Uncovering Atomic-scale Dynamics in Solid Catalysts via X-ray-based Methods.

Deciphering the structural intricacies of catalysts is essential to advance their atomic-scale engineering. Solid catalysts are complex, with structural features spanning multiple length scales and involving dynamics, which possess challenges in understanding structure-performance relationships. However, advanced operando X-ray characterization techniques, including X-ray absorption spectroscopy (XAS), diffraction (XRD), and pair distribution function analysis (PDF) allow elucidation of structural features under working conditions, discovering transitions from supported nanocrystals to dispersed sites, from solid solutions to supported nanoparticles, or structural changes at the local level. In this mini-review, we discuss case studies exploring the structure of catalysts over different lengths and time scales under different applications, such as CO2 hydrogenation to methanol or the dry reforming of methane, using a combination of operando XAS, XRD and PDF.

Implications for the Hydrogenation of Propyne and Propene with Parahydrogen due to the in situ Transformation of Rh2C to Rh0/C.

NMR spectroscopy studies using parahydrogen-induced polarization have previously established the existence of the pairwise hydrogen addition route in the hydrogenation of unsaturated hydrocarbons over heterogeneous catalysts, including those based on rhodium (Rh0). This pathway requires the incorporation of both hydrogen atoms from one hydrogen molecule to the same product molecule. However, the underlying mechanism for such pairwise hydrogen addition must be better understood. The involvement of carbon, either in the form of carbonaceous deposits on the surface of a catalyst or as a metal carbide phase, is known to modify catalytic properties significantly and thus could also affect the pairwise hydrogen addition route. Here, we explored carbon's role by studying the hydrogenation of propene and propyne with parahydrogen on a Rh2C catalyst and comparing the results with those for a Rh0/C catalyst obtained from Rh2C via H2 pretreatment. While the catalysts Rh2C and Rh0/C differ notably in the rate of conversion of parahydrogen to normal hydrogen as well as in terms of hydrogenation activity, our findings suggest that the carbide phase does not play a significant role in the pairwise H2 addition route on rhodium catalysts.

Meta-analysis reveals the effects of microbial inoculants on the biomass and diversity of soil microbial communities.

Microbial inoculation involves transplanting microorganisms from their natural habitat to new plants or soils to improve plant performance, and it is being increasingly used in agriculture and ecological restoration. However, microbial inoculants can invade and alter the composition of native microbial communities; thus, a comprehensive analysis is urgently needed to understand the overall impact of microbial inoculants on the biomass, diversity, structure and network complexity of native communities. Here we provide a meta-analysis of 335 studies revealing a positive effect of microbial inoculants on soil microbial biomass. This positive effect was weakened by environmental stress and enhanced by the use of fertilizers and native inoculants. Although microbial inoculants did not alter microbial diversity, they induced major changes in the structure and bacterial composition of soil microbial communities, reducing the complexity of bacterial networks and increasing network stability. Finally, higher initial levels of soil nutrients amplified the positive impact of microbial inoculants on fungal biomass, actinobacterial biomass, microbial biomass carbon and microbial biomass nitrogen. Together, our results highlight the positive effects of microbial inoculants on soil microbial biomass, emphasizing the benefits of native inoculants and the important regulatory roles of soil nutrient levels and environmental stress.

DHCR24 inhibitor SH42 increases desmosterol without preventing atherosclerosis development in mice.

The liver X receptor (LXR) is considered a therapeutic target for atherosclerosis treatment, but synthetic LXR agonists generally also cause hepatic steatosis and hypertriglyceridemia. Desmosterol, a final intermediate in cholesterol biosynthesis, has been identified as a selective LXR ligand that suppresses inflammation without inducing lipogenesis. Δ24-Dehydrocholesterol reductase (DHCR24) converts desmosterol into cholesterol, and we previously showed that the DHCR24 inhibitor SH42 increases desmosterol to activate LXR and attenuate experimental peritonitis and metabolic dysfunction-associated steatotic liver disease. Here, we aimed to evaluate the effect of SH42 on atherosclerosis development in APOE∗3-Leiden.CETP mice and low-density lipoproteins (LDL) receptor knockout mice, models for lipid- and inflammation-driven atherosclerosis, respectively. In both models, SH42 increased desmosterol without affecting plasma lipids. While reducing liver lipids in APOE∗3-Leiden.CETP mice, and regulating populations of circulating monocytes in LDL receptor knockout mice, SH42 did not attenuate atherosclerosis in either model.

Redistribution of nitrogen to feed the people on a safer planet.

Lack of nitrogen limits food production in poor countries while excessive nitrogen use in industrial countries has led to transgression of the planetary boundary. However, the potential of spatial redistribution of nitrogen input for food security when returning to the safe boundary has not been quantified in a robust manner. Using an emulator of a global gridded crop model ensemble, we found that redistribution of current nitrogen input to major cereals among countries can double production in the most food-insecure countries, while increasing global production of these crops by 12% with no notable regional loss or reducing the nitrogen input to the current production by one-third. Redistribution of the input within the boundary increased production by 6-8% compared to the current relative distribution, increasing production in the food-insecure countries by two-thirds. Our findings provide georeferenced guidelines for redistributing nitrogen use to enhance food security while safeguarding the planet.

Illuminating Neuropeptide Y Y4 Receptor Binding: Fluorescent Cyclic Peptides with Subnanomolar Binding Affinity as Novel Molecular Tools.

The neuropeptide Y (NPY) Y4 receptor (Y4R), a member of the family of NPY receptors, is physiologically activated by the linear 36-amino acid peptide pancreatic polypeptide (PP). The Y4R is involved in the regulation of various biological processes, most importantly pancreatic secretion, gastrointestinal motility, and regulation of food intake. So far, Y4R binding affinities have been mostly studied in radiochemical binding assays. Except for a few fluorescently labeled PP derivatives, fluorescence-tagged Y4R ligands with high affinity have not been reported. Here, we introduce differently fluorescence-labeled (Sulfo-Cy5, Cy3B, Py-1, Py-5) Y4R ligands derived from recently reported cyclic hexapeptides showing picomolar Y4R binding affinity. With pKi values of 9.22-9.71 (radioligand competition binding assay), all fluorescent ligands (16-19) showed excellent Y4R affinity. Y4R saturation binding, binding kinetics, and competition binding with reference ligands were studied using different fluorescence-based methods: flow cytometry (Sulfo-Cy5, Cy3B, and Py-1 label), fluorescence anisotropy (Cy3B label), and NanoBRET (Cy3B label) binding assays. These experiments confirmed the high binding affinity to Y4R (equilibrium pKd: 9.02-9.9) and proved the applicability of the probes for fluorescence-based Y4R competition binding studies and imaging techniques such as single-receptor molecule tracking.

Soil recalcitrant but not labile organic nitrogen mineralization contributes to microbial nitrogen immobilization and plant nitrogen uptake.

Soil organic nitrogen (N) mineralization not only supports ecosystem productivity but also weakens carbon and N accumulation in soils. Recalcitrant (mainly mineral-associated organic matter) and labile (mainly particulate organic matter) organic materials differ dramatically in nature. Yet, the patterns and drivers of recalcitrant (MNrec) and labile (MNlab) organic N mineralization rates and their consequences on ecosystem N retention are still unclear. By collecting MNrec (299 observations) and MNlab (299 observations) from 57 15N tracing studies, we found that soil pH and total N were the master factors controlling MNrec and MNlab, respectively. This was consistent with the significantly higher rates of MNrec in alkaline soils and of MNlab in natural ecosystems. Interestingly, our analysis revealed that MNrec directly stimulated microbial N immobilization and plant N uptake, while MNlab stimulated the soil gross autotrophic nitrification which discouraged ammonium immobilization and accelerated nitrate production. We also noted that MNrec was more efficient at lower precipitation and higher temperatures due to increased soil pH. In contrast, MNlab was more efficient at higher precipitation and lower temperatures due to increased soil total N. Overall, we suggest that increasing MNrec may lead to a conservative N cycle, improving the ecosystem services and functions, while increasing MNlab may stimulate the potential risk of soil N loss.

Multiresidue analysis of bat guano using GC-MS/MS.

Bats are the second largest mammalian order and are an endangered species group with a strong need for contamination monitoring. To facilitate non-invasive monitoring of the ecological burden in bat populations, a multiresidue method for the simultaneous quantification of 119 analytes including pesticides, persistent organic pollutants (POPs), active pharmaceutical ingredients (APIs), polycyclic aromatic hydrocarbons (PAHs), UV blockers, plasticizers, and other emerging pollutants in bat guano with gas chromatography tandem mass spectrometry (GC-MS/MS) was developed. Sample preparation and clean-up were performed with a modified QuEChERS approach based on DIN EN 15662. The method uses 1.00 g bat guano as sample with acetonitrile and water for liquid-liquid extraction. Phase separation is assisted by citrate-buffered salting out agent. For clean-up of the extract, primary secondary amine (PSA) was combined with graphitized carbon black (GCB). The lower limits of quantification (LLOQ) ranged between 2.5 and 250 µg kg-1. Linearity was shown in a concentration range from the respective LLOQs to 1250 µg kg-1. The median of the mean recovery was 102.4%. Precision was tested at three concentrations. Method and injection precision were adequate with a relative standard deviation (RSD) below 20%. Furthermore, the comparative analysis with LC-MS/MS demonstrated the reliability of the results and provided a valuable extension of the analytical scope. As proof of concept, three guano samples from a German nursery roost of Myotis myotis were analysed. The results show a time-dependent change in contaminant concentration, highlighting the strong need for non-invasive contamination monitoring of whole bat populations.

Towards a unified picture of polarization transfer - pulsed DNP and chemically equivalent PHIP.

Nuclear spin hyperpolarization techniques, such as dynamic nuclear polarization (DNP) and parahydrogen-induced polarization (PHIP), have revolutionized nuclear magnetic resonance and magnetic resonance imaging. In these methods, a readily available source of high spin order, either electron spins in DNP or singlet states in hydrogen for PHIP, is brought into close proximity with nuclear spin targets, enabling efficient transfer of spin order under external quantum control. Despite vast disparities in energy scales and interaction mechanisms between electron spins in DNP and nuclear singlet states in PHIP, a pseudo-spin formalism allows us to establish an intriguing equivalence. As a result, the important low-field polarization transfer regime of PHIP can be mapped onto an analogous system equivalent to pulsed-DNP. This establishes a correspondence between key polarization transfer sequences in PHIP and DNP, facilitating the transfer of sequence development concepts. This promises fresh insights and significant cross-pollination between DNP and PHIP polarization sequence developers.

Warming-Induced Stimulation of Soil N2O Emissions Counteracted by Elevated CO2 from Nine-Year Agroecosystem Temperature and Free Air Carbon Dioxide Enrichment.

Globally, agricultural soils account for approximately one-third of anthropogenic emissions of the potent greenhouse gas and stratospheric ozone-depleting substance nitrous oxide (N2O). Emissions of N2O from agricultural soils are affected by a number of global change factors, such as elevated air temperatures and elevated atmospheric carbon dioxide (CO2). Yet, a mechanistic understanding of how these climatic factors affect N2O emissions in agricultural soils remains largely unresolved. Here, we investigate the soil N2O emission pathway using a 15N tracing approach in a nine-year field experiment using a combined temperature and free air carbon dioxide enrichment (T-FACE). We show that the effect of CO2 enrichment completely counteracts warming-induced stimulation of both nitrification- and denitrification-derived N2O emissions. The elevated CO2 induced decrease in pH and labile organic nitrogen (N) masked the stimulation of organic carbon and N by warming. Unexpectedly, both elevated CO2 and warming had little effect on the abundances of the nitrifying and denitrifying genes. Overall, our study confirms the importance of multifactorial experiments to understand N2O emission pathways from agricultural soils under climate change. This better understanding is a prerequisite for more accurate models and the development of effective options to combat climate change.

Probing Surface Transformations of Lanthanum Nickelate Electrocatalysts during Oxygen Evolution Reaction.

Monitoring the spontaneous reconstruction of the surface of metal oxides under electrocatalytic reaction conditions is critical to identifying the active sites and establishing structure-activity relationships. Here, we report on a self-terminated surface reconstruction of Ruddlesden-Popper lanthanum nickel oxide (La2NiO4+δ) that occurs spontaneously during reaction with alkaline electrolyte species. Using a combination of high-resolution scanning transmission electron microscopy (HR-STEM), surface-sensitive X-ray photoelectron spectroscopy (XPS), and soft X-ray absorption spectroscopy (sXAS), as well as electrochemical techniques, we identify the structure of the reconstructed surface layer as an amorphous (oxy)hydroxide phase that features abundant under-coordinated nickel sites. No further amorphization of the crystalline oxide lattice (beyond the ∼2 nm thick layer formed) was observed during oxygen evolution reaction (OER) cycling experiments. Notably, the formation of the reconstructed surface layer increases the material's oxygen evolution reaction (OER) activity by a factor of 45 when compared to that of the pristine crystalline surface. In contrast, a related perovskite phase, i.e., LaNiO3, did not show noticeable surface reconstruction, and also no increase in its OER activity was observed. This work provides detailed insight into a surface reconstruction behavior dictated by the crystal structure of the parent oxide and highlights the importance of surface dynamics under reaction conditions.

Protocol of a randomised, controlled trial comparing immediate curative therapy with conservative treatment in men aged ≥75 years with non-metastatic high-risk prostate cancer (SPCG 19/GRand-P).

BACKGROUND: Older men (aged ≥75 years) with high risk, non-metastatic prostate cancer (PCa) are increasingly treated with curative therapy (surgery or radiotherapy). However, it is unclear if curative therapy prolongs life and improves health-related quality of life (HRQoL) in this age group compared to conservative therapy, which has evolved considerably during the last decade. STUDY DESIGN: The Scandinavian Prostate Cancer Group (SPCG) 19/Norwegian Get-Randomized Research Group-Prostate (GRand-P) is a randomised, two-armed, controlled, multicentre, phase III trial carried out at study centres in Norway, Denmark, Finland, and Sweden. ENDPOINTS: The primary endpoints are overall survival and HRQoL (burden of disease scale, European Organisation for the Research and Treatment of Cancer [EORTC] Elderly Cancer patients). Secondary endpoints are PCa-specific survival, metastasis-free survival, role-functioning scale (EORTC quality of life questionnaire 30-item core), urinary irritative/obstructive scale (26-item Expanded Prostate Cancer Index Composite [EPIC-26]), bowel scale (EPIC-26), intervention-free survival, PCa morbidity, use of secondary and tertiary systemic therapies, mean quality-adjusted life-years (QALYs), and mean total healthcare costs. PATIENTS AND METHODS: A total of 980 men (aged ≥75 years) with non-metastatic, high-risk PCa will initially be screened with Geriatric 8 (G8) health status screening tool and Mini-COG© brief cognitive test. Participants identified by G8 as 'fit' or 'frail' will be randomised (ratio 1:1) to either immediate curative therapy (radiotherapy or prostatectomy) or conservative therapy (endocrine therapy or observation). Participants who are unable or unwilling to participate in randomisation will be enrolled in a separate observation group. Randomised patients will be followed for 10 years. TRIAL REGISTRATION: Ethics approval has been granted in Norway (457593), Denmark (H-22051998), Finland (R23043) and Sweden (Dnr 2023-05296-01). The trial is registered on Clinicaltrials.org (NCT05448547).

The Impact of Oxygen Surface Coverage and Carbidic Carbon on the Activity and Selectivity of Two-Dimensional Molybdenum Carbide (2D-Mo2C) in Fischer-Tropsch Synthesis.

Transformations of oxygenates (CO2, CO, H2O, etc.) via Mo2C-based catalysts are facilitated by the high oxophilicity of the material; however, this can lead to the formation of oxycarbides and complicate the identification of the (most) active catalyst state and active sites. In this context, the two-dimensional (2D) MXene molybdenum carbide Mo2CTx (Tx are passivating surface groups) contains only surface Mo sites and is therefore a highly suitable model catalyst for structure-activity studies. Here, we report that the catalytic activity of Mo2CTx in Fischer-Tropsch (FT) synthesis increases with a decreasing coverage of surface passivating groups (mostly O*). The in situ removal of Tx species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H2 at 400 °C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of Tx groups reaching a catalyst state that is close to 2D-Mo2C (i.e., a material containing no passivating surface groups). Under steady-state FT conditions, 2D-Mo2C yields higher hydrocarbons (C5+ alkanes) with 55% selectivity. Alkanes up to the kerosine range form, with value of α = 0.87, which is ca. twice higher than the α value reported for 3D-Mo2C catalysts. The steady-state productivity of 2D-Mo2C to C5+ hydrocarbons is ca. 2 orders of magnitude higher relative to a reference ß-Μo2C catalyst that shows no in situ activation under identical FT conditions. The passivating Tx groups of Mo2CTx can be reductively defunctionalized also by using a higher H2 pretreatment temperature of 500 °C. Yet, this approach leads to a removal of carbidic carbon (as methane), resulting in a 2D-Mo2C1-x catalyst that converts CO to CH4 with 61% selectivity in preference to C5+ hydrocarbons that are formed with only 2% selectivity. Density functional theory (DFT) results attribute the observed selectivity of 2D-Mo2C to C5+ alkanes to a higher energy barrier for the hydrogenation of surface alkyl species relative to the energy barriers for C-C coupling. The removal of O* is the rate-determining step in the FT reaction over 2D-Mo2C, and O* is favorably removed in the form of CO2 relative to H2O, consistent with the observation of a high CO2 selectivity (ca. 50%). The absence of other carbon oxygenates is explained by the energetic favoring of the direct over the hydrogen-assisted dissociative adsorption of CO.

Initial evidence on the effect of copper on global cropland nitrogen cycling: A meta-analysis.

Copper (Cu) is a key cofactor in ammonia monooxygenase functioning responsible for the first step of nitrification, but its excess availability impairs soil microbial functions and plant growth. Yet, the impact of Cu on nitrogen (N) cycling and process-related variables in cropland soils remains unexplored globally. Through a meta-analysis of 1209-paired and 319-single observations from 94 publications, we found that Cu (Cu addition or Cu-polluted soil) reduced soil potential nitrification by 33.8% and nitrite content by 73.5% due to reduced soil enzyme activities of nitrification and urease, microbial biomass content, and ammonia oxidizing archaea abundance. The response ratio of potential nitrification decreased with increasing Cu concentration, soil total N, and clay content. We further noted that soil potential nitrification inhibited by 46.5% only when Cu concentration was higher than 150 mg kg-1, while low Cu concentration (less than 150 mg kg-1) stimulated soil nitrate by 99.0%. Increasing initial soil Cu content stimulated gross N mineralization rate due to increased soil organic carbon and total N, but inhibited gross nitrification rate, which ultimately stimulated gross N immobilization rate as a result of increased the residence time of ammonium. This resulted in a lower ratio of gross nitrification rate to gross N immobilization rate, implying a lower potential risk of N loss as evidenced by decreased nitrous oxide emissions with increasing initial soil Cu content. Our analysis offers initial global evidence that Cu has an important role in controlling soil N availability and loss through its effect on N production and consumption.

Climate controls on nitrate dynamics and gross nitrogen cycling response to nitrogen deposition in global forest soils.

Understanding the patterns and controls regulating nitrogen (N) transformation and its response to N enrichment is critical to re-evaluating soil N limitation or availability and its environmental consequences. Nevertheless, how climatic conditions affect nitrate dynamics and the response of gross N cycling rates to N enrichment in forest soils is still only rudimentarily known. Through collecting and analyzing 4426-single and 769-paired observations from 231 15N labeling studies, we found that nitrification capacity [the ratio of gross autotrophic nitrification (GAN) to gross N mineralization (GNM)] was significantly lower in tropical/subtropical (19%) than in temperate (68%) forest soils, mainly due to the higher GNM and lower GAN in tropical/subtropical regions resulting from low C/N ratio and high precipitation, respectively. However, nitrate retention capacity [the ratio of dissimilatory nitrate reduction to ammonium (DNRA) plus gross nitrate immobilization (INO3) to gross nitrification] was significantly higher in tropical/subtropical (86%) than in temperate (54%) forest soils, mainly due to the higher precipitation and GNM of tropical/subtropical regions, which stimulated DNRA and INO3. As a result, the ratio of GAN to ammonium immobilization (INH4) was significantly higher in temperate than in tropical/subtropical soils. Climatic rather than edaphic factors control heterotrophic nitrification rate (GHN) in forest soils. GHN significantly increased with increasing temperature in temperate regions and with decreasing precipitation in tropical/subtropical regions. In temperate forest soils, gross N transformation rates were insensitive to N enrichment. In tropical/subtropical forests, however, N enrichment significantly stimulated GNM, GAN and GAN to INH4 ratio, but inhibited INH4 and INO3 due to reduced microbial biomass and pH. We propose that temperate forest soils have higher nitrification capacity and lower nitrate retention capacity, implying a higher potential risk of N losses. However, tropical/subtropical forest systems shift from a conservative to a leaky N-cycling system in response to N enrichment.

Land Use Change from Natural Tropical Forests to Managed Ecosystems Reduces Gross Nitrogen Production Rates and Increases the Soil Microbial Nitrogen Limitation.

Understanding the underlying mechanisms of soil microbial nitrogen (N) utilization under land use change is critical to evaluating soil N availability or limitation and its environmental consequences. A combination of soil gross N production and ecoenzymatic stoichiometry provides a promising avenue for nutrient limitation assessment in soil microbial metabolism. Gross N production via 15N tracing and ecoenzymatic stoichiometry through the vector and threshold element ratio (Vector-TER) model were quantified to evaluate the soil microbial N limitation in response to land use changes. We used tropical soil samples from a natural forest ecosystem and three managed ecosystems (paddy, rubber, and eucalyptus sites). Soil extracellular enzyme activities were significantly lower in managed ecosystems than in a natural forest. The Vector-TER model results indicated microbial carbon (C) and N limitations in the natural forest soil, and land use change from the natural forest to managed ecosystems increased the soil microbial N limitation. The soil microbial N limitation was positively related to gross N mineralization (GNM) and nitrification (GN) rates. The decrease in microbial biomass C and N as well as hydrolyzable ammonium N in managed ecosystems led to the decrease in N-acquiring enzymes, inhibiting GNM and GN rates and ultimately increasing the microbial N limitation. Soil GNM was also positively correlated with leucine aminopeptidase and ß-N-acetylglucosaminidase. The results highlight that converting tropical natural forests to managed ecosystems can increase the soil microbial N limitation through reducing the soil microbial biomass and gross N production.

Structure and Role of a Ga-Promoter in Ni-Based Catalysts for the Selective Hydrogenation of CO2 to Methanol.

Supported, bimetallic catalysts have shown great promise for the selective hydrogenation of CO2 to methanol. In this study, we decipher the catalytically active structure of Ni-Ga-based catalysts. To this end, model Ni-Ga-based catalysts, with varying Ni:Ga ratios, were prepared by a surface organometallic chemistry approach. In situ differential pair distribution function (d-PDF) analysis revealed that catalyst activation in H2 leads to the formation of nanoparticles based on a Ni-Ga face-centered cubic (fcc) alloy along with a small quantity of GaOx. Structure refinements of the d-PDF data enabled us to determine the amount of both alloyed Ga and GaOx species. In situ X-ray absorption spectroscopy experiments confirmed the presence of alloyed Ga and GaOx and indicated that alloying with Ga affects the electronic structure of metallic Ni (viz., Niδ-). Both the Ni:Ga ratio in the alloy and the quantity of GaOx are found to minimize methanation and to determine the methanol formation rate and the resulting methanol selectivity. The highest formation rate and methanol selectivity are found for a Ni-Ga alloy having a Ni:Ga ratio of ∼75:25 along with a small quantity of oxidized Ga species (0.14 molNi-1). Furthermore, operando infrared spectroscopy experiments indicate that GaOx species play a role in the stabilization of formate surface intermediates, which are subsequently further hydrogenated to methoxy species and ultimately to methanol. Notably, operando XAS shows that alloying between Ni and Ga is maintained under reaction conditions and is key to attaining a high methanol selectivity (by minimizing CO and CH4 formation), while oxidized Ga species enhance the methanol formation rate.

High leaching potential combined with a low leaching amount of fertilizer-derived nitrate in conservation tillage cropland of Northeast China.

Stover mulching in no-tillage farming has been widely proposed as an optimized agricultural management practice to increase soil carbon storage and improve fertilizer nitrogen (N) use efficiency in current agroecosystems. However, the regulation of soil internal gross N transformation dynamics on NO3--N leaching potential in response to long-term conservation tillage practices is still lacking. Here, based on a combination of 15N-tracing incubation and in situ monitoring experiments, we investigated the effect of 9-year no-tillage and maize stover mulching on the vertical migration of fertilizer-derived NO3--N into a deeper soil profile and the associated gross NO3--N transformation dynamics in the Mollisol of Northeast China. The net positive NO3--N production rates (varied from 3.14 to 6.22 mg N kg-1 d-1) were observed across all management practices in the studied Mollisol, indicating a relatively high NO3--N leaching potential in the cropland of Northeast China, which was further confirmed by an average of 7.4 % fertilizer-derived NO3--N being vertically transferred to the 80-100 cm soil layer after a complete maize growing period. Compared with traditional ridge tillage, long-term stover mulching in no-tillage farming significantly reduced total NO3--N production by decreasing autotrophic nitrification while simultaneously enhancing total NO3--N consumption by stimulating nitrate reduction and microbial NO3--N immobilization, revealing a markedly reduction of net NO3--N production in the no-tillage agroecosystem. Therefore, converting traditional ridge tillage toward no-tillage with maize stover mulching can effectively decrease fertilizer-derived NO3--N leaching amounts and thus formulate targeted mitigation strategies for sustainable agriculture in Mollisols of Northeast China.

IgE to cross-reactive carbohydrate determinants (CCD) in childhood: Prevalence, risk factors, putative origins.

BACKGROUND: IgE antibodies to cross-reactive carbohydrate determinants (CCD) are usually clinically irrelevant but they can be a cause of false positive outcomes of allergen-specific IgE tests in vitro. Their prevalence and levels have been so far cross-sectionally examined among adult allergic patients and much less is known about their origins and relevance in childhood. METHODS: We examined CCD with a cross-sectional approach in 1263 Italian pollen allergic children (Panallergen in Paediatrics, PAN-PED), as well as with a longitudinal approach in 612 German children (Multicenter Allergy Study, MAS), whose cutaneous and IgE sensitization profile to a broad panel of allergen extracts and molecules was already known. The presence and levels of IgE to CCD were examined in the sera of both cohorts using bromelain (MUXF3) as reagent and a novel chemiluminescence detection system, operating in a solid phase of fluorescently labelled and streptavidin-coated paramagnetic microparticles (NOVEOS, HYCOR, USA). RESULTS: IgE to CCD was found in 22% of the Italian pollen allergic children, mainly in association with an IgE response to grass pollen. Children with IgE to CCD had higher total IgE levels and were sensitized to more allergenic molecules of Phleum pratense than those with no IgE to CCD. Among participants of the German MAS birth cohort study, IgE to CCD emerged early in life (even at pre-school age), with IgE sensitization to group 1 and 4 allergen molecules of grasses, and almost invariably persisted over the full observation period. CONCLUSIONS: Our results contribute to dissect the immunological origins, onset, evolution and risk factors of CCD-sIgE response in childhood, and raise the hypothesis that group 1 and/or 4 allergen molecules of grass pollen are major inducers of these antibodies through an antigen-specific, T-B cell cognate interaction.