundwaters and soils in a small forested catchment on the Canadian Shield in central Ontario. A significant fraction (greater than 50%) of DOC in major inflows to the lake is composed of carbon incorporated into organic matter, solubilized and flushed into the stream within the last 40 years. In contrast,14C in groundwater DOC was old indicating extensive recycling of forest floor derived organic carbon in the soil column before elution to groundwater in the lower B and C soil horizons. A small upland basin had a wide range in14C from old groundwater values at baseflow under dry basin conditions to relatively modern values during high flow or wetter antecedent conditions. Wetlands export mainly recently fixed carbon with little seasonal range. DOC in streams entering the small lake may be composed of two pools; an older recalcitrant pool delivered by groundwater and a young labile pool derived from recent organic matter. The relative proportion of these two pools changes seasonally due the changes in the water flowpaths and organic carbon dynamics. Although changes in local climate (temperature and/or precipitation) may alter the relative proportions of the old and young pools, the older pool is likely to be more refractory to sedimentation and decomposition in the lake setting. Delivery of older pool DOC from the catchment and susceptibility of this older pool to photochemical decomposition may consequently be important in governing the minimum DOC concentration limit in lakes.

Export of dissolved organic carbon (DOC) from forested catchments is governed by competing processes of production, decomposition, sorption and flushing. To examine the sources of DOC, carbon isotopes (14C and13C) were analyzed in DOC from surface waters, groundwaters and soils in a small forested catchment on the Canadian Shield in central Ontario. A significant fraction (greater than 50%) of DOC in major inflows to the lake is composed of carbon incorporated into organic matter, solubilized and flushed into the stream within the last 40 years. In contrast,14C in groundwater DOC was old indicating extensive recycling of forest floor derived organic carbon in the soil column before elution to groundwater in the lower B and C soil horizons. A small upland basin had a wide range in14C from old groundwater values at baseflow under dry basin conditions to relatively modern values during high flow or wetter antecedent conditions. Wetlands export mainly recently fixed carbon with little seasonal range. DOC in streams entering the small lake may be composed of two pools; an older recalcitrant pool delivered by groundwater and a young labile pool derived from recent organic matter. The relative proportion of these two pools changes seasonally due the changes in the water flowpaths and organic carbon dynamics. Although changes in local climate (temperature and/or precipitation) may alter the relative proportions of the old and young pools, the older pool is likely to be more refractory to sedimentation and decomposition in the lake setting. Delivery of older pool DOC from the catchment and susceptibility of this older pool to photochemical decomposition may consequently be important in governing the minimum DOC concentration limit in lakes.

We assessed stream ecosystem-level response to a drought-induced defoliation event by gypsy moth caterpillars (Lymantria dispar) with high-frequency water quality sensors. The defoliation event was compared to the prior year of data. Based on long-term records of precipitation and drought indices, the drought of 2015-2016 in Rhode Island, USA was an extreme climatic event that preceded and likely precipitated the defoliation from insect infestation. Canopy cover in the riparian area was reduced by over 50% increasing light availability which warmed the stream and stimulated autotrophic activity. Frass and leaf detritus contributed particulate carbon and organic nutrients to the stream. Based on locally calibrated s::can spectro::lyser data, nitrate concentration and flux did not significantly increase during defoliation while orthophosphate concentration and flux did significantly increase during part of the defoliation period. Lower mean daily dissolved oxygen (DO) levels and wider diel cycles of DO indicated higher biological activity during the defoliation event. Stream metabolism metrics were also significantly higher during defoliation and pointed to heterotrophic activity dominating in the stream. The increases in stream metabolism were low compared to other studies; in streams with higher nutrient levels (e.g., in agricultural or urban watersheds) the increase in light and temperature could have a stronger influence on stream metabolism. The in-stream metabolic processes and nutrient fluxes observed in response to the drought-driven defoliation event resulted from the long-term deployment of high-frequency water sensors. The proliferation of these water sensors now enable studies that assess ecosystem responses to stochastic, unusual disturbances. [ABSTRACT FROM AUTHOR]

Headwater streams are foci for nutrient and energy loading from terrestrial landscapes, in situ nutrient transformations, and downstream transport. Despite the prominent role that headwater streams can have in regulating downstream water quality, the relative importance of processes that can influence nutrient uptake have not been fully compared in heterotrophic aquatic systems. To address this research need, we assessed the seasonality of dissolved organic carbon (DOC) and nitrate (NO3−) uptake, compared the relative influence of hydrologic and biogeochemical drivers on observed seasonal trends in nutrient uptake, and estimated the influence of these biological transformations on watershed scale nutrient retention and export. We determined that seasonal reductions in DOC and NO3− concentrations led to decreases in the potential for the biotic community to take up nutrients, and that seasonality of DOC and NO3− uptake was consistent with the seasonal dynamics of ecosystem metabolism. We calculated that that during the post-snowmelt period (June to August), biotic retention of both dissolved organic carbon and nitrate exceeded export fluxes from this headwater catchment, highlighting the potential for biological processes to regulate downstream water quality. [ABSTRACT FROM AUTHOR]

Two intense rainfalls [Hurricane Joaquin (2015) and Hurricane Matthew (2016)], one year apart, provided a unique opportunity to examine changes in dissolved organic matter (DOM) dynamics in coastal blackwater rivers under extreme flooding conditions in the southeastern United States. Two sites along Waccamaw River (a coastal blackwater river) and the outflow of 18 sub-basins of Yadkin-Pee Dee Basin were sampled during and after the flooding events. The peaks of dissolved organic carbon (DOC) and nitrogen (DON) concentrations were observed 18 and 23 days after peak discharge in 2015 and 2016, respectively. Moreover, DOM aromaticity and abundance of humic substances significantly increased during the same period. Separation of discharge hydrograph into surface runoff and subsurface flow suggested that temporal changes were mainly due to contributions from subsurface flow flushing organic matter from wetlands and organic-rich riparian zones. The spatial analysis highlighted the key role of the forested wetlands as the only land use that significantly correlated with both DOM quantity (DOC and DON load) and DOM composition (i.e., aromaticity). The Yadkin-Pee Dee River basin alone exported more than 474 million kg DOC into the ocean during high-flow conditions from the 2016 event, indicating that such extreme short-term events mobilized enormous amounts of organic carbon and nitrogen to the ocean. Considering the predicted increase in frequency and intensity of extreme rainfall events in the eastern U.S., the results of this study can shed light on changes in DOM dynamics that may occur under such conditions in the near future. [ABSTRACT FROM AUTHOR]

The perhumid coastal temperate rainforest (PCTR) of southeast Alaska has some of the densest soil organic carbon (SOC) stocks in the world (>300 Mg C ha) but the fate of this SOC with continued warming remains largely unknown. We quantified dissolved organic carbon (DOC) and carbon dioxide (CO) yields from four different wetland types (rich fen, poor fen, forested wetland and cedar wetland) using controlled laboratory incubations of surface (10 cm) and subsurface (25 cm) soils incubated at 8 and 15 °C for 37 weeks. Furthermore, we used fluorescence characterization of DOC and laboratory bioassays to assess how climate-induced soil warming may impact the quality and bioavailability of DOC delivered to fluvial systems. Soil temperature was the strongest control on SOC turnover, with wetland type and soil depth less important in controlling CO flux and extractable DOC. The high temperature incubation increased average CO yield by ~40 and ~25% for DOC suggesting PCTR soils contain a sizeable pool of readily biodegradable SOC that can be mineralized to DOC and CO with future climate warming. Fluxes of CO were positively correlated to both extractable DOC and percent bioavailable DOC during the last few months of the incubation suggesting mineralization of SOC to DOC is a strong control of soil respiration rates. Whether the net result is increased export of either carbon form will depend on the balance between the land to water transport of DOC and the ability of soil microbial communities to mineralize DOC to CO. [ABSTRACT FROM AUTHOR]

Estimates of gaseous carbon (C) fluxes in wetlands are heavily based on temperature. However, isolating specific effects of temperature on anaerobic C processing from other controls (C quality and nutrients) has proven difficult. Here, we test the hypothesis that temperature sensitivity of soil organic matter (SOM) decomposition is more influenced by C quality than nutrient availability in subtropical freshwater, sawgrass ( Cladium jamaicense)-based peats. Carbon age (characterized by depth: 0-10 and 10-20 cm) was used as a surrogate of C quality while two sites were selected with contrasting levels of nutrient (P) availability. In anaerobic laboratory incubations temperature was increased in 5 °C steps to assess the proportion of C available at a given temperature (i.e. thermo-labile C) as productions of gaseous (CO and CH) and dissolved organic C (DOC) fractions. Thermo-labile C increased 3.1-3.6 times from 15 °C to 30 °C in all soils. Disproportionate increase in the production of gaseous forms versus DOC as well as CH:CO was observed with warming. Observed Q values followed the trend of CH (~14) ≫ CO (~2.5) > DOC (~1.7) and temperature sensitivity was more dependent on C quality than nutrient availability over the entire temperature range. Spectral analysis indicated more bio-available DOC production at higher temperature. Regression analysis also indicated that C quality primarily influenced SOM decomposition at lower temperature, while at higher temperature nutrient limitation dominantly controlled SOM decomposition. These findings confirm the role of C quality in temperature sensitivity of warm peat soils, but also indicate an increased importance of nutrient limitation at higher temperature. [ABSTRACT FROM AUTHOR]