Challenges in measuring nitrogen isotope signatures in inorganic nitrogen forms: An interlaboratory comparison of three common measurement approaches.

RATIONALE: Stable isotope approaches are increasingly applied to better understand the cycling of inorganic nitrogen (Ni ) forms, key limiting nutrients in terrestrial and aquatic ecosystems. A systematic comparison of the accuracy and precision of the most commonly used methods to analyze δ15 N in NO3 - and NH4 + and interlaboratory comparison tests to evaluate the comparability of isotope results between laboratories are, however, still lacking. METHODS: Here, we conducted an interlaboratory comparison involving 10 European laboratories to compare different methods and laboratory performance to measure δ15 N in NO3 - and NH4 + . The approaches tested were (a) microdiffusion (MD), (b) chemical conversion (CM), which transforms Ni to either N2 O (CM-N2 O) or N2 (CM-N2 ), and (c) the denitrifier (DN) methods. RESULTS: The study showed that standards in their single forms were reasonably replicated by the different methods and laboratories, with laboratories applying CM-N2 O performing superior for both NO3 - and NH4 + , followed by DN. Laboratories using MD significantly underestimated the "true" values due to incomplete recovery and also those using CM-N2 showed issues with isotope fractionation. Most methods and laboratories underestimated the at%15 N of Ni of labeled standards in their single forms, but relative errors were within maximal 6% deviation from the real value and therefore acceptable. The results showed further that MD is strongly biased by nonspecificity. The results of the environmental samples were generally highly variable, with standard deviations (SD) of up to ± 8.4‰ for NO3 - and ± 32.9‰ for NH4 + ; SDs within laboratories were found to be considerably lower (on average 3.1‰). The variability could not be connected to any single factor but next to errors due to blank contamination, isotope normalization, and fractionation, and also matrix effects and analytical errors have to be considered. CONCLUSIONS: The inconsistency among all methods and laboratories raises concern about reported δ15 N values particularly from environmental samples.

Nitrification is the primary source for NO in N-saturated subtropical forest soils: Results from in situ 15 N labeling.

RATIONALE: Acidic subtropical forest soils that receive high atmospheric nitrogen (N) deposition have been identified as important sources of nitric oxide (NO). The relative importance of major processes producing NO is unclear. METHODS: To partition NO sources, we conducted an in situ tracing experiment with 15 NH4 NO3 and NH4 15 NO3 in well-drained acid soils of an N-saturated subtropical forest in Chongqing, southwest China. RESULTS: In the 15 NH4 NO3 treatment, the 15 N signature of NO emitted from the foot of the hillslope (Lower site) was similar to that of the NH4 + pool, indicating predominant autotrophic nitrification for NO formation. In the NH4 15 NO3 treatment, the 15 N enrichment of NO was smaller than that of the NO3 - pool, suggesting minor contribution of denitrification to NO production (~15%). CONCLUSIONS: Nitrification is the main process responsible for NO emissions, even in monsoonal summers when soil water-filled pore space values are relatively high.

Denitrification as a major regional nitrogen sink in subtropical forest catchments: Evidence from multi-site dual nitrate isotopes.

Increasing nitrogen (N) deposition in subtropical forests in south China causes N saturation, associated with significant nitrate (NO3- ) leaching. Strong N attenuation may occur in groundwater discharge zones hydrologically connected to well-drained hillslopes, as has been shown for the subtropical headwater catchment "TieShanPing", where dual NO3- isotopes indicated that groundwater discharge zones act as an important N sink and hotspot for denitrification. Here, we present a regional study reporting inorganic N fluxes over two years together with dual NO3- isotope signatures obtained in two summer campaigns from seven forested catchments in China, representing a gradient in climate and atmospheric N input. In all catchments, fluxes of dissolved inorganic N indicated efficient conversion of NH4+ to NO3- on well-drained hillslopes, and subsequent interflow of NO3- over the argic B-horizons to groundwater discharge zones. Depletion of 15 N- and 18 O-NO3- on hillslopes suggested nitrification as the main source of NO3- . In all catchments, except one of the northern sites, which had low N deposition rates, NO3- attenuation by denitrification occurred in groundwater discharge zones, as indicated by simultaneous 15 N and 18 O enrichment in residual NO3- . By contrast to the southern sites, the northern catchments lack continuous and well-developed groundwater discharge zones, explaining less efficient N removal. Using a model based on 15 NO3- signatures, we estimated denitrification fluxes from 2.4 to 21.7 kg N ha-1 year-1 for the southern sites, accounting for more than half of the observed N removal. Across the southern catchments, estimated denitrification scaled proportionally with N deposition. Together, this indicates that N removal by denitrification is an important component of the N budget of southern Chinese forests and that natural NO3- attenuation may increase with increasing N input, thus partly counteracting further aggravation of N contamination of surface waters in the region.

Modified Method for Trapping and Analyzing 15N in NO Released from Soils.

15N isotope tracing is an effective and direct approach to investigate sources of nitric oxide (NO) formed in soils. However, NO is highly reactive and rapidly converted to nitrogen dioxide (NO2) in the presence of ozone, making it impossible to directly measure 15N in NO. Various wet-chemical methods for conversion of NO to nitrite (NO2-) and nitrate (NO3-) have been proposed for 15N analysis in high-concentration NO sources, such as combustion processes. In contrast, NO concentrations in the soil surface-near air are usually small (ppbv-range), posing major challenges to conversion efficiency and blank correction. Here, we present a modified method in which NO is oxidized quantitatively to NO2 by chromium trioxide (CrO3), before conversion to NO2- and NO3- in an alkaline hydrogen peroxide (H2O2) solution. A denitrifier method was used to reduce NO2- and NO3- in the trapping solution quantitatively to nitrous oxide (N2O) for subsequent 15N analysis. NO trapping efficiencies of >85% were obtained with 50 ppb NO in a 0.5 L min-1 air stream bubbling through a solution of 1.2 M H2O2 and 0.5 M NaOH. In a laboratory test with distinct 15NO abundances, the overall precision was 0.29‰ (δ-values) for natural abundance NO and 0.13 atom % for labeled NO, suggesting that our method can be used for both natural abundance studies and 15N labeling experiments. In a soil incubation experiment with 15NH4NO3, NH415NO3, or Na15NO2 amendments, we found distinct 15N abundances in NO, indicating that our method is well suited to investigate NO sources in soils.

Multiyear dual nitrate isotope signatures suggest that N-saturated subtropical forested catchments can act as robust N sinks.

In forests of the humid subtropics of China, chronically elevated nitrogen (N) deposition, predominantly as ammonium (NH4+ ), causes significant nitrate (NO3- ) leaching from well-drained acid forest soils on hill slopes (HS), whereas significant retention of NO3- occurs in near-stream environments (groundwater discharge zones, GDZ). To aid our understanding of N transformations on the catchment level, we studied spatial and temporal variabilities of concentration and natural abundance (δ15 N and δ18 O) of nitrate (NO3- ) in soil pore water along a hydrological continuum in the N-saturated Tieshanping (TSP) catchment, southwest China. Our data show that effective removal of atmogenic NH4+ and production of NO3- in soils on HS were associated with a significant decrease in δ15 N-NO3- , suggesting efficient nitrification despite low soil pH. The concentration of NO3- declined sharply along the hydrological flow path in the GDZ. This decline was associated with a significant increase in both δ15 N and δ18 O of residual NO3- , providing evidence that the GDZ acts as an N sink due to denitrification. The observed apparent 15 N enrichment factor (ε) of NO3- of about -5‰ in the GDZ is similar to values previously reported for efficient denitrification in riparian and groundwater systems. Episode studies in the summers of 2009, 2010 and 2013 revealed that the spatial pattern of δ15 N and δ18 O-NO3- in soil water was remarkably similar from year to year. The importance of denitrification as a major N sink was also seen at the catchment scale, as largest δ15 N-NO3- values in stream water were observed at lowest discharge, confirming the importance of the relatively small GDZ for N removal under base flow conditions. This study, explicitly recognizing hydrologically connected landscape elements, reveals an overlooked but robust N sink in N-saturated, subtropical forests with important implications for regional N budgets.

Light and temperature controls of aquatic plant photosynthesis downstream of a hydropower plant and the effect of plant removal.

Many rivers worldwide are regulated, and the altered hydrology can lead to mass development of aquatic plants. Plant invasions are often seen as a nuisance for human activities leading to costly remedial actions with uncertain implications for aquatic biodiversity and ecosystem functioning. Mechanical harvesting is often used to remove aquatic plants and knowledge of plant growth rate could improve management decisions. Here, we used a simple light-temperature theoretical model to make a priori prediction of aquatic plant photosynthesis. These predictions were assessed through an open-channel diel change in O2 mass balance approach. A Michaelis-Menten type model was fitted to observed gross primary production (GPP) standardised at 10 °C using a temperature dependence from thermodynamic theory of enzyme kinetics. The model explained 87 % of the variability in GPP of a submerged aquatic plant (Juncus bulbosus L.) throughout an annual cycle in the River Otra, Norway. The annual net plant production was about 2.4 (1.0-3.8) times the standing biomass of J. bulbosus. This suggests a high continuous mass loss due to hydraulic stress and natural mechanical breakage of stems, as the biomass of J. bulbosus remained relatively constant throughout the year. J. bulbosus was predicted to be resilient to mechanical harvesting with photosynthetic capacity recovered within two years following 50-85 % plant removal. The predicted recovery was confirmed through a field experiment where 72 % of J. bulbosus biomass was mechanically removed. We emphasise the value of using a theoretical approach, like metabolic theory, over statistical models where a posteriori results are not always easy to interpret. Finally, the ability to predict ecosystem resilience of aquatic photosynthesis in response to varying management scenarios offers a valuable tool for estimating aquatic ecosystem services, such as carbon regulation. This tool can benefit the EU Biodiversity Strategy and UN Sustainable Development Goals.

Sorption of pure N2O to biochars and other organic and inorganic materials under anhydrous conditions.

Suppression of nitrous oxide (N2O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N2O sorption to biochar. The sorption of N2O and carbon dioxide (CO2) to four biochars was measured in an anhydrous system with pure N2O. The biochar data were compared to those for two activated carbons and other components potentially present in soils-uncharred pine wood and peat-and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities (Qmax) for N2O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17-73 cm(3) g(-1) at 20 °C (median 51 cm(3) g(-1)), with Langmuir affinities (b) of 2-5 atm(-1) (median 3.4 atm(-1)). Both Qmax and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [Qmax 1-34 cm(3) g(-1) (median 7 cm(3) g(-1)); b 0.4-1.7 atm(-1) (median 0.7 atm(-1))]. This indicates that biochar can bind N2O more strongly than both mineral and organic soil materials. Qmax and b for CO2 were comparable to those for N2O. Modeled sorption coefficients obtained with an independent polyparameter-linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5-24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N2O were mostly between -20 and -30 kJ mol(-1), slightly more exothermic than enthalpies of condensation (-16.1 kJ mol(-1)). Qmax of N2O on biochar (50000-130000 µg g(-1) biochar at 20 °C) exceeded the N2O emission suppressions observed in the literature (range 0.5-960 µg g(-1) biochar; median 16 µg g(-1)) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N2O to biochar is a mechanism of N2O emission suppression.

Estimation of ecosystem respiration and photosynthesis in supersaturated stream water downstream of a hydropower plant.

The estimation of whole stream metabolism, as determined by photosynthesis and respiration, is critical to our understanding of carbon cycling and carbon subsidies to aquatic food-webs. The mass development of aquatic plants is a worldwide problem for human activities and often occurs in regulated rivers, altering biodiversity and ecosystem functions. Hydropower plants supersaturate water with gases and prevent the use of common whole stream metabolism models to estimate ecosystem respiration. Here we used the inert noble gas argon to parse out biological from physical processes in stream metabolism calculations. We coupled the O2:Ar ratio determined by gas chromatography in grab samples with in-situ oxygen concentrations measured by an optode to estimate aquatic plant photosynthesis and ecosystem respiration during supersaturation events through a parsimonious approach. The results compared well with a more complicated two-station model based on O2 mass balances in non-supersatured water, and with associated changes in dissolved CO2 (or dissolved inorganic carbon). This new method provides an independent approach to evaluate alternative corrections of dissolved oxygen data (e.g. through the use of total dissolved gases) in long term studies. The use of photosynthesis-irradiance models allows the determination of light parameters such as the onset of light saturation or low light use efficiency, which could be used for inverse modelling. The use of the O2:Ar approach to correct for oversaturation may become more applicable with the emergence of portable mass inlet mass spectrometers (MIMS). Photosynthesis was modest (2.9-5.8 g O2 m2 day-1) compared to other rivers with submerged vegetation, likely indicating nutrient co-limitations (CO2, inorganic N and P). Respiration was very low (-2.1 to -3.9 g O2 m2 day-1) likely due to a lack of allochthonous carbon supply and sandy sediment.

Activity and abundance of methanotrophic bacteria in a northern mountainous gradient of wetlands.

Methane uptake and diversity of methanotrophic bacteria was investigated across six hydrologically connected wetlands in a mountainous forest landscape upstream of lake Langtjern, southern Norway. From floodplain through shrubs, forest and sedges to a Sphagnum covered site, growing season CH4 production was insufficiently consumed to balance release into the atmosphere. Emission increased by soil moisture ranging 0.6-6.8 mg CH4 m-2  h-1 . Top soils of all sites consumed CH4 including at the lowest 78 ppmv CH4 supplied, thus potentially oxidizing 17-51 nmol CH4 g-1 dw h-1 , with highest Vmax 440 nmol g-1 dw h-1 under Sphagnum and lowest Km 559 nM under hummocked Carex. Nine genera and several less understood type I and type II methanotrophs were detected by the key functional gene pmoA involved in methane oxidation. Microarray signal intensities from all sites revealed Methylococcus, the affiliated Lake Washington cluster, Methylocaldum, a Japanese rice cluster, Methylosinus, Methylocystis and the affiliated Peat264 cluster. Notably enriched by site was a floodplain Methylomonas and a Methylocapsa-affiliated watershed cluster in the Sphagnum site. The climate sensitive water table was shown to be a strong controlling factor highlighting its link with the CH4 cycle in elevated wetlands.

Trajectories of freshwater microbial genomics and greenhouse gas saturation upon glacial retreat.

Due to climate warming, ice sheets around the world are losing mass, contributing to changes across terrestrial landscapes on decadal time spans. However, landscape repercussions on climate are poorly constrained mostly due to limited knowledge on microbial responses to deglaciation. Here, we reveal the genomic succession from chemolithotrophy to photo- and heterotrophy and increases in methane supersaturation in freshwater lakes upon glacial retreat. Arctic lakes at Svalbard also revealed strong microbial signatures form nutrient fertilization by birds. Although methanotrophs were present and increased along lake chronosequences, methane consumption rates were low even in supersaturated systems. Nitrous oxide oversaturation and genomic information suggest active nitrogen cycling across the entire deglaciated landscape, and in the high Arctic, increasing bird populations serve as major modulators at many sites. Our findings show diverse microbial succession patterns, and trajectories in carbon and nitrogen cycle processes representing a positive feedback loop of deglaciation on climate warming.

Nitrite stimulates HONO and NOx but not N2O emissions in Chinese agricultural soils during nitrification.

The long-lived greenhouse gas nitrous oxide (N2O) and short-lived reactive nitrogen (Nr) gases such as ammonia (NH3), nitrous acid (HONO), and nitrogen oxides (NOx) are produced and emitted from fertilized soils and play a critical role for climate warming and air quality. However, only few studies have quantified the production and emission potentials for long- and short-lived gaseous nitrogen (N) species simultaneously in agricultural soils. To link the gaseous N species to intermediate N compounds [ammonium (NH4+), hydroxylamine (NH2OH), and nitrite (NO2-)] and estimate their temperature change potential, ex-situ dry-out experiments were conducted with three Chinese agricultural soils. We found that HONO and NOx (NO + NO2) emissions mainly depend on NO2-, while NH3 and N2O emissions are stimulated by NH4+ and NH2OH, respectively. Addition of 3,4-dimethylpyrazole phosphate (DMPP) and acetylene significantly reduced HONO and NOx emissions, while NH3 emissions were significantly enhanced in an alkaline Fluvo-aquic soil. These results suggested that ammonia-oxidizing bacteria (AOB) and complete ammonia-oxidizing bacteria (comammox Nitrospira) dominate HONO and NOx emissions in the alkaline Fluvo-aquic soil, while ammonia-oxidizing archaea (AOA) are dominant in the acidic Mollisol. DMPP effectively mitigated the warming effect in the Fluvo-aquic soil and the Ultisol. In conclusion, our findings highlight NO2- significantly stimulates HONO and NOx emissions from dryland agricultural soils, dominated by nitrification. In addition, subtle differences of soil NH3, N2O, HONO, and NOx emissions indicated different N turnover processes, and should be considered in biogeochemical and atmospheric chemistry models.

Drivers and variability of CO2:O2 saturation along a gradient from boreal to Arctic lakes.

Lakes are significant players for the global climate since they sequester terrestrially derived dissolved organic carbon (DOC), and emit greenhouse gases like CO2 to the atmosphere. However, the differences in environmental drivers of CO2 concentrations are not well constrained along latitudinal and thus climate gradients. Our aim here is to provide a better understanding of net heterotrophy and gas balance at the catchment scale in a set of boreal, sub-Arctic and high-Arctic lakes. We assessed water chemistry and concentrations of dissolved O2 and CO2, as well as the CO2:O2 ratio in three groups of lakes separated by steps of approximately 10 degrees latitude in South-Eastern Norway (near 60° N), sub-Arctic lakes in the northernmost part of the Norwegian mainland (near 70° N) and high-Arctic lakes on Svalbard (near 80° N). Across all regions, CO2 saturation levels varied more (6-1374%) than O2 saturation levels (85-148%) and hence CO2 saturation governed the CO2:O2 ratio. The boreal lakes were generally undersaturated with O2, while the sub-Arctic and high-Arctic lakes ranged from O2 saturated to oversaturated. Regardless of location, the majority of the lakes were CO2 supersaturated. In the boreal lakes the CO2:O2 ratio was mainly related to DOC concentration, in contrast to the sub-Arctic and high-Arctic localities, where conductivity was the major statistical determinant. While the southern part is dominated by granitic and metamorphic bedrock, the sub-Arctic sites are scattered across a range of granitic to sedimentary bed rocks, and the majority of the high-Arctic lakes are situated on limestone, resulting in contrasting lake alkalinities between the regions. DOC dependency of the CO2:O2 ratio in the boreal region together with low alkalinity suggests that in-lake heterotrophic respiration was a major source of lake CO2. Contrastingly, the conductivity dependency indicates that CO2 saturation in the sub-Arctic and high-Arctic lakes was to a large part explained by DIC input from catchment respiration and carbonate weathering.

Soil acidification and loss of base cations in a subtropical agricultural watershed.

Soil acidification along with base cations loss degrades soil quality and is a major environmental problem, especially in agroecosystems with extensive nitrogen (N) fertilization. So far, the rates of proton (H+) production and real soil acidification (loss of base cations) remain unclear in subtropical agricultural watersheds. To assess the current status and future risk of soil acidification in subtropical red soil region of China, a two-year monitoring was conducted in a typical agricultural watershed with upland, paddy fields, and orchards where high N fertilizers are applied (320 kg N ha-1 yr-1). H+ production, neutralization and base cations losses were quantified based on the inputs (rainwater, inflow of water, and fertilizer) and outputs (outflow of water, groundwater drainage, and plant uptake) of major elements (K+, Ca2+, Na+, Mg2+, Al3+, NH4+, NO3-, SO42-, Cl-, and H+). The result showed that total H+ production in the watershed was 5152 molc ha-1 yr-1. N transformation was the most important H+ source (68%), followed by excess plant uptake of cations (25%) and H+ deposition (7%). Base cations exchange and weathering of minerals (3842 molc ha-1 yr-1) dominated H+ neutralization, followed by SO42- adsorption (1081 molc ha-1 yr-1), while H+ and Al3+ leaching amounted to 431 molc ha-1 yr-1, only. These results state clearly that despite significant soil acidification, the acidification of surface waters is minor, implying that soils have buffered substantially the net H+ addition. As a result of soil buffering, there was abundant loss of base cations, whose rate is significantly higher than the previously reported weathering rate of minerals in red soils (3842 vs 230-1080 molc ha-1 yr-1). This suggests that the pool of exchangeable base cations is being depleted in the watershed, increasing the vulnerability of the watershed, and posing a serious threat to future recovery of soils from acidification.

Nitrate runoff loss and source apportionment in a typical subtropical agricultural watershed.

Nitrate (NO3-) loss and enrichment in water bodies caused by fertilization are a major environmental problem in agricultural areas. However, the quantitative contribution of different NO3- sources, especially chemical fertilizers (CF) and soil organic nitrogen (SON), to NO3- runoff loss remains unclear. In this study, a systematic investigation of NO3- runoff and its sources was conducted in a subtropical agricultural watershed located in Yujiang County, Jiangxi Province, China. A semi-monthly sampling was performed at the inlet and outlet from March 2018 to February 2019. Hydrochemical and dual NO3- isotope (15 N and 18O) approaches were combined to estimate the NO3- runoff loss and quantify the contribution of different sources with a Bayesian isotope mixing model. Source apportionment by Stable Isotope Analysis in R (SIAR) suggested that NO3- in runoff was mainly derived from nitrification of ammonium (NH4+) mineralized from SON (37-52%) and manure/sewage (M&S) (25-47%), while the contribution of CF was relatively small (14-25%). The contribution of various sources showed seasonal variations, with a greater contribution of CF in the wet growing season (March to August). Compared with the inlet which contributed 37-40% to runoff NO3-, SON contributed more at the outlet (49-52%). Denitrification in the runoff was small and appeared to be confined to the dry season (September to February), with an estimated NO3- loss of 2.73 kg N ha-1. The net NO3- runoff loss of the watershed was 34.5 kg N ha-1 yr-1, accounting for 15% of the annual fertilization rate (229 kg N ha-1 yr-1). Besides M&S (22%), fertilization and remineralization of SON (CF + SON) were the main sources for the NO3- runoff loss (78%), suggesting accelerated nitrification of NH4+ from CF (24%) and SON mineralization (54%). Our study indicates that NO3- runoff loss in subtropical agricultural watersheds is dominated by nonpoint source pollution from fertilization. SON played a more important role than CF. Besides, the contribution of sewage should not be neglected. Our data suggest that a combination of more rational fertilizer N application (CF), better management of SON, and better treatment of domestic sewage could alleviate NO3- pollution in subtropical China.

Seasonal dynamics of soil pH and N transformation as affected by N fertilization in subtropical China: An in situ 15N labeling study.

Nitrogen (N)-induced soil acidification has received much attention worldwide. Nitrification and soil N mineralization are two key N cycle processes that affect soil acidification. However, the seasonal dynamics of soil pH under their combined influence is unclear. We studied the effect of N fertilization on soil pH and N transformations using 15N tracing in field lysimeters with soils developed from different parent materials (Quaternary red clay, sandstone, and basalt). Maize was planted with 200 kg N ha-1 yr-115N-labeled urea addition. During 7-45 days after fertilization, proton (H+) production due to nitrification of fertilizer N, nitrate (NO3-) leaching, and plant uptake exceeded H+ consumption by base cations mobilization and leaching, resulting in a significant soil pH decline. When nitrification activity decreased (after 45 days), due to exhausted ammonium (NH4+) availability, soil pH rose again. During the fallow period, acid neutralization due to base cation mobilization, and ammonification of soil organic N (SON) offset H+ production caused by nitrification of mineralized SON, leading to a sustained rise in soil pH. After the one-year experiment, no significant soil pH decrease was observed in any of the soils. Parent material had little effect on the seasonal dynamics of soil acidification, which appeared to be controlled by fertilization, environmental factors (temperature and moisture), and plant uptake. In subtropical regions, monitoring of soil pH on an annual basis may mask the effect of N fertilization on soil acidification.

Small-scale on-site treatment of fecal matter: comparison of treatments for resource recovery and sanitization.

On-site small-scale sanitation is common in rural areas and areas without infrastructure, but the treatment of the collected fecal matter can be inefficient and is seldom directed to resource recovery. The aim of this study was to compare low-technology solutions such as composting and lactic acid fermentation (LAF) followed by vermicomposting in terms of treatment efficiency, potential human and environmental risks, and stabilization of the material for reuse in agriculture. A specific and novel focus of the study was the fate of native pharmaceutical compounds in the fecal matter. Composting, with and without the addition of biochar, was monitored by temperature and CO2 production and compared with LAF. All treatments were run at three different ambient temperatures (7, 20, and 38°C) and followed by vermicomposting at room temperature. Materials resulting from composting and LAF were analyzed for fecal indicators, physicochemical characteristics, and residues of ten commonly used pharmaceuticals and compared to the initial substrate. Vermicomposting was used as secondary treatment and assessed by enumeration of Escherichia coli, worm density, and physicochemical characteristics. Composting at 38°C induced the highest microbial activity and resulted in better stability of the treated material, higher N content, lower numbers of fecal indicators, and less pharmaceutical compounds as compared to LAF. Even though analysis of pH after LAF suggested incomplete fermentation, E. coli cell numbers were significantly lower in all LAF treatments compared to composting at 7°C, and some of the anionic pharmaceutical compounds were detected in lower concentrations. The addition of approximately 5 vol % biochar to the composting did not yield significant differences in measured parameters. Vermicomposting further stabilized the material, and the treatments previously composted at 7°C and 20°C had the highest worm density. These results suggest that in small-scale decentralized sanitary facilities, the ambient temperatures can significantly influence the treatment and the options for safe reuse of the material.

Topography-related controls on N2O emission and CH4 uptake in a tropical rainforest catchment.

Forest soils in the warm-humid tropics significantly contribute to the regional greenhouse gas (GHG) budgets. However, spatial heterogeneity of GHG fluxes is often overlooked. Here, we present a study of N2O and CH4 fluxes over 1.5 years, along a topographic gradient in a rainforest catchment in Xishuangbanna, SW China. From the upper hillslope to the foot of the hillslope, and further to the flat groundwater discharge zone, we observed a decrease of N2O emission associated with an increase of soil water-filled-pore-space (WFPS), which we tentatively attribute to more complete denitrification to N2 at larger WFPS. In the well-drained soils on the hillslope, denitrification at anaerobic microsites or under transient water-saturation was the potential N2O source. Negative CH4 fluxes across the catchment indicated a net soil CH4 sink. As the oxidation of atmospheric CH4 is diffusion-limited, soil CH4 consumption rates were negatively related to WFPS, reflecting the topographic control. Our observations also suggest that during dry seasons N2O emission was significantly dampened (<10 µg N2O-N m-2 h-1) and CH4 uptake was strongly enhanced (83 µg CH4-C m-2 h-1) relative to wet seasons (17 µg N2O-N m-2 h-1 and 56 µg CH4-C m-2 h-1). In a post-drought period, several rain episodes induced exceptionally high N2O emissions (450 µg N2O-N m-2 h-1) in the groundwater discharge zone, likely driven by flushing of labile organic carbon accumulated during drought. Considering the global warming potential associated with both GHGs, we found that N2O emissions largely offset the C sink contributed by CH4 uptake in soils (more significant in the groundwater discharge zone). Our study illustrates important topographic controls on N2O and CH4 fluxes in forest soils. With projected climate change in the tropics, weather extremes may interact with these controls in regulating forest GHG fluxes, which should be accounted for in future studies.

Nitrous oxide emissions from oilseed rape cultivation were unaffected by flash pyrolysis biochar of different type, rate and field ageing.

Nitrous oxide (N2O) emission from winter oilseed rape (WOSR) cultivation may compromise the sustainability of oilseed rape biodiesel. Typically, greenhouse gas budgets of WOSR cultivation assume an N2O emission factor (EF) of 1% of the N added in fertilizer and crop residues. Management options to reduce direct soil emissions of N2O include the application of biochar, but efficacy and mechanisms of N2O suppression are elusive. We measured N2O emissions in a WOSR field trial on a sandy loam soil in Denmark over 402 days in 2017-2018, comparing biochar applications from two feedstocks (wheat straw and pig manure fibers), two application rates (1.5 and 15 Mg ha-1) and field ageing of up to three years. Further, a controlled incubation experiment was performed to examine the effect of biochar dose and ageing on N2O production and consumption by denitrification. Biochar treatments had no significant effects on cumulative N2O emissions (1.71-2.78 kg N ha-1 yr-1). Likewise, no significant effects were found on crop yield, yield-scaled N2O emission, soil mineral N content, gravimetric soil moisture or pH. The fertilizer induced EF was 0.51% which is well below the IPCC Tier 1 EF of 1%. High doses of fresh, but not field-aged biochar suppressed N2O production under anoxic conditions ex situ, suggesting that biochar with sufficient liming capacity could mitigate N2O emissions from denitrification also under field conditions. Yet, rates of up to 15 Mg ha-1 flash pyrolysis biochar in the current in situ study, which comprised a pronounced summer drought, showed no significant N2O mitigation. This highlights the need for selecting dedicated biochars and doses and test them in multi-year studies to conclude on their N2O mitigating effect. Yet, in relation to sustainability of WOSR cultivation for biodiesel, the current study suggests that C sequestration by biochar is not compromised by increased N2O emissions.

Phosphorus Availability Promotes Bacterial DOC-Mineralization, but Not Cumulative CO2-Production.

The current trend of increasing input of terrestrially derived dissolved organic carbon (DOC) to boreal freshwater systems is causing increased levels of carbon dioxide (CO2) supersaturation and degassing. Phosphorus (P) is often the most limiting nutrient for bacterial growth and would thus be expected to increase overall mineralization rates and CO2 production. However, high carbon (C) to P ratios of terrestrially derived DOC could also cause elevated cell-specific respiration of the excess C in heterotrophic bacteria. Using data from a survey of 75 Scandinavian lakes along an ecosystem gradient of DOC, we estimated in situ CO2 production rates. These rates showed a unimodal response with DOC-specific CO2 production negatively related to DOC:total phosphorus (TP) ratio, and a turning point at 5 mg C L-1, indicating higher DOC turnover rates in productive than in unproductive lakes. To further assess the dependency of bacterial respiration (BR) on DOC and P, we monitored CO2 production in incubations of water with a gradient of DOC crossed with two levels of inorganic P. Finally, we crossed DOC and P with a temperature gradient to test the temperature dependency of respiration rates [as oxygen (O2) consumption]. While total CO2 production seemed to be unaffected by P additions, respiration rates, and growth yields, as estimated by ribosomal gene copy numbers, suggest increased bacterial growth and decreased cell-specific respiration under non-limited P conditions. Respiration rates showed a sigmoid response to increasing DOC availability reaching a plateau at about 20 mg C L-1 of initial DOC concentrations. In addition to these P and DOC level effects, respiration rates responded in a non-monotonic fashion to temperature with an increase in respiration rates by a factor of 2.6 (±0.2) from 15 to 25°C and a decrease above 30°C. The combined results from the survey and experiments highlight DOC as the major determinant of CO2 production in boreal lakes, with P and temperature as significant modulators of respiration kinetics.

Corrigendum: Phosphorus Availability Promotes Bacterial DOC-Mineralization, but Not Cumulative CO2-Production.

[This corrects the article DOI: 10.3389/fmicb.2020.569879.].