A comparison of Tier 1, 2, and 3 methods for quantifying nitrous oxide emissions from soils amended with biosolids.

Municipal biosolids are a nitrogen (N)-rich agricultural fertilizer which may emit nitrous oxide (N2O) after rainfall events. Due to sparse empirical data, there is a lack of biosolids-specific N2O emission factors to determine how land-applied biosolids contribute to the national greenhouse gas inventory. This study estimated N2O emissions from biosolids-amended land in Canada using Tier 1, Tier 2 (Canadian), and Tier 3 (Denitrification and Decomposition model [DNDC]) methodologies recommended by the Intergovernmental Panel on Climate Change (IPCC). Field data was from replicated plots at 8 site-years between 2017 and 2019 in the provinces of Quebec, Nova Scotia and Alberta, Canada, representing three distinct ecozones. Municipal biosolids were the major N source for the crop, applied as mesophilic anaerobically digested biosolids, composted biosolids, or alkaline-stabilized biosolids alone or combined with an equal amount of urea-N fertilizer to meet the crop N requirements. Fluxes of N2O were measured during the growing season with manual chambers and compared to N2O emissions estimated using the IPCC methods. In all site-years, the mean emission of N2O in the growing season was greater with digested biosolids than other biosolids sources or urea fertilizer alone. The emissions of N2O in the growing season were similar with composted or alkaline-stabilized biosolids, and no greater than the unfertilized control. The best estimates of N2O emissions, relative to measured values, were with the Tier 3 > adapted Tier 2 with biosolids-specific correction factors > standard Tier 2 = Tier 1 methods of the IPCC, according to the root mean square error statistic. The Tier 3 IPCC method was the best estimator of N2O emissions in the Canadian ecozones evaluated in this study. These results will be used to improve methods for estimating N2O emissions from agricultural soils amended with biosolids and to generate more accurate GHG inventories.

Experimental Realization of a Three-Dimensional Dirac Semimetal Phase with a Tunable Lifshitz Transition in Au_{2}Pb.

Three-dimensional Dirac semimetals are an exotic state of matter that continue to attract increasing attention due to the unique properties of their low-energy excitations. Here, by performing angle-resolved photoemission spectroscopy, we investigate the electronic structure of Au_{2}Pb across a wide temperature range. Our experimental studies on the (111)-cleaved surface unambiguously demonstrate that Au_{2}Pb is a three-dimensional Dirac semimetal characterized by the presence of a bulk Dirac cone projected off-center of the bulk Brillouin zone (BZ), in agreement with our theoretical calculations. Unusually, we observe that the bulk Dirac cone is significantly shifted by more than 0.4 eV to higher binding energies with reducing temperature, eventually going through a Lifshitz transition. The pronounced downward shift is qualitatively reproduced by our calculations indicating that an enhanced orbital overlap upon compression of the lattice, which preserves C_{4} rotational symmetry, is the main driving mechanism for the Lifshitz transition. These findings not only broaden the range of currently known materials exhibiting three-dimensional Dirac phases, but also show a viable mechanism by which it could be possible to switch on and off the contribution of the degeneracy point to electron transport without external doping.

On the problem of Dirac cones in fullerenes on gold.

Artificial graphene based on molecular networks enables the creation of novel 2D materials with unique electronic and topological properties. Landau quantization has been demonstrated by CO molecules arranged on the two-dimensional electron gas on Cu(111) and the observation of electron quantization may succeed based on the created gauge fields. Recently, it was reported that instead of individual manipulation of CO molecules, simple deposition of nonpolar C60 molecules on Cu(111) and Au(111) produces artificial graphene as evidenced by Dirac cones in photoemission spectroscopy. Here, we show that C60-induced Dirac cones on Au(111) have a different origin. We argue that those are related to umklapp diffraction of surface electronic bands of Au on the molecular grid of C60 in the final state of photoemission. We test this alternative explanation by precisely probing the dimensionality of the observed conical features in the photoemission spectra, by varying both the incident photon energy and the degree of charge doping via alkali adatoms. Using density functional theory calculations and spin-resolved photoemission we reveal the origin of the replicating Au(111) bands and resolve them as deep leaky surface resonances derived from the bulk Au sp-band residing at the boundary of its surface projection. We also discuss the manifold nature of these resonances which gives rise to an onion-like Fermi surface of Au(111).

Greenhouse gas emissions following biosolids application to farmland: Estimates from the DeNitrification and DeComposition model.

Municipal wastewater sludge may be processed into biosolids and applied to farmland for crop production, rather than be disposed of in landfills. Biosolids supply plant nutrients and increase soil organic carbon but also contribute to the production of greenhouse gases (GHGs). Computational models must therefore be refined to estimate the contribution of these gases to national GHG inventories. The DeNitrification and DeComposition (DNDC) model was evaluated for processes regulating crop growth, GHGs and soil C&N dynamics to determine its suitability for informing policy decision-making and advancing Canada's GHG inventory. Three years (2017-2019) of data were collected from replicated corn (Zea mays L.) plots in Quebec, Canada. The plots received 120 kg of available N ha-1 y-1 in mesophilic anaerobically digested biosolids, composted biosolids, alkaline-stabilized biosolids, urea, or combinations of these, while control plots were left unfertilized. Treatments receiving digested biosolids emitted more nitrous oxide (N2O) during the growing season than other treatments, while carbon dioxide (CO2) emissions were similar between treatments. After calibration, DNDC estimates were within the 95% confidence interval of the measured variables. Correlation coefficients (r) indicated discrepancies in trends between the estimated and measured values for daily CO2 and N2O emissions. These emissions were underestimated in the early and mid-growing season of 2018. They were more variable from plots fertilized with composted or alkaline-stabilized biosolids than from those with digested biosolids. Annual N2O emissions (r = 0.8), crop yields (r = 0.5), and soil organic carbon (r = 0.4) were modelled with higher accuracy than cumulative CO2 emissions (r = 0.3) and total soil N (r = 0.1). These findings suggest that DNDC is suitable for estimating field-scale N2O emissions following biosolids application, but estimates of CO2 emissions could be improved, perhaps by disaggregating the biosolids from the soil organic matter pools in the decomposition subroutines.

Probing spin correlations using angle-resolved photoemission in a coupled metallic/Mott insulator system.

A nearly free electron metal and a Mott insulating state can be thought of as opposite ends of the spectrum of possibilities for the motion of electrons in a solid. Understanding their interaction lies at the heart of the correlated electron problem. In the magnetic oxide metal PdCrO2, nearly free and Mott-localized electrons exist in alternating layers, forming natural heterostructures. Using angle-resolved photoemission spectroscopy, quantitatively supported by a strong coupling analysis, we show that the coupling between these layers leads to an "intertwined" excitation that is a convolution of the charge spectrum of the metallic layer and the spin susceptibility of the Mott layer. Our findings establish PdCrO2 as a model system in which to probe Kondo lattice physics and also open new routes to use the a priori nonmagnetic probe of photoemission to gain insights into the spin susceptibility of correlated electron materials.

Weyl-like points from band inversions of spin-polarised surface states in NbGeSb.

Band inversions are key to stabilising a variety of novel electronic states in solids, from topological surface states to the formation of symmetry-protected three-dimensional Dirac and Weyl points and nodal-line semimetals. Here, we create a band inversion not of bulk states, but rather between manifolds of surface states. We realise this by aliovalent substitution of Nb for Zr and Sb for S in the ZrSiS family of nonsymmorphic semimetals. Using angle-resolved photoemission and density-functional theory, we show how two pairs of surface states, known from ZrSiS, are driven to intersect each other near the Fermi level in NbGeSb, and to develop pronounced spin splittings. We demonstrate how mirror symmetry leads to protected crossing points in the resulting spin-orbital entangled surface band structure, thereby stabilising surface state analogues of three-dimensional Weyl points. More generally, our observations suggest new opportunities for engineering topologically and symmetry-protected states via band inversions of surface states.

The effects of temperature and duration of thermal pretreatment on the solid-state anaerobic digestion of dairy cow manure.

Cellulosic substrates such as dairy cow manure often yield low volumes of biogas and low concentrations of methane when digested anaerobically. Thermal pretreatment of dairy cow manure was investigated to determine if pretreatment temperature and duration can be optimized to maximize biogas yield and methane concentration. A central composite rotatable design was used to select combinations of temperature and duration. Based on measured data, statistical models were generated to estimate the biogas yield and methane concentration during digestion. The highest biogas yields were from the untreated samples and samples treated at the center temperature and duration of the statistical model (125 °C, 37.5 min). The model predicted the optimum pretreatment conditions of 140 °C for 30 minutes. Under the conditions of this experiment, temperature and duration had no significant effect on the biogas yield and methane concentration. This lack of significance may indicate that thermal pretreatment may be an unnecessary step in the anaerobic digestion of dairy cow manure, which could reduce capital and operating costs for the industry.

Fermiology and Superconductivity of Topological Surface States in PdTe_{2}.

We study the low-energy surface electronic structure of the transition-metal dichalcogenide superconductor PdTe_{2} by spin- and angle-resolved photoemission, scanning tunneling microscopy, and density-functional theory-based supercell calculations. Comparing PdTe_{2} with its sister compound PtSe_{2}, we demonstrate how enhanced interlayer hopping in the Te-based material drives a band inversion within the antibonding p-orbital manifold well above the Fermi level. We show how this mediates spin-polarized topological surface states which form rich multivalley Fermi surfaces with complex spin textures. Scanning tunneling spectroscopy reveals type-II superconductivity at the surface, and moreover shows no evidence for an unconventional component of its superconducting order parameter, despite the presence of topological surface states.

Ubiquitous formation of bulk Dirac cones and topological surface states from a single orbital manifold in transition-metal dichalcogenides.

Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.

Maximal Rashba-like spin splitting via kinetic-energy-coupled inversion-symmetry breaking.

Engineering and enhancing the breaking of inversion symmetry in solids-that is, allowing electrons to differentiate between 'up' and 'down'-is a key goal in condensed-matter physics and materials science because it can be used to stabilize states that are of fundamental interest and also have potential practical applications. Examples include improved ferroelectrics for memory devices and materials that host Majorana zero modes for quantum computing. Although inversion symmetry is naturally broken in several crystalline environments, such as at surfaces and interfaces, maximizing the influence of this effect on the electronic states of interest remains a challenge. Here we present a mechanism for realizing a much larger coupling of inversion-symmetry breaking to itinerant surface electrons than is typically achieved. The key element is a pronounced asymmetry of surface hopping energies-that is, a kinetic-energy-coupled inversion-symmetry breaking, the energy scale of which is a substantial fraction of the bandwidth. Using spin- and angle-resolved photoemission spectroscopy, we demonstrate that such a strong inversion-symmetry breaking, when combined with spin-orbit interactions, can mediate Rashba-like spin splittings that are much larger than would typically be expected. The energy scale of the inversion-symmetry breaking that we achieve is so large that the spin splitting in the CoO2- and RhO2-derived surface states of delafossite oxides becomes controlled by the full atomic spin-orbit coupling of the 3d and 4d transition metals, resulting in some of the largest known Rashba-like spin splittings. The core structural building blocks that facilitate the bandwidth-scaled inversion-symmetry breaking are common to numerous materials. Our findings therefore provide opportunities for creating spin-textured states and suggest routes to interfacial control of inversion-symmetry breaking in designer heterostructures of oxides and other material classes.

A MOLECULARLY CHARACTERIZED INTERSTITIAL DELETION ENCOMPASSING THE 11q14.1-q23.3 REGION IN A CASE WITH MULTIPLE CONGENITAL ABNORMALITIES.

Interstitial deletion of chromosome 11 long arm is a rare event. In most of the interstitial deletions on the long arm of chromosome 11 both the position and the size of these deletions are heterogeneous making a precise karyotype-phenotype correlation. In only a few of the reported cases has the deletion been molecularly characterized. Our patient was a 13-year-old male presented; mental motor retardation, strabismus, myopia, retinopathy, sensorineural hearing loss, a long and triangular face, a broad forehead, hypotelorism, nasal septal deviation, a beaked nose, hypoplastic ala nasie, bilateral low-set ears, a high arched palate, crowded teeth, retrognathia, thin lips, a long neck, and sloping shoulders, hyperactive behavior, pulmonary stenosis and lumbar scoliosis. Conventional cytogenetic analysis revealed 46,XY,del(11)(q14.1-q23.3) karyotype in the patient. Array-CGH analysis of the patient's DNA revealed an interstitial deletion encompassing 33.2 Mb in the 11q14.1-q23.3 genomic region (chr11: 83,161,443-116,401,751 ; Hg19). In this report, we present a patient with an interstitial deletion on the long arm of chromosome 11 that encompassed the 11q14.1-q23.3 region; and, using array-CGH analysis, we molecularly characterized the deleted region.

Bioavailability of Sodium and Trace Metals under Direct and Indirect Effects of Compost in Urban Soils.

The contamination of urban soil with sodium (Na) and trace metals can be one of the major concerns for groundwater contamination and street tree health. The bioavailability of Na, copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb) in urban soil amended with 0, 5, and 10% w/w compost was evaluated at none, medium, and high contamination levels of soil mixtures. The relationship between soil properties, compost addition, contamination level and metal uptake by barley ( L.) was determined using multivariate linear regression and path analysis. The results indicated the direct negative effect of compost on metal absorption possibly through specific complexation for Cu, Zn, Cd, and Pb. Compost can also affect the absorption of Na and Cd indirectly by means of cation exchange capacity (CEC) and pH. The degree of soil contamination with metals can affect the competition of cations for the complexing sites of the soil mixtures and, therefore, can induce changes in metal availability for plants. Compost addition to the soil also increased nutrient availability, except for ammonium (NH) and nitrate (NO). We concluded that in the short term, the addition of compost significantly reduced metal bioavailability and improved nutrient availability. However, more studies are required to monitor the long-term ability of the compost to reduce Na and trace metal bioavailability in urban soil.

The clinical spectrum of a rare chromosomal abnormality: Isochromosome 18p.

Isochromosome 18p is a rare chromosomal disorder that occurs with a frequency of approximately one in every 180,000 live births, and affects both genders equally. MOst cases result from a de novo formation. In the literature, there are currently only a small number of reports that describe the phenotypic and clinical features of Isochromosome 18p. In this article, we report six cases that displayed the phenotypic and clinical features of Isochromosome 18p, and which were subsequently confirmed by conventional karyotyping and fluorescence in situ hybridization. We also discuss the clinical features of these patients in the context of the cases previously reported in the literature.

22q11.2 syndrome due to maternal translocation t(18;22) (pl1.2;q11.2).

22q11.2 deletion syndrome is a pattern of malformations resulting from abnormalities during cephalic neural crest migration and during the development of the third and fourth branchial arch. It is also known as DiGeorge syndrome, as it is most often associated with a de novo 3 Mb hemizygous 22q11.2 deletion. The recognition of similarities and phenotypic overlap between DiGeorge syndrome and other disorders associated with genetic defects in 22q11 has led to an expanded description of the phenotypic features of this syndrome. Indeed, the extent of this phenotypic variability can often make it difficult to accurately diagnose DiGeorge syndrome. Tertiary monosomy resulting from the 3:1 segregation of the respective chromosomal segments of the chromosomes involved in a balanced translocation in meiosis is rarely reported in the literature. In this report, we present a female infant with dysmorphic facial features, microcephaly, a cleft palate, unilateral membranous choanal atresia, convulsions, hypocalcemia, semilobar holoporencephaly and echocardiographic abnormalities. To the best of our knowledge, this is the first description of a newborn displaying both DiGeorge syndrome and deletion 18p syndromes.

Ring chromosome 21 and monosomy 21 mosaicism in a patient with azoospermia.

In this report, we describe a patient with azoospermia in conjection with de novo ring chromosome 21 and monosomy 21 mosaicism. Inter-phase fluorescence in situ hybridisation (FISH) studies on uncultured peripheral blood and epithelial cells obtained by buccal smear revealed that 25% of the uncultured blood cells and 11% of the epithelial cells were monosomic for chromosome 21. Y chromosome microdeletion analysis ruled out the presence of any genomic deletions in the azoospermic factor a,b,c regions on the long arm of chromosome Y. Additionally, through subtelomeric FISH analysis, it was found that there was no deletion in the subtelomeric region of ring chromosome 21. Our results indicate that ring chromosome 21 is a rare, but recurrent chromosomal abnormality in male factor infertility. Furthermore, in individuals with ring chromosome 21, defective spermatogenesis is not associated with the deletion of any gene or genes located in the subtelomeric region of chromosome 21.

Trace metal contamination influenced by land use, soil age, and organic matter in montreal tree pit soil.

The short life span of many street trees in the Montreal downtown area may be due in part to higher than standard concentrations of trace metals in the tree pit soils. The effects of land use, soil organic matter, and time since tree planting in a given tree pit (soil age) were studied with respect to the total concentration of trace metals (Cr, Ni, Cu, Zn, Cd, and Pb) in soil collected from tree pits on commercial and residential streets. Contingency table analysis and multiple linear regression were applied to study how these variables were related to the total concentrations of trace metals in soil. Other variables, such as pH, street width, distance of the tree pit from the curb, and tree pit volume, were also used as input to statistical analysis to increase the analysis' explanatory power. Significantly higher concentrations of Cu, Cd, Zn, and Pb were observed in soils from commercial streets, possibly as a result of heavier traffic as compared with residential streets. Soil organic matter was positively correlated with the concentrations of Cu and Pb, probably due to the ability of organic matter to retain these trace metals. Nickel, Cu, Zn, Cd, and Pb were positively correlated with the soil age presumably because trace metals accumulate in the tree pit soil over time. This knowledge can be helpful in providing soil quality standards aimed at improving the longevity of downtown street trees.

A simple device prevents hysterotomy extensions during cesarean delivery for failed second stage of labor.

BACKGROUND/AIMS: [corrected] During arrest of descent, maternal tissues conform to the fetal head, resulting in a suction-cup like effect during cesarean delivery. We hypothesize that breaking this suction might ease delivery. A novel device was designed for this purpose and tested in this series of 23 patients. METHODS: University-based retrospective cohort feasibility study. Term pregnant women with second-stage labor arrest (n = 23) provided written consent for use of the experimental device, inserted vaginally prior to cesarean delivery. Delivering obstetricians rated device effectiveness. Following case collection, the presence of hysterotomy extensions in study patients was retrospectively compared with controls (n = 49) from the same study period. RESULTS: On a 7-point Likert scale, consultant obstetricians rated overall device effectiveness as 6.0, and resident obstetricians rated it 6.3, consistent with a moderate improvement in ease of delivery. The device performed optimally at mid-pelvic stations (0 to +1), with no hysterotomy extensions (n = 0/17), which was significantly better than controls (n = 14/41, 34%, p < 0.01). CONCLUSION: A simple device prevented hysterotomy extension during second-stage cesarean delivery at 0 and +1 station. Obstetricians perceived that the device afforded a moderate improvement in delivery compared with previous deliveries in which the device was not used.