scispace - formally typeset
Search or ask a question

Showing papers in "Biogeochemistry in 2017"


Journal ArticleDOI
TL;DR: In this paper, the interactions between soil P availability and P nutrition strategies of European beech (Fagus sylvatica) forests were quantified, and it was shown that plants and microorganisms of P-rich forests carry over mineral-bound P into the biogeochemical P cycle (acquiring strategy).
Abstract: Phosphorus availability may shape plant–microorganism–soil interactions in forest ecosystems. Our aim was to quantify the interactions between soil P availability and P nutrition strategies of European beech (Fagus sylvatica) forests. We assumed that plants and microorganisms of P-rich forests carry over mineral-bound P into the biogeochemical P cycle (acquiring strategy). In contrast, P-poor ecosystems establish tight P cycles to sustain their P demand (recycling strategy). We tested if this conceptual model on supply-controlled P nutrition strategies was consistent with data from five European beech forest ecosystems with different parent materials (geosequence), covering a wide range of total soil P stocks (160–900 g P m−2; <1 m depth). We analyzed numerous soil chemical and biological properties. Especially P-rich beech ecosystems accumulated P in topsoil horizons in moderately labile forms. Forest floor turnover rates decreased with decreasing total P stocks (from 1/5 to 1/40 per year) while ratios between organic carbon and organic phosphorus (C:Porg) increased from 110 to 984 (A horizons). High proportions of fine-root biomass in forest floors seemed to favor tight P recycling. Phosphorus in fine-root biomass increased relative to microbial P with decreasing P stocks. Concomitantly, phosphodiesterase activity decreased, which might explain increasing proportions of diester-P remaining in the soil organic matter. With decreasing P supply indicator values for P acquisition decreased and those for recycling increased, implying adjustment of plant–microorganism–soil feedbacks to soil P availability. Intense recycling improves the P use efficiency of beech forests.

141 citations


Journal ArticleDOI
TL;DR: The impact of human activities on the concentrations and composition of dissolved organic matter and particulate organic matter (POM) was investigated in the Walloon Region of the Meuse River basin (Belgium) as discussed by the authors.
Abstract: The impact of human activities on the concentrations and composition of dissolved organic matter (DOM) and particulate organic matter (POM) was investigated in the Walloon Region of the Meuse River basin (Belgium). Water samples were collected at different hydrological periods along a gradient of human disturbance (50 sampling sites ranging from 8.0 to 20,407 km2) and during a 1.5 year monitoring of the Meuse River at the city of Liege. This dataset was completed by the characterization of the DOM pool in groundwaters. The composition of DOM and POM was investigated through elemental (C:N ratios), isotopic (δ13C) and optical measurements including excitation emission matrix fluorescence with parallel factor analysis (EEM–PARAFAC). Land use was a major driver on fluvial OM composition at the regional scale of the Meuse Basin, the composition of both fluvial DOM and POM pools showing a shift toward a more microbial/algal and less plant/soil-derived character as human disturbance increased. The comparison of DOM composition between surface and groundwaters demonstrated that this pattern can be attributed in part to the transformation of terrestrial sources by agricultural practices that promote the decomposition of soil organic matter in agricultural lands and subsequent microbial inputs in terrestrial sources. In parallel, human land had contrasting effects on the autochthonous production of DOM and POM. While the in-stream generation of fresh DOM through biological activity was promoted in urban areas, summer autochthonous POM production was not influenced by land use. Finally, soil erosion by agricultural management practices favored the transfer of terrestrial organic matter via the particulate phase. Stable isotope data suggest that the hydrological transfer of terrestrial DOM and POM in human-impacted catchment are not subject to the same controls, and that physical exchange between these two pools of organic matter is limited.

128 citations


Journal ArticleDOI
TL;DR: In this paper, the authors show that changing precipitation patterns, resulting from climate change, interact with agricultural land use to deteriorate water quality, and that increased weather whiplash will, in part, increase the frequency of riverine N exceeding drinking water standards.
Abstract: Excess nitrogen (N) impairs inland water quality and creates hypoxia in coastal ecosystems. Agriculture is the primary source of N; agricultural management and hydrology together control aquatic ecosystem N loading. Future N loading will be determined by how agriculture and hydrology intersect with climate change, yet the interactions between changing climate and water quality remain poorly understood. Here, we show that changing precipitation patterns, resulting from climate change, interact with agricultural land use to deteriorate water quality. We focus on the 2012–2013 Midwestern U.S. drought as a “natural experiment”. The transition from drought conditions in 2012 to a wet spring in 2013 was abrupt; the media dubbed this “weather whiplash”. We use recent (2010–2015) and historical data (1950–2015) to connect weather whiplash (drought-to-flood transitions) to increases in riverine N loads and concentrations. The drought likely created highly N-enriched soils; this excess N mobilized during heavy spring rains (2013), resulting in a 34% increase (10.5 vs. 7.8 mg N L−1) in the flow-weighted mean annual nitrate concentration compared to recent years. Furthermore, we show that climate change will likely intensify weather whiplash. Increased weather whiplash will, in part, increase the frequency of riverine N exceeding E.P.A. drinking water standards. Thus, our observations suggest increased climatic variation will amplify negative trends in water quality in a region already grappling with severe impairments.

123 citations


Journal ArticleDOI
TL;DR: In this article, the authors analyzed shifts in the biomolecular composition of bulk soils and individual particle size fractions that were incubated in the laboratory for 345 days and found that plant-derived lipids and lignin were abundant in particulate organic matter (POM) fractions of sand-, silt-, and clay-size.
Abstract: Physical separation of soil into different soil organic matter (SOM) fractions is widely used to identify organic carbon pools that are differently stabilized and have distinct chemical composition. However, the mechanisms underlying these differences in stability and chemical composition are only partly understood. To provide new insights into the stabilization of different chemical compound classes in physically-separated SOM fractions, we assessed shifts in the biomolecular composition of bulk soils and individual particle size fractions that were incubated in the laboratory for 345 days. After the incubation, also the incubated bulk soil was fractionated. The chemical composition of organic matter in bulk soils and fractions was characterized by 13C-CPMAS nuclear magnetic resonance spectroscopy and sequential chemical extraction followed by GC/MS measurements. Plant-derived lipids and lignin were abundant in particulate organic matter (POM) fractions of sand-, silt-, and clay-size and the mineral-bound, clay-sized organic matter. These results indicate that recent conceptualizations of SOM stabilization probably understate the contribution of plant-derived organic matter to stable SOM pools. Although our data indicate that inherent recalcitrance could be important in soils with limited aggregation, organo-mineral interactions and aggregation were responsible for long-term SOM stabilization. In particular, we observed consistently higher concentrations of plant-derived lipids in POM fractions that were incubated individually, where aggregates were disrupted, as compared to those incubated as bulk soil, where aggregates stayed intact. This finding emphasizes the importance of aggregation for the stabilization of less ‘recalcitrant’ biomolecules in the POM fractions. Because also the abundance of lipids and lignin in clay-sized, mineral-associated SOM was substantially influenced by aggregation, the bioavailability of mineral-associated SOM likely increases after the destruction of intact soil structures.

106 citations


Journal ArticleDOI
TL;DR: In this article, the influence of catchment land use and seasonality on the composition of dissolved organic matter (DOM) and ecosystem metabolism in headwater streams of a Kenyan river was assessed.
Abstract: Headwater streams influence the biogeochemical characteristics of large rivers and play important roles in regional and global carbon budgets. The combined effects of seasonality and land use change on the biogeochemistry of headwater streams, however, are not well understood. In this study we assessed the influence of catchment land use and seasonality on the composition of dissolved organic matter (DOM) and ecosystem metabolism in headwater streams of a Kenyan river. Fifty sites in 34 streams draining a gradient of catchment land use from 100% natural forest to 100% agriculture were sampled to determine temporal and spatial variation in DOM composition. Gross primary production (GPP) and ecosystem respiration (ER) were determined in 10 streams draining primarily forest or agricultural catchments. Absorbance and fluorescence spectrophotometry of DOM reflected notable shifts in composition along the land use gradient and with season. During the dry season, forest streams contained higher molecular weight and terrestrially derived DOM, whereas agricultural streams were dominated by autochthonous production and low molecular weight DOM. During the rainy season, aromaticity and high molecular weight DOM increased in agricultural streams, coinciding with seasonal erosion of soils and inputs of organic matter from farmlands. Most of the streams were heterotrophic. However, GPP and ER were generally greater in agricultural streams, driven by higher dissolved nutrient (mainly TDN) concentrations, light availability (open canopy) and temperature compared with forest streams. There were correlations between freshly and autochthonously produced DOM, GPP and ER during both the dry and wet seasons. This is one of the few studies to link land-use with organic carbon dynamics and DOM composition. Measures of ecosystem metabolism in these streams help to affirm the role of tropical streams and rivers as important components of the global carbon cycle and demonstrate that even semi-intensive, smallholder agriculture can have measurable effects on riverine ecosystem functioning.

65 citations


Journal ArticleDOI
TL;DR: In this paper, the physicochemical properties of the common low molecular weight organic substances (LMWOSs) allow predicting their microbial uptake from soil solution and subsequent partitioning of C within microbial biomass.
Abstract: The fate of low molecular weight organic substances (LMWOSs) in soil is regulated by microbial uptake. However, C oxidation state, the number of C atoms and –COOH groups in the LMWOS can affect their microbial utilization. Thus, the aim of this study was to reveal the effects of substance chemical properties on initial uptake and utilization of sugars, carboxylic and amino acids by microorganisms. Soil solution, spiked with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the soil solution, CO2, cytosol, and soil organic carbon (SOC) over 24 h. The half-life time of all LMWOS in the soil solution varied between 0.6 min (formic acid) and 5.0 min (sugars), indicating its dependence on C oxidation state of the substances. The half-life time of 14C in the fast mineralized pool in microorganisms, ranged between 30 (malic acid) and 80 (glycine) min and was independent on either C oxidation state, the number of C atoms, or number of –COOH groups. This suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The portion of mineralized LMWOS increased with their C oxidation state (20% for sugars vs. 90% for formic acid) corresponding to the decrease of C incorporated into the cytosol and SOC pools. Concluding, the physicochemical properties of the common LMWOS allow predicting their microbial uptake from soil solution and subsequent partitioning of C within microbial biomass.

59 citations


Journal ArticleDOI
TL;DR: In this paper, the authors present the trend in land-based nutrient use in the Baltic Sea watershed between 2000 and 2010 and show a strong linear relationship between regional net nutrient inputs and riverine nutrient fluxes.
Abstract: In order to assess the progress toward eutrophication management goals, it is important to understand trends in land-based nutrient use. Here we present net anthropogenic nitrogen and phosphorus inputs (NANI and NAPI, respectively) for 2000 and 2010 for the Baltic Sea watershed. Overall, across the entire Baltic, between the 5-year periods centered on 2000 and 2010, NANI and NAPI decreased modestly by −6 and −4%, respectively, but with substantial regional variation, including major increases in the Gulf of Riga drainage basin (+19 and +58%, respectively) and decreases in the Danish Straits drainage basin (−25 and −40% respectively). The changes were due primarily to changes in mineral fertilizer use. Mineral fertilizers dominated inputs, at 57% of both NANI and NAPI in 2000, increasing to 68 and 70%, respectively, by 2010. Net food and feed imports declined over that period, corresponding to increased crop production; either fewer imports of food and feedstocks were required to feed humans and livestock, or more of these commodities were exported. A strong linear relationship exists between regional net nutrient inputs and riverine nutrient fluxes for both periods. About 17% of NANI and 4.7% of NAPI were exported to the sea in 2000; these relationships did not significantly differ from those for 2010. Changes in NANI from 2000 to 2010 across basins were directly proportional rather than linearly related to changes in total N (TN) fluxes to the sea (i.e., no change in NANI suggests no change in TN flux). Similarly, for all basins except those draining to the Baltic Proper, changes in NAPI were proportional to changes in total P (TP) fluxes. The Danish Straits decreased most between 2000 and 2010, where NANI and NAPI declined by 25 and 40%, respectively, and corresponding fluxes of TN and TP declined 31 and 18%, respectively. For the Baltic Proper, NAPI was relatively unchanged between 2000 and 2010, while riverine TP fluxes decreased 25%, due possibly to lagged effects of fertilizer reduction resulting from socio-political changes in the early 1990s or improvements in sewage treatment capabilities. For most regions, further reductions in NANI and NAPI could be achieved by more efficient production and greater substitution of manure for imported mineral fertilizers.

59 citations


Journal ArticleDOI
TL;DR: In this paper, changes in atmospheric deposition, stream water chemistry, and solute fluxes were assessed across 15 small forested catchments across 15 different watersheds, and the average flux of dissolved inorganic nitrogen was best predicted by average runoff, soil chemistry (forest floor C/N) and levels of acid deposition (both S and N).
Abstract: Changes in atmospheric deposition, stream water chemistry, and solute fluxes were assessed across 15 small forested catchments. Dramatic changes in atmospheric deposition have occurred over the last three decades, including a 70% reduction in sulphur (S) deposition. These changes in atmospheric inputs have been associated with expected changes in levels of acidity, sulphate and base cations in streams. Soil retention of S appeared to partially explain rates of chemical recovery. In addition to these changes in acid–base chemistry we also observed unexpected changes in nitrogen (N) biogeochemistry and nutrient stoichiometry of stream water, including decreased stream N concentrations. Among all catchments the average flux of dissolved inorganic nitrogen (DIN) was best predicted by average runoff, soil chemistry (forest floor C/N) and levels of acid deposition (both S and N). The rate of change in stream DIN flux, however, was much more closely correlated with reductions in rates of S deposition rather than those of DIN. Unlike DIN fluxes, the average concentrations as well as the rates of decline in streamwater nitrate (NO3) concentration over time were tightly linked to stream dissolved organic carbon/dissolved organic nitrogen ratios DOC/DON and DON/TP rather than catchment characteristics. Declines in phosphorus adsorption with increasing soil pH appear to contribute to the relationship between C, N, and P in our study catchments. Our observations suggest that catchment P availability and its alteration due to environmental changes (e.g. acidification) might have profound effects on N cycling and catchment N retention that have been largely unrecognized.

56 citations


Journal ArticleDOI
TL;DR: In this paper, the authors show that changes in organo-mineral associations drive subsoil carbon:nitrogen (C:N) and 15N isotopic enrichment patterns more than in situ organic matter decay.
Abstract: Plant residues show carbon:nitrogen (C:N) decreases, 15N isotopic enrichment and preferential loss of labile substrates during microbial decay. In soil profiles, strikingly similar patterns of decreasing C:N and 15N isotopic enrichment with increasing depth are well documented. The parallel trend in organic matter composition with soil depth and during plant residue decay has been used as evidence to suggest that organic products accumulate or develop in the subsoil due to increasing intensity of microbially-driven processing, although no studies to date have verified this. Here, by applying sequential density fractionation, specific surface area, oxalate extractable Fe and Al, C:N and δ15N measures with depth to soils with relatively uniform soil mineralogy (Oxisols), climates and vegetation we show that changes in organo-mineral associations drive subsoil C:N and δ15N and C:N depth patterns more than in situ organic matter decay. Our results provide the first direct evidence that soil depth trends could be driven by mineral association instead of in situ processing.

56 citations


Journal ArticleDOI
TL;DR: In this article, the authors quantified the amount of Fe and Al in operationally defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containing mineral-associated carbon.
Abstract: Soil organic carbon (SOC) can be stabilized via association with iron (Fe) and aluminum (Al) minerals. Fe and Al can be strong predictors of SOC storage and turnover in soils with relatively high extractable metals content and moderately acidic to circumneutral pH. Here we test whether pedogenic Fe and Al influence SOC content and turnover in soils with low Fe and Al content and acidic pH. In soils from four sites spanning three soil orders, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containing mineral-associated carbon. We evaluated the correlations of Fe and Al concentrations, mean annual precipitation (MAP), mean annual temperature (MAT), and pH with SOC content and 14C-based turnover times. We found that poorly crystalline Fe and Al content predicted SOC turnover times (p < 0.0001) consistent with findings of previous studies, while organically-complexed Fe and Al content was a better predictor of SOC concentration (p < 0.0001). Greater site-level MAP (p < 0.0001) and colder site-level MAT (p < 0.0001) were correlated with longer SOC turnover times but were not correlated with SOC content. Our results suggest that poorly crystalline Fe and Al effectively slow the turnover of SOC in these acidic soils, even when their combined content in the soil is less than 2% by mass. However, in the strongly acidic Spodosol, organo-metal complexes tended to be less stable resulting in a more actively cycling mineral-associated SOC pool.

54 citations


Journal ArticleDOI
TL;DR: It was demonstrated that DON was important in supporting phytoplankton throughout the yearly production cycle, and the higher-than-expected urea uptake rates and large fraction of the spring bloom production supported by DON suggested that organic N not only contributes to regenerated production and to the nutrition of the small phy Topolankton fraction, but can also contribute substantially to new production of the larger phy toplankston in coastal waters.
Abstract: Dissolved organic nitrogen (DON) is recognised as an important N source for phytoplankton. However, its relative importance for phytoplankton nutrition and community composition has not been studied comprehensively. This study, conducted in a typical Scottish fjord, representative of near-pristine coastal environments, evaluates the utilisation of DON and dissolved inorganic nitrogen (DIN) by different microbial size fractions and the relationship of phytoplankton community composition with DON and other parameters. The study demonstrated that DON was important in supporting phytoplankton throughout the yearly production cycle. The higher-than-expected urea uptake rates and large fraction of the spring bloom production supported by DON suggested that organic N not only contributes to regenerated production and to the nutrition of the small phytoplankton fraction, but can also contribute substantially to new production of the larger phytoplankton in coastal waters. Multivariate statistical techniques revealed two phytoplankton assemblages with peaks in abundance at different times of the year: a spring group dominated by Skeletonema spp., Thalassiosira spp., and Pseudo-nitzschia spp. group delicatissima; and a summer/autumn group dominated by Chaetoceros spp., Scrippsiella spp., and Pseudo-nitzschia spp. group seriata. The multivariate pattern in community composition and abundance of these taxa was significantly correlated with the multivariate pattern of DON, urea, dissolved free amino acids, DIN, temperature, salinity, and daylength, with daylength and urea being particularly important, suggesting both physical and chemical controls on community composition.

Journal ArticleDOI
TL;DR: In this paper, the authors focused on a primary peat swamp forest and two oil palm plantations aged 1 (OP2012) and 6 years (OP2007) and monitored total and heterotrophic soil respiration over 13 months in paired control and trenched plots.
Abstract: Heterotrophic respiration is a major component of the soil C balance however we critically lack understanding of its variation upon conversion of peat swamp forests in tropical areas. Our research focused on a primary peat swamp forest and two oil palm plantations aged 1 (OP2012) and 6 years (OP2007). Total and heterotrophic soil respiration were monitored over 13 months in paired control and trenched plots. Spatial variability was taken into account by differentiating hummocks from hollows in the forest; close to palm from far from palm positions in the plantations. Annual total soil respiration was the highest in the oldest plantation (13.8 ± 0.3 Mg C ha−1 year−1) followed by the forest and youngest plantation (12.9 ± 0.3 and 11.7 ± 0.4 Mg C ha−1 year−1, respectively). In contrast, the contribution of heterotrophic to total respiration and annual heterotrophic respiration were lower in the forest (55.1 ± 2.8%; 7.1 ± 0.4 Mg C ha−1 year−1) than in the plantations (82.5 ± 5.8 and 61.0 ± 2.3%; 9.6 ± 0.8 and 8.4 ± 0.3 Mg C ha−1 year−1 in the OP2012 and OP2007, respectively). The use of total soil respiration rates measured far from palms as an indicator of heterotrophic respiration, as proposed in the literature, overestimates peat and litter mineralization by around 21%. Preliminary budget estimates suggest that over the monitoring period, the peat was a net C source in all land uses; C loss in the plantations was more than twice the loss observed in the forest.

Journal ArticleDOI
TL;DR: S spatially predicted the mass of particulate organic carbon stored in the top 10 cm of shelf sediments in parts of the North Sea, English Channel and Celtic Sea using a Random Forest model, POC measurements on surface sediments from those seas and relevant predictor variables, and it is possible to predict future changes to the POC stock.
Abstract: Shelf seas and their associated benthic habitats represent key systems in the global carbon cycle. However, the quantification of the related stocks and flows of carbon are often poorly constrained. To address benthic carbon storage in the North–West European continental shelf, we have spatially predicted the mass of particulate organic carbon (POC) stored in the top 10 cm of shelf sediments in parts of the North Sea, English Channel and Celtic Sea using a Random Forest model, POC measurements on surface sediments from those seas and relevant predictor variables. The presented model explains 78% of the variance in the data and we estimate that approximately 250 Mt of POC are stored in surficial sediments of the study area (633,000 km2). Upscaling to the North–West European continental shelf area (1,111,812 km2) yielded a range of 230–882 Mt of POC with the most likely estimate being on the order of 476 Mt. We demonstrate that the largest POC stocks are associated with coarse-grained sediments due to their wide-spread occurrence and high dry bulk densities. Our results also highlight the importance of coastal sediments for carbon storage and sequestration. Important predictors for POC include mud content in surficial sediments, annual average bottom temperature and distance to shoreline, with the latter possibly a proxy for terrestrial inputs. Now that key variables in determining the spatial distribution of POC have been identified, it is possible to predict future changes to the POC stock, with the presented maps providing an accurate baseline against which to assess predicted changes.

Journal ArticleDOI
TL;DR: Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23–31 µmol m−2 day−1) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(I) concentrations are highest, and oxic continental shelves can supply dFe to the water column.
Abstract: Shelf sediments underlying temperate and oxic waters of the Celtic Sea (NW European Shelf) were found to have shallow oxygen penetrations depths from late spring to late summer (2.2 to 5.8 mm below seafloor) with the shallowest during/after the spring-bloom (mid-April to mid-May) when the organic carbon content was highest. Sediment porewater dissolved iron (dFe, 85 %) consisted of reduced Fe(II) and gradually increased from 0.4 to 15 μM at the sediment surface to ~100 to 170 μM at about 6 cm depth. During the late spring this Fe(II) was found to be mainly present as soluble Fe(II) (> 85 % sFe, 7 hours. Iron(II) oxidation experiments in core top and bottom waters also showed removal from solution but at rates up to 5-times slower than predicted from theoretical reaction kinetics. These data imply the presence of ligands capable of complexing Fe(II) and supressing oxidation rates. The lower oxidation rate allows more time for the diffusion of Fe(II) from the sediments into the overlying water column. Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23-31 μmol m-2 d-1) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(II) concentrations are highest. In the water column this stabilised Fe(II) will gradually be oxidised and become part of the dFe(III) pool. Thus oxic continental shelves can supply dFe to the water column, which is enhanced during a small period of the year after phytoplankton bloom events when organic matter is transferred to the seafloor. This input is based on conservative assumptions for solute exchange (diffusionreaction), whereas (bio)physical advection and resuspension events are likely to accelerate these solute exchanges in shelf-seas.

Journal ArticleDOI
TL;DR: In this paper, the authors investigated the influence of extreme wet conditions on porewater chemistry and factors controlling soil GHGs fluxes in a temperate forested watershed in the piedmont region of Maryland.
Abstract: Climate models predict increased frequency and intensity of storm events, but it is unclear how extreme precipitation events influence the dynamics of soil fluxes for multiple greenhouse gases (GHGs). Intact soil mesocosms (0–10 cm depth) from a temperate forested watershed in the piedmont region of Maryland [two upland forest soils, and two hydric soils (i.e., wetland, creek bank)] were exposed to experimental water pulses with periods of drying, forcing soils towards extreme wet conditions under controlled temperature. Automated measurements (hourly resolution) of soil CO2, CH4, and N2O fluxes were coupled with porewater chemistry analyses (i.e., pH, Eh, Fe, S, NO3 −), and polymerase chain reaction–denaturing gradient gel electrophoresis to characterize changes in microbial community structure. Automated measurements quantified unexpected increases in emissions up to 245% for CO2 (Wetland), >23,000% for CH4 (Creek), and >110,000% for N2O (Forest Soils) following pulse events. The Creek soil produced the highest soil CO2 emissions, the Wetland soil produced the highest CH4 emissions, and the Forest soils produced the highest N2O emissions during the experiment. Using carbon dioxide equivalencies of the three GHGs, we determined the Creek soil contributed the most to a 20-year global warming potential (GWP; 30.3%). Forest soils contributed the most to the 100-year GWP (up to 53.7%) as a result of large N2O emissions. These results provide insights on the influence of extreme wet conditions on porewater chemistry and factors controlling soil GHGs fluxes. Finally, this study addresses the need to test biogeochemical thresholds and responses of ecosystem functions to climate extremes.

Journal ArticleDOI
TL;DR: A review of the challenges and opportunities of isotope complexity of Nitrous Oxide (N2O) can be found in this paper, where the two isotopes of N and the three isotope of O combine to form a total of 12 possible isotopic molecules of N2O, including bulk (δ15N, δ18O), position dependent (site preference), mass independent (Δ17O), multiply-substituted or clumped isotope compositions.
Abstract: Nitrous oxide (N2O) is an important focus of international greenhouse gas accounting agreements and mitigation of emissions will likely depend on understanding the mechanisms of its formation and reduction. Consequently, applications of stable isotope techniques to understand N2O cycling are proliferating and recent advances in technology are enabling (1) increases in the frequency of isotope analyses and (2) analyses not previously possible. The two isotopes of N and 3 isotopes of O combine to form a total of 12 possible isotopic molecules of N2O. Consequently, this remarkably simple molecule contains a wealth of isotopic information in the form of bulk (δ15N, δ18O), position dependent (site preference), mass independent (Δ17O) and multiply-substituted or clumped isotope compositions. With recent developments in high-mass resolution double sector instruments all 12 isotopic molecules will likely be resolved in the near future. Advances in spectroscopic instruments hold the promise of substantial increases in sample throughput; however, spectroscopic analyses require corrections due to interferences from other gases and frequent and accurate calibration. Mass spectrometric approaches require mass overlap corrections that are not uniform between research groups and interlaboratory comparisons remain imprecise. The continued lack of attention to calibration by both funding agencies and investigators can only perpetuate disagreement between laboratories in reported isotope values for N2O that, in turn, will compromise global assessments of N2O sources and sinks based on isotope ratios. This review discusses the challenges and opportunities offered by the isotopic complexity of N2O.

Journal ArticleDOI
TL;DR: Fixed 15N–N2 became quickly available to non-diazotroph associated plants in all investigated vegetation types, proving that N2 fixation is an actual source of available N in pristine ecosystems.
Abstract: Biological nitrogen (N2) fixation performed by diazotrophs (N2 fixing bacteria) is thought to be one of the main sources of plant available N in pristine ecosystems like arctic tundra. However, direct evidence of a transfer of fixed N2 to non-diazotroph associated plants is lacking to date. Here, we present results from an in situ 15N–N2 labelling study in the High Arctic. Three dominant vegetation types (organic crust composed of free-living cyanobacteria, mosses, cotton grass) were subjected to acetylene reduction assays (ARA) performed regularly throughout the growing season, as well as 15N–N2 incubations. The 15N-label was followed into the dominant N2 fixer associations, soil, soil microbial biomass and non-diazotroph associated plants three days and three weeks after labelling. Mosses contributed most to habitat N2 fixation throughout the measuring campaigns, and N2 fixation activity was highest at the beginning of the growing season in all plots. Fixed 15N–N2 became quickly (within 3 days) available to non-diazotroph associated plants in all investigated vegetation types, proving that N2 fixation is an actual source of available N in pristine ecosystems.

Journal ArticleDOI
TL;DR: Overall, restored Unionid populations may enhance P retention in soft tissues and shells and N loss via denitrification and Ecosystem managers may find greater support for restoration of Unionids with careful calculations of their ecosystem role in nutrient retention and removal.
Abstract: Consumers contribute to nutrient cycling in aquatic ecosystems by nutrient retention in tissues, metabolic transformations and excretion, and promoting microbial processes that remove nutrients (i.e., nitrogen (N) loss via denitrification). Freshwater mussels (Unionidae) form dense assemblages in rivers, and affect nutrient transformations through feeding, biodeposition, and bioturbation. However, the effects of Unionid mussels on N and phosphorus (P) retention are not commonly measured. We quantified rates of filtration, retention, and biodeposition of carbon (C), N, and P for two Unionid species: Lasmigona complanata and Pyganodon grandis. We used continuous-flow cores with 15N tracers to measure denitrification in sediments alone and with a single individual of each species. We conducted measurements in an urban river near Chicago, IL, USA that is a target for Unionid restoration. Both Unionid species showed high rates of P-specific feeding and retention, but low N-specific rates. This was in agreement with high N:P ratio in the water column. Each species significantly increased denitrification relative to sediment alone. 15N tracers suggested direct denitrification of nitrate increased denitrification, although enhanced coupled nitrification–denitrification likely also contributed to denitrification. Finally, denitrification rates with and without mussels were used to estimate the value of N loss under different scenarios for mussel restoration at the river scale. Overall, restored Unionid populations may enhance P retention in soft tissues and shells and N loss via denitrification. Ecosystem managers may find greater support for restoration of Unionid populations with careful calculations of their ecosystem role in nutrient retention and removal.

Journal ArticleDOI
TL;DR: In this article, the authors found that concentrations of nitrogen and phosphorus in lakes may be differentially impacted by climate-driven changes in nutrient loading and by direct impacts of temperature and wind speed on intern...
Abstract: Concentrations of nitrogen (N) and phosphorus (P) in lakes may be differentially impacted by climate-driven changes in nutrient loading and by direct impacts of temperature and wind speed on intern ...

Journal ArticleDOI
TL;DR: In this article, a decade-long field study that traced the decomposition of 13C-and 15N-labeled Pinus ponderosa needle and fine root litter placed in O or A soil horizons of a sandy Alfisol under a coniferous forest was conducted.
Abstract: How plant inputs from above- versus below-ground affect long term carbon (C) and nitrogen (N) retention and stabilization in soils is not well known We present results of a decade-long field study that traced the decomposition of 13C- and 15N-labeled Pinus ponderosa needle and fine root litter placed in O or A soil horizons of a sandy Alfisol under a coniferous forest We measured the retention of litter-derived C and N in particulate (>2 mm) and bulk soil (<2 mm) fractions, as well as in density-separated free light and three mineral-associated fractions After 10 years, the influence of slower initial mineralization of root litter compared to needle litter was still evident: almost twice as much root litter (44% of C) was retained than needle litter (22–28% of C) After 10 years, the O horizon retained more litter in coarse particulate matter implying the crucial comminution step was slower than in the A horizon, while the A horizon retained more litter in the finer bulk soil, where it was recovered in organo-mineral associations Retention in these A horizon mineral-associated fractions was similar for roots and needles Nearly 5% of the applied litter C (and almost 15% of the applied N) was in organo-mineral associations, which had centennial residence times and potential for long-term stabilization Vertical movement of litter-derived C was minimal after a decade, but N was significantly more mobile Overall, the legacy of initial litter quality influences total SOM retention; however, the potential for and mechanisms of long-term SOM stabilization are influenced not by litter type but by soil horizon

Journal ArticleDOI
TL;DR: In this paper, the effects of degraded patch formation on soil properties (i.e., total carbon, total nitrogen, ammonium nitrogen, nitrate nitrogen, available phosphorus, dissolved organic carbon, moisture, δ15N, Δ13C, and pH) and NCMs (based on nifH, amoA, narG, nirK, and nirS genes and their transcripts) across three Tibetan alpine meadows at different degradation stages.
Abstract: Alpine meadows on the Tibetan Plateau have experienced severe degradation in recent decades. Although the effects of alpine meadow degradation on soil properties have been well documented, there is still a paucity of knowledge regarding the responses of nitrogen-cycling microbes (NCMs) to degradation and their links to the changes in soil properties. Here, we systematically determined the effects of degraded patch formation on soil properties (i.e., total carbon, total nitrogen, ammonium nitrogen, nitrate nitrogen, available phosphorus, dissolved organic carbon, moisture, δ15N, δ13C, and pH) and NCMs (based on nifH, amoA, narG, nirK, and nirS genes and their transcripts) across three Tibetan alpine meadows at different degradation stages. Results showed that compared to the original grassed patches, the contents of most soil nutrients (e.g., carbon, nitrogen, and phosphorus) were significantly decreased in the degraded patches across the study sites. Degraded patches also tended to have higher soil δ15N values and nitrate contents. Among the aforementioned NCMs, soil diazotrophs and denitrifiers only showed weak responses to the patch formation, while ammonia-oxidizing microbes showed the highest consistency and sensitivity in response to the patch formation across the study sites. The abundance of amoA gene and archaeal amoA mRNA significantly increased in the degraded patches, and they were positively correlated with soil δ15N values and nitrate nitrogen contents, but negatively correlated with soil total nitrogen and inorganic nitrogen contents. These results suggest that the increased ammonia-oxidizing microbial abundance may be an important driver of soil nitrogen loss during degraded patch formation in alpine meadows.

Journal ArticleDOI
TL;DR: In this paper, the authors quantified the gas fluxes and substrate availability in a subtropical coastal wetland off the coast of southeast Queensland, Australia over a complete wet-dry seasonal cycle.
Abstract: Currently, there is a lack of knowledge about GHG emissions, specifically N2O and CH4, in subtropical coastal freshwater wetland and mangroves in the southern hemisphere. In this study, we quantified the gas fluxes and substrate availability in a subtropical coastal wetland off the coast of southeast Queensland, Australia over a complete wet-dry seasonal cycle. Sites were selected along a salinity gradient ranging from marine (34 psu) in a mangrove forest to freshwater (0.05 psu) wetland, encompassing the range of tidal influence. Fluxes were quantified for CH4 (range −0.4–483 mg C–CH4 h−1 m−2) and N2O (−5.5–126.4 μg N–N2O h−1 m−2), with the system acting as an overall source for CH4 and N2O (mean N2O and CH4 fluxes: 52.8 μg N–N2O h−1 m−2 and 48.7 mg C–CH4 h−1 m−2, respectively). Significantly higher N2O fluxes were measured during the summer months (summer mean 64.2 ± 22.2 μg N–N2O h−1 m−2; winter mean 33.1 ± 24.4 µg N–N2O h–1 m−2) but not CH4 fluxes (summer mean 30.2 ± 81.1 mg C–CH4 h−1 m−2; winter mean 37.4 ± 79.6 mg C–CH4 h−1 m−2). The changes with season are primarily driven by temperature and precipitation controls on the dissolved inorganic nitrogen (DIN) concentration. A significant spatial pattern was observed based on location within the study site, with highest fluxes observed in the freshwater tidal wetland and decreasing through the mangrove forest. The dissolved organic carbon (DOC) varied throughout the landscape and was correlated with higher CH4 fluxes, but this was a nonlinear trend. DIN availability was dominated by N–NH4 and correlated to changes in N2O fluxes throughout the landscape. Overall, we did not observe linear relationships between CH4 and N2O fluxes and salinity, oxygen or substrate availability along the fresh-marine continuum, suggesting that this ecosystem is a mosaic of processes and responses to environmental changes.

Journal ArticleDOI
TL;DR: In this article, the authors examined soil nutrients and heterotrophic N-fixation across a gradient of 24 temperate conifer forests shaped by legacies of symbiotic Nfixing trees.
Abstract: Multiple nutrient cycles regulate biological nitrogen (N) fixation in forests, yet long-term feedbacks between N-fixation and coupled element cycles remain largely unexplored We examined soil nutrients and heterotrophic N-fixation across a gradient of 24 temperate conifer forests shaped by legacies of symbiotic N-fixing trees We observed positive relationships among mineral soil pools of N, carbon (C), organic molybdenum (Mo), and organic phosphorus (P) across sites, evidence that legacies of symbiotic N-fixing trees can increase the abundance of multiple elements important to heterotrophic N-fixation Soil N accumulation lowered rates of heterotrophic N-fixation in organic horizons due to both N inhibition of nitrogenase enzymes and declines in soil organic matter quality Experimental fertilization of organic horizon soil revealed widespread Mo limitation of heterotrophic N-fixation, especially at sites where soil Mo was scarce relative to C Fertilization also revealed widespread absence of P limitation, consistent with high soil P:Mo ratios Responses of heterotrophic N-fixation to added Mo (positive) and N (negative) were correlated across sites, evidence that multiple nutrient controls of heterotrophic N-fixation were more common than single-nutrient effects We propose a conceptual model where symbiotic N-fixation promotes coupled N, C, P, and Mo accumulation in soil, leading to positive feedback that relaxes nutrient limitation of overall N-fixation, though heterotrophic N-fixation is primarily suppressed by strong negative feedback from long-term soil N accumulation

Journal ArticleDOI
TL;DR: In this paper, the authors examined changes in dissolved organic matter (DOM) dynamics in coastal blackwater rivers under extreme flooding conditions in the southeastern United States and found that DOM aromaticity and abundance of humic substances significantly increased during the same period.
Abstract: 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.

Journal ArticleDOI
TL;DR: The results suggest that microbial resource allocation for phosphatase synthesis is primarily controlled by available inorganic P concentration and soil pH, but the effects of soil types and land uses are also significant.
Abstract: According to the resource allocation model for extracellular enzyme synthesis, microorganisms should preferentially allocate their resources to phosphorus (P)-acquiring enzyme synthesis when P availability is low in soils. However, the validity of this model across different soil types and soils differing in their microbial community composition has not been well demonstrated. Here we investigated whether the resource allocation model for phosphatase synthesis is applicable across different soil types (Andosols, Acrisols, Cambisols, and Fluvisols) and land uses (arable and forest), and we examined which soil test P and/or P fraction microorganisms responded to when investing their resources in phosphatase synthesis in the soils. The ratio of alkaline phosphatase (ALP) to β-d-glucosidase (BG) activities in the arable soils and the ratio of acid phosphatase (ACP) to BG activities in the forest soils were significantly negatively related with the available inorganic P concentration. We also observed significant effects of available inorganic P, pH, soil types, and land uses on the (ACP + ALP)/BG ratio when the data for the arable and forest soils were combined and used in a stepwise multiple regression analysis. These results suggest that microbial resource allocation for phosphatase synthesis is primarily controlled by available inorganic P concentration and soil pH, but the effects of soil types and land uses are also significant.

Journal ArticleDOI
TL;DR: In this paper, the authors examined the Baltic Sea carbon, nitrogen, and phosphorus cycling and quantified key fluxes in the C, N, and P cycling, and found that while the external supplies of total N and P (TN and TP) are largely balanced by internal removal processes, the total carbon (TC) supply is mainly compensated by a net export out of the system.
Abstract: In this study we examine pools of carbon (C), nitrogen (N), and phosphorus (P) in the Baltic Sea, both simulated and reconstructed from observations. We further quantify key fluxes in the C, N, and P cycling. Our calculations include pelagic reservoirs as well as the storage in the active sediment layer, which allows a complete coverage of the overall C, N, and P cycling on a system-scale. A striking property of C versus N and P cycling is that while the external supplies of total N and P (TN and TP) are largely balanced by internal removal processes, the total carbon (TC) supply is mainly compensated by a net export out of the system. In other words, external inputs of TN and TP are, in contrast to TC, rather efficiently filtered within the Baltic Sea. Further, there is a net export of TN and TP out of the system, but a net import of dissolved inorganic N and P (DIN and DIP). There is on the contrary a net export of both the organic and inorganic fractions of TC. While the pelagic pools of TC and TP are dominated by inorganic compounds, TN largely consists of organic N because allochthonous organic N is poorly degradable. There are however large basin-wise differences in C, N, and P elemental ratios as well as in inorganic versus organic fractions. These differences reflect both the differing ratios in external loads and differing oxygen conditions determining the redox-dependent fluxes of DIN and DIP.

Journal ArticleDOI
TL;DR: In this article, the authors assessed the annual loads of suspended particulate matter (SPM), dissolved organic carbon (DOC), total nitrogen (TN) and total phosphorus (TP) at the Lake Ontario inlet of the St. Lawrence River (SLR) and its estuarine outlet at Quebec City (12,090m3−s−1).
Abstract: Increased flux of carbon and nutrients from human activities in river basins were linked to acidification and deepwater hypoxia in estuaries and coastal areas worldwide. Annual loads (1995–2011) of suspended particulate matter (SPM), dissolved organic carbon (DOC), total nitrogen (TN) and total phosphorus (TP) were assessed at the Lake Ontario inlet of the St. Lawrence River (SLR) (7110 m3 s−1) and its estuarine outlet at Quebec City (12,090 m3 s−1). Internal loads from the Ottawa River (1950 m3 s−1), seventeen other tributaries, urban wastewaters, atmospheric deposition and erosion were also estimated. Erosion (65% of SPM, 29% of TP), inflow from Lake Ontario (42% of DOC, 47% of TN) and Ottawa River (28% of DOC) contributed important flux to the estuary. Loads from other tributaries (20 and 27% of TN and TP at Quebec City) largely exceeded municipal sources (6% of exported TN and TP) and require future remediation. Aquatic plants fixed 277,000 t of C, 49,000 t of N and 7000 t of P (May–Sept.), delaying the nutrient flux to the estuary and turning the SLR into a nutrient sink over summers of lowest discharge. Degradation of exported organic C could consume 5.4–7.1 million t O2 year−1 in the estuary whereas SLR flux of N and P represent 31–47% and 7–14% of total annual estuarine flux, respectively. Carbon and Nitrogen flux from freshwaters partly explain the decline in pH and oxygen concentrations in deep estuarine waters thus highlighting the need to reduce diffuse sources of nutrients in the entire watershed.

Journal ArticleDOI
TL;DR: In this paper, a multi-sensor approach was proposed to simultaneously measure temperature and moisture of the biocrust surface layer and the deeper soil profile, concurrent with automated measurement of surface soil CO2 effluxes.
Abstract: Carbon cycling associated with biological soil crusts, which occupy interspaces between vascular plants in drylands globally, may be an important part of the coupled climate-carbon cycle of the Earth system. A major challenge to understanding CO2 fluxes in these systems is that much of the biotic and biogeochemical activity occurs in the upper few mm of the soil surface layer (i.e., the ‘mantle of fertility’), which exhibits highly dynamic and difficult to measure temperature and moisture fluctuations. Here, we report a multi-sensor approach to simultaneously measuring temperature and moisture of this biocrust surface layer (0–2 mm), and the deeper soil profile, concurrent with automated measurement of surface soil CO2 effluxes. Our results illuminate robust relationships between biocrust water content and field CO2 pulses that have previously been difficult to detect and explain. All observed CO2 pulses over the measurement period corresponded to surface wetting events, including when the wetting events did not penetrate into the soil below the biocrust layer (0–2 mm). The variability of temperature and moisture of the biocrust surface layer was much greater than even in the 0–5 cm layer of the soil beneath the biocrust, or deeper in the soil profile. We therefore suggest that coupling surface measurements of biocrust moisture and temperature to automated CO2 flux measurements may greatly improve our understanding of the climatic sensitivity of carbon cycling in biocrusted interspaces in our study region, and that this method may be globally relevant and applicable.

Journal ArticleDOI
TL;DR: In this paper, the authors examined long-term winter data (30+ years, 2-3 sample events per winter) in 7 temperate lakes of forested northern Wisconsin, USA.
Abstract: In lakes that experience seasonal ice cover, understanding of nitrogen–oxygen coupling and nitrification has been dominated by observations during open water, ice-free conditions. To address knowledge gaps about nitrogen–oxygen linkages under ice, we examined long-term winter data (30 + years, 2–3 sample events per winter) in 7 temperate lakes of forested northern Wisconsin, USA. Across lakes and depths, there were strong negative relationships between dissolved oxygen (DO) and the number of days since ice-on, reflecting consistent DO consumption rates under ice. In two bog lakes that routinely experience prolonged winter DO concentrations below 1.0 mg L−1, nitrate accumulated near the ice surface mainly in late winter, suggesting nitrification may depend on biogenic oxygen from photosynthesis. In contrast, within five oligotrophic-mesotrophic lakes, nitrate accumulated more consistently over winter and often throughout the water column, especially at intermediate depths. Exogenous inputs of nitrate to these lakes were minimal compared to rates of nitrate accumulation. To produce the nitrate via in-lake nitrification, substantial oxygen consumption by ammonium oxidizing microbes would be required. Among lakes and depths that had significant DO depletion over winter, the stoichiometric nitrifier oxygen demand ranged from 1 to 25% of the DO depletion rate. These estimates of nitrifier-driven DO decline are likely conservative because we did not account for nitrate consumed by algal uptake or denitrification. Our results provide an example of nitrification at temperatures < 5 degrees C having a substantial influence on ecosystem-level nitrogen and oxygen availability in seasonally-frozen, northern forested lakes. Consequently, models of under-ice dissolved oxygen dynamics may be advanced through consideration of nitrification, and more broadly, coupled nitrogen and oxygen cycling.

Journal ArticleDOI
TL;DR: In this article, isotope signatures of N2O (δ15Nbulk, δ18O, and 15N-N2O site preference) were analyzed with an isotope ratio mass spectrometer.
Abstract: Nitrite (NO2 −) as an important intermediate of the biological nitrogen cycle is particularly reactive in acidic soils and acts as a source of N2O and NOx (NO and NO2). However, abiotic and biotic pathways of NO2 −-driven N2O and NOx production in forest soil and the role of soil organic matter (SOM) in these processes are still unclear. In this study, NO2 − was applied to both unsterile and sterilized soil samples as well as to different SOM fractions from a Norway spruce forest. Biotic and abiotic N2O emission was measured with an infrared absorption analyzer and gas chromatography, while NOx emission was quantified with a chemiluminescence analyzer. Isotopic signatures of N2O (δ15Nbulk, δ18O, and 15N-N2O site preference) were analyzed with an isotope ratio mass spectrometer. After NO2 − addition, a large amount of NOx was emitted immediately, while N2O emission occurred 15–60 min later and was much lower compared to NOx. Sterilization of soil decreased N2O emission significantly, but not NOx emission. The 15N site preference of N2O ranged from 7.98 to 11.58‰ for abiotic and 4.69–7.42‰ for biotic sources. The fulvic acid fraction contributed the most to abiotic N2O emission, while the fastest NO and N2O emission occurred after NO2 −application to the humin fraction, followed by the humic acid fraction. These results are important for the future understanding of NOx and N2O sources, as well as the use of isotopic signatures for source-partitioning N2O emission from soil.