Ammonia emissions from a dairy housing and wastewater treatment plant quantified with an inverse dispersion method accounting for deposition loss

Ammonia (NH3) emissions negatively impact air, soil, and water quality, hence human health and biodiversity. Significant emissions, including the largest sources, originate from single or multiple structures, such as livestock facilities and wastewater treatment plants (WWTPs). The inverse dispersion method (IDM) is effective in measuring total emissions from such sources, although depositional loss between the source and point of measurement is often not accounted for. We applied IDM with a deposition correction to determine total emissions from a representative dairy housing and WWTP during several months in autumn and winter in Switzerland. Total emissions were 1.19?±?0.48 and 2.27?±?1.53?kg NH3 d?1 for the dairy housing and WWTP, respectively, which compared well with literature values, despite the paucity of WWTP data. A concurrent comparison with an inhouse tracer ratio method at the dairy housing indicated an offset of the IDM emissions by?<?20%. Diurnal emission patterns were evident at both sites mostly driven by changes in air temperature with potential lag effects such as following sludge agitation. Modeled deposition corrections to adjust the concentration loss detected at the measurement point with the associated footprint were 22?28% of the total emissions and the cumulative fraction of deposition to emission modeled with distance from the source was between 7% and 12% for the measurement distances (60?150?m). Although estimates of depositional loss were plausible, the approach is still connected with substantial uncertainty, which calls for future validation measurements. Longer measurement periods encompassing more management activities and environmental conditions are required to assess predictor variable importance on emission dynamics. Combined, IDM with deposition correction will allow the determination of emission factors at reduced efforts and costs, thereby supporting the development and assessment of emission reducing methods and expand the data availability for emission inventories. Implications: Ammonia emissions must be measured to determine emission factors and reporting national inventories. Measurements from structures like farms and industrial plants are complex due to the many different emitting surfaces and the building configuration leading to a poor data availability. Micrometeorological methods provide high resolution emission data from the entire structure, but suffer from uncertainties, as the instruments must be placed at a distance from the structure resulting in a greater loss of the emitted ammonia via dry deposition before it reaches the measurement. This study constrains such emission measurements from a dairy housing and wastewater treatment plant by applying a simple correction to account for the deposition loss and compares the results to other methods

Stable Isotope Analysis of Greenhouse Gases Requires Analyte Preconcentration

Nitrous oxide (N2O) is an important trace gas contributing to global warming and depletion of ozone in the stratosphere. Its increasing abundance is caused mainly by anthropogenic sources, such as application of fertilizers in agriculture or emissions from industry. To understand the N2O global budget, its sources and sinks need to be well-described and quantified. In this project, a new method for N2O source appointment was developed that can help with this task. The method is based on analysis of the eight most abundant isotopic molecules of N2O, using quantum cascade laser absorption spectroscopy (QCLAS). The applicability of the method towards the N2O biogeochemical cycle was demonstrated on a prominent N2O source (bacterial denitrification) and the most important N2O sink (UV photolysis) on samples prepared in laboratory experiments. An extension of the QCLAS method to natural samples can be achieved by hyphenation with a preconcentration technique that increases concentration of the analyte and standardizes the sample matrix. This article provides an overview of currently applied preconcentration techniques in the field of greenhouse-gas analysis and a description of the preconcentration device TREX that will be employed in future projects with the developed QCLAS method

Comparison of Methane Emission Patterns from Dairy Housings with Solid and Slatted Floors at Two Locations

Methane (CH4) emissions from dairy husbandry are a hot topic in the context of active climate protection, where housing systems with slatted floors and slurry storage inside are in general expected to emit more than systems with solid floors. There are multiple factors, including climate conditions, that modulate the emission pattern. In this study, we investigated interrelations between CH4 emission patterns and climate conditions as well as differences between farm locations versus floor effects. We considered three data sets with 265, 264 and 275 hourly emission values from two housing systems (one slatted, one solid floor) in Switzerland and one system with solid floors in Germany. Each data set incorporated measurements in summer, winter and a transition season. The average CH4 emission was highest for the slatted floor system. For the solid floor systems, CH4 emissions at the Swiss location were around 30% higher compared to the German location. The shape of the distributions for the two solid floor systems was rather similar but very different from the distribution for the slatted floor system, which showed higher prevalence for extreme emissions. Rank correlations, which measure the degree of similarity between two rankings in terms of linear relation, were not able to detect dependencies at the selected significance level. In contrast, mutual information, which measures more general statistical dependencies in terms of shared information, revealed highly significant dependencies for almost all variable pairs. The weakest statistical relation was found between winds speed and CH4 emission, but the convection regime was found to play a key role. Clustering was consistent among the three data sets with five typical clusters related to high/low temperature and wind speed, respectively, as well as in some cases to morning and evening hours. Our analysis showed that despite the disparate and often insignificant correlation between environmental variables and CH4 emission, there is a strong relation between both, which shapes the emission pattern in many aspects much more in addition to differences in the floor type. Although a clear distinction of high and low emission condition clusters based on the selected environmental variables was not possible, trends were clearly visible. Further research with larger data sets is advisable to verify the detected trends and enable prognoses for husbandry systems under different climate conditions

Methane preconcentration by adsorption: a methodology for materials and conditions selection

Methane (CH $$_4$$ 4 ) adsorption has been widely studied, mainly in the context of natural gas purification. A much less prominent, but highly relevant application is the preconcentration of CH $$_4$$ 4 from ambient air. In this study, we compare six different commercial adsorbent materials with respect to their effectiveness for methane preconcentration: a macroporous polymeric resin (HayeSep D), multi-walled carbon nanotubes, two microporous metal-organic frameworks (HKUST-1 and ZIF-8), and two zeolites (5A and 13X). The most relevant properties, such as isosteric enthalpy of adsorption, specific surface area and the selectivity for CH $$_4$$ 4 adsorption over N $$_2$$ 2 were characterized by analyzing adsorption/desorption isotherms. Using these parameters, we discuss the tested adsorbents with respect to the most important properties and identify the most promising candidates. Furthermore we identify the experimental conditions that are expected to give the best results with respect to practical applications

Assessment of the inverse dispersion method for the determination of methane emissions from a dairy housing

Methane (CH4) emissions from dairy housings, mainly originating from enteric fermentation of ruminating animals, are a significant source of greenhouse gases. The quantification of emissions from naturally ventilated dairy housings is challenging due to the spatial distribution of sources (animals, housing areas) and variable air exchange. The inverse dispersion method (IDM) is a promising option, which is increasingly used to determine gaseous emissions from stationary sources, as it offers high flexibility in the application at reasonable costs. We used a backward Lagrangian stochastic model combined with concentration measurements by open-path tunable diode laser spectrometers placed up- and downwind of a naturally ventilated housing with 40 dairy cows to determine the CH4 emissions. The average emissions per livestock unit (LU) were 317 (±44) g LU−1 d−1 and 267 (±43) g LU−1 d−1 for the first and second campaign, in September – October and November – December, respectively. For each campaign, inhouse tracer ratio measurements (iTRM) were conducted in parallel during two subperiods. For simultaneous measurements, IDM showed average emissions which were lower by 8% and 1% than that of iTRM, respectively, for the two campaigns. The differences are within the uncertainty range of any of the two methods. The IDM CH4 emissions were further analysed by wind direction and atmospheric stability and no differences in emissions were found. Overall, IDM showed its aptitude to accurately determine CH4 emissions from dairy housings or other stationary sources if the site allows adequate placement of sensors up- and downwind in the prevailing wind direction. To acquire reliable emission data, depending on the data loss during measurements due to quality filtering or instrument failure, a measuring time of at least 10 days is required

In-depth analysis of N2O fluxes in tropical forest soils of the Congo Basin combining isotope and functional gene analysis

Primary tropical forests generally exhibit large gaseous nitrogen (N) losses, occurring as nitric oxide (NO), nitrous oxide (N2O) or elemental nitrogen (N2). The release of N2O is of particular concern due to its high global warming potential and destruction of stratospheric ozone. Tropical forest soils are predicted to be among the largest natural sources of N2O; however, despite being the world’s second-largest rainforest, measurements of gaseous N-losses from forest soils of the Congo Basin are scarce. In addition, long-term studies investigating N2O fluxes from different forest ecosystem types (lowland and montane forests) are scarce. In this study we show that fluxes measured in the Congo Basin were lower than fluxes measured in the Neotropics, and in the tropical forests of Australia and South East Asia. In addition, we show that despite different climatic conditions, average annual N2O fluxes in the Congo Basin’s lowland forests (0.97 ± 0.53 kg N ha−1 year−1) were comparable to those in its montane forest (0.88 ± 0.97 kg N ha−1 year−1). Measurements of soil pore air N2O isotope data at multiple depths suggests that a microbial reduction of N2O to N2 within the soil may account for the observed low surface N2O fluxes and low soil pore N2O concentrations. The potential for microbial reduction is corroborated by a significant abundance and expression of the gene nosZ in soil samples from both study sites. Although isotopic and functional gene analyses indicate an enzymatic potential for complete denitrification, combined gaseous N-losses (N2O, N2) are unlikely to account for the missing N-sink in these forests. Other N-losses such as NO, N2 via Feammox or hydrological particulate organic nitrogen export could play an important role in soils of the Congo Basin and should be the focus of future research

Congenital Lipoid Adrenal Hyperplasia: Functional Characterization of Three Novel Mutations in the STAR Gene

AbstractContext: The steroidogenic acute regulatory protein (StAR) has been shown to be essential for steroidogenesis by mediating cholesterol transfer into mitochondria. Inactivating StAR mutations cause the typical clinical picture of congenital lipoid adrenal hyperplasia.Objective: The objective of the investigation was to study the functional and structural consequences of three novel StAR mutations (p.N148K in an Italian patient; p.P129fs and p.Q128R in a Turkish patient).Methods and Results: Transient in vitro expression of the mutant proteins together with P450 side-chain cleavage enzyme, adrenodoxin, and adrenodoxin reductase yielded severely diminished cholesterol conversion of the p.N148K mutant, the combined p.P129fs and p.Q128R mutant, and the p.P129fs mutant by itself. The p.Q128R mutant led to a higher cholesterol conversion than the wild-type StAR protein. As derived from three-dimensional protein modeling, the residue N148 is lining the ligand cavity of StAR. A positively charged lysine residue at position 148 disturbs the hydrophobic cluster formed by the α4-helix and the sterol binding pocket. The frame shift mutation p.P129fs truncates the StAR protein. Residue p.Q128 is situated at the surface of the molecule and is not part of any functionally characterized region of the protein.Conclusion: The mutations p.N148K and p.P129fs cause adrenal insufficiency in both cases and lead to a disorder of sex development with complete sex reversal in the 46, XY case. The mutation p.Q128R, which is not relevant for the patient's phenotype, is the first reported variant showing a gain of function. We speculate that the substitution of hydrophilic glutamine with basic arginine at the surface of the molecule may accelerate cholesterol transfer

Impact of lattice dynamics on the phase stability of metamagnetic FeRh: Bulk and thin films

We present phonon dispersions, element-resolved vibrational density of states (VDOS) and corresponding thermodynamic properties obtained by a combination of density functional theory (DFT) and nuclear resonant inelastic X-ray scattering (NRIXS) across the metamagnetic transition of B2 FeRh in the bulk material and thin epitaxial films. We see distinct differences in the VDOS of the antiferromagnetic (AF) and ferromagnetic (FM) phase which provide a microscopic proof of strong spin-phonon coupling in FeRh. The FM VDOS exhibits a particular sensitivity to the slight tetragonal distortions present in epitaxial films, which is not encountered in the AF phase. This results in a notable change in lattice entropy, which is important for the comparison between thin film and bulk results. Our calculations confirm the recently reported lattice instability in the AF phase. The imaginary frequencies at the $X$-point depend critically on the Fe magnetic moment and atomic volume. Analyzing these non vibrational modes leads to the discovery of a stable monoclinic ground state structure which is robustly predicted from DFT but not verified in our thin film experiments. Specific heat, entropy and free energy calculated within the quasiharmonic approximation suggest that the new phase is possibly suppressed because of its relatively smaller lattice entropy. In the bulk phase, lattice degrees of freedom contribute with the same sign and in similar magnitude to the isostructural AF-FM phase transition as the electronic and magnetic subsystems and therefore needs to be included in thermodynamic modeling.Comment: 15 pages, 12 figure

N2O isotopocule measurements using laser spectroscopy:analyzer characterization and intercomparison

For the past two decades, the measurement of nitrous oxide (N2O) isotopocules – isotopically substituted molecules 14N15N16O, 15N14N16O and 14N14N18O of the main isotopic species 14N14N16O – has been a promising technique for understanding N2O production and consumption pathways. The coupling of non-cryogenic and tuneable light sources with different detection schemes, such as direct absorption quantum cascade laser absorption spectroscopy (QCLAS), cavity ring-down spectroscopy (CRDS) and off-axis integrated cavity output spectroscopy (OA-ICOS), has enabled the production of commercially available and field-deployable N2O isotopic analyzers. In contrast to traditional isotope-ratio mass spectrometry (IRMS), these instruments are inherently selective for position-specific 15N substitution and provide real-time data, with minimal or no sample pretreatment, which is highly attractive for process studies. Here, we compared the performance of N2O isotope laser spectrometers with the three most common detection schemes: OA-ICOS (N2OIA-30e-EP, ABB – Los Gatos Research Inc.), CRDS (G5131-i, Picarro Inc.) and QCLAS (dual QCLAS and preconcentration, trace gas extractor (TREX)-mini QCLAS, Aerodyne Research Inc.). For each instrument, the precision, drift and repeatability of N2O mole fraction [N2O] and isotope data were tested. The analyzers were then characterized for their dependence on [N2O], gas matrix composition (O2, Ar) and spectral interferences caused by H2O, CO2, CH4 and CO to develop analyzer-specific correction functions. Subsequently, a simulated two-end-member mixing experiment was used to compare the accuracy and repeatability of corrected and calibrated isotope measurements that could be acquired using the different laser spectrometers. Our results show that N2O isotope laser spectrometer performance is governed by an interplay between instrumental precision, drift, matrix effects and spectral interferences. To retrieve compatible and accurate results, it is necessary to include appropriate reference materials following the identical treatment (IT) principle during every measurement. Remaining differences between sample and reference gas compositions have to be corrected by applying analyzer-specific correction algorithms. These matrix and trace gas correction equations vary considerably according to N2O mole fraction, complicating the procedure further. Thus, researchers should strive to minimize differences in composition between sample and reference gases. In closing, we provide a calibration workflow to guide researchers in the operation of N2O isotope laser spectrometers in order to acquire accurate N2O isotope analyses. We anticipate that this workflow will assist in applications where matrix and trace gas compositions vary considerably (e.g., laboratory incubations, N2O liberated from wastewater or groundwater), as well as extend to future analyzer models and instruments focusing on isotopic species of other molecules.ISSN:1867-1381ISSN:1867-854