Temporal, spatial, and management variability in the carbon footprint of New Zealand milk.

The carbon footprint of milk from year-round grazed-pasture dairy systems and its variability has had limited research. The objective of this study was to determine temporal, regional, and farm system variability in the carbon footprint of milk from New Zealand (NZ) average dairy production. Farm production and input data were collected from a national database for 2010/11 to 2017/18 across regions of NZ and weighted on relative production supplied to the major dairy cooperative Fonterra to produce an NZ-average. Total greenhouse gas emissions were calculated using a life cycle assessment methodology for the cradle-to-farm gate, covering all on- and off-farm contributing sources. The NZ-average carbon footprint of milk varied from 0.81 kg of CO2 equivalent (CO2eq)/kg of fat- and protein-corrected milk (FPCM) in 2010/11 (with widespread drought) to 0.75 to 0.78 kg of CO2eq/kg of FPCM in 2013/14 to 2017/18, with a trend for a small decrease over time. Regional variation occurred with highest carbon footprint values for the Northland region due to greatest climatic and soil limitations on pasture production. Dairy cattle diet was approximately 85% from grazed pasture with up to 15% from brought-in feeds (mainly forages and by-products). The CO2 emissions from direct fuel and electricity use constituted <2% of total CO2eq emissions, whereas enteric methane was near 70% of the total. An estimate of potential contribution from direct land use change (plantation forest to pasture) was 0.13 kg of CO2eq/kg of FPCM. This was not included because nationally there has been a net increase in forest land and a decrease in pasture land over the last 20 yr. Data used were highly representative, as evident by the same estimated carbon footprint from 368 farms (in 2017/18) from the national database compared with that from a direct survey of 7,146 farms. New Zealand-specific nitrous oxide emission factors were used, based on many validated field trials and as used in the NZ greenhouse gas inventory, resulting in an 18% lower carbon footprint than if default Intergovernmental Panel on Climate Change factors had been used. Evaluation of the upper and lower quartiles of farms based on per-cow milk production (6,044 vs. 3,542 kg of FPCM/cow) showed a 15% lower carbon footprint for the upper quartile of farms, illustrating the potential for further decrease in carbon footprint with improved farm management practices.

Ultrafast dynamics of spin and orbital correlations in quantum materials: an energy- and momentum-resolved perspective.

Many remarkable properties of quantum materials emerge from states with intricate coupling between the charge, spin and orbital degrees of freedom. Ultrafast photo-excitation of these materials holds great promise for understanding and controlling the properties of these states. Here, we introduce time-resolved resonant inelastic X-ray scattering (tr-RIXS) as a means of measuring the charge, spin and orbital excitations out of equilibrium. These excitations encode the correlations and interactions that determine the detailed properties of the states generated. After outlining the basic principles and instrumentations of tr-RIXS, we review our first observations of transient antiferromagnetic correlations in quasi two dimensions in a photo-excited Mott insulator and present possible future routes of this fast-developing technique. The increasing number of X-ray free electron laser facilities not only enables tackling long-standing fundamental scientific problems, but also promises to unleash novel inelastic X-ray scattering spectroscopies. This article is part of the theme issue 'Measurement of ultrafast electronic and structural dynamics with X-rays'.

Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr2IrO4.

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity. Recently, photo-excitation has been used to induce similarly exotic states transiently. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr2IrO4. We find that the non-equilibrium state, 2 ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. The marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.

Spatially resolved ultrafast magnetic dynamics initiated at a complex oxide heterointerface.

Static strain in complex oxide heterostructures has been extensively used to engineer electronic and magnetic properties at equilibrium. In the same spirit, deformations of the crystal lattice with light may be used to achieve functional control across heterointerfaces dynamically. Here, by exciting large-amplitude infrared-active vibrations in a LaAlO3 substrate we induce magnetic order melting in a NdNiO3 film across a heterointerface. Femtosecond resonant soft X-ray diffraction is used to determine the spatiotemporal evolution of the magnetic disordering. We observe a magnetic melt front that propagates from the substrate interface into the film, at a speed that suggests electronically driven motion. Light control and ultrafast phase front propagation at heterointerfaces may lead to new opportunities in optomagnetism, for example by driving domain wall motion to transport information across suitably designed devices.

Persistence of magnetic excitations in La(2-x)Sr(x)CuO4 from the undoped insulator to the heavily overdoped non-superconducting metal.

One of the most intensely studied scenarios of high-temperature superconductivity (HTS) postulates pairing by exchange of magnetic excitations. Indeed, such excitations have been observed up to optimal doping in the cuprates. In the heavily overdoped regime, neutron scattering measurements indicate that magnetic excitations have effectively disappeared, and this has been argued to cause the demise of HTS with overdoping. Here we use resonant inelastic X-ray scattering, which is sensitive to complementary parts of reciprocal space, to measure the evolution of the magnetic excitations in La(2-x)Sr(x)CuO4 across the entire phase diagram, from a strongly correlated insulator (x = 0) to a non-superconducting metal (x = 0.40). For x = 0, well-defined magnon excitations are observed. These magnons broaden with doping, but they persist with a similar dispersion and comparable intensity all the way to the non-superconducting, heavily overdoped metallic phase. The destruction of HTS with overdoping is therefore caused neither by the general disappearance nor by the overall softening of magnetic excitations. Other factors, such as the redistribution of spectral weight, must be considered.

Melting of charge stripes in vibrationally driven La(1.875)Ba(0.125)CuO4: assessing the respective roles of electronic and lattice order in frustrated superconductors.

We report femtosecond resonant soft x-ray diffraction measurements of the dynamics of the charge order and of the crystal lattice in nonsuperconducting, stripe-ordered La1.875Ba0.125CuO4. Excitation of the in-plane Cu-O stretching phonon with a midinfrared pulse has been previously shown to induce a transient superconducting state in the closely related compound La1.675Eu0.2Sr0.125CuO4. In La1.875Ba0.125CuO4, we find that the charge stripe order melts promptly on a subpicosecond time scale. Surprisingly, the low temperature tetragonal (LTT) distortion is only weakly reduced, reacting on significantly longer time scales that do not correlate with light-induced superconductivity. This experiment suggests that charge modulations alone, and not the LTT distortion, prevent superconductivity in equilibrium.

Spin excitations in a single La2CuO4 layer.

Cuprates and other high-temperature superconductors consist of two-dimensional layers that are crucial to their properties. The dynamics of the quantum spins in these layers lie at the heart of the mystery of the cuprates. In bulk cuprates such as La(2)CuO(4), the presence of a weak coupling between the two-dimensional layers stabilizes a three-dimensional magnetic order up to high temperatures. In a truly two-dimensional system however, thermal spin fluctuations melt long-range order at any finite temperature. Here, we measure the spin response of isolated layers of La(2)CuO(4) that are only one-unit-cell-thick. We show that coherent magnetic excitations, magnons, known from the bulk order, persist even in a single layer of La(2)CuO(4), with no evidence for more complex correlations such as resonating valence bond correlations. These magnons are, therefore, well described by spin-wave theory (SWT). On the other hand, we also observe a high-energy magnetic continuum in the isotropic magnetic response that is not well described by two-magnon SWT, or indeed any existing theories.

Ferromagnetic exchange anisotropy from antiferromagnetic superexchange in the mixed 3d-5d transition-metal compound Sr3CuIrO6.

We report a combined experimental and theoretical study of the unusual ferromagnetism in the one-dimensional copper-iridium oxide Sr(3)CuIrO(6). Utilizing Ir L(3) edge resonant inelastic x-ray scattering, we reveal a large gap magnetic excitation spectrum. We find that it is caused by an unusual exchange anisotropy generating mechanism, namely, strong ferromagnetic anisotropy arising from antiferromagnetic superexchange, driven by the alternating strong and weak spin-orbit coupling on the 5d Ir and 3d Cu magnetic ions, respectively. From symmetry consideration, this novel mechanism is generally present in systems with edge-sharing Cu(2+)O(4) plaquettes and Ir(4+)O(6) octahedra. Our results point to unusual magnetic behavior to be expected in mixed 3d-5d transition-metal compounds via exchange pathways that are absent in pure 3d or 5d compounds.

High-energy magnetic excitations in the cuprate superconductor Bi(2)Sr(2)CaCu(2)O(8+δ): towards a unified description of its electronic and magnetic degrees of freedom.

We investigate the high-energy magnetic excitation spectrum of the high-T(c) cuprate superconductor Bi(2)Sr(2)CaCu(2)O(8+δ) (Bi-2212) using Cu L(3) edge resonant inelastic x-ray scattering. Broad, dispersive magnetic excitations are observed, with a zone boundary energy of ∼ 300 meV and a weak dependence on doping. These excitations are strikingly similar to the bosons proposed to explain the high-energy "kink" observed in photoemission. A phenomenological calculation of the spin response, based on a parametrization of the the angle-resolved photoemission spectroscopy derived electronic structure and Yang-Rice-Zhang quasiparticles, provides a reasonable prediction of the energy dispersion of the observed magnetic excitations. These results indicate a possible unified framework to reconcile the magnetic and electronic properties of the cuprates and we discuss the advantages and disadvantages of such an approach.

Crystal-field splitting and correlation effect on the electronic structure of A2IrO3.

The electronic structure of the honeycomb lattice iridates Na(2)IrO(3) and Li(2)IrO(3) has been investigated using resonant inelastic x-ray scattering (RIXS). Crystal-field-split d-d excitations are resolved in the high-resolution RIXS spectra. In particular, the splitting due to noncubic crystal fields, derived from the splitting of j(eff)=3/2 states, is much smaller than the typical spin-orbit energy scale in iridates, validating the applicability of j(eff) physics in A(2)IrO(3). We also find excitonic enhancement of the particle-hole excitation gap around 0.4 eV, indicating that the nearest-neighbor Coulomb interaction could be large. These findings suggest that both Na(2)IrO(3) and Li(2)IrO(3) can be described as spin-orbit Mott insulators, similar to the square lattice iridate Sr(2)IrO(4).

Testing the validity of the strong spin-orbit-coupling limit for octahedrally coordinated iridate compounds in a model system Sr3CuIrO6.

The electronic structure of Sr3CuIrO6, a model system for the 5d Ir ion in an octahedral environment, is studied through a combination of resonant inelastic x-ray scattering and theoretical calculations. Resonant inelastic x-ray scattering spectra at the Ir L3 edge reveal an Ir t(2g) manifold that is split into three levels, in contrast to the expectations of the strong spin-orbit-coupling limit. Effective Hamiltonian and ab inito quantum chemistry calculations find a strikingly large noncubic crystal field splitting comparable to the spin-orbit coupling, which results in a strong mixing of the j(eff)=1/2 and j(eff)=3/2 states and modifies the isotropic wave functions on which many theoretical models are based.

Observation of electronic ferroelectric polarization in multiferroic YMn2O5.

We report the observation of a magnetic polarization of the O 2p states in YMn(2)O(5) through the use of soft x-ray resonant scattering at the oxygen K edge. Remarkably, we find that the temperature dependence of the integrated intensity of this signal closely follows the macroscopic electric polarization, and hence is proportional to the ferroelectric order parameter. This is in contrast with the temperature dependence observed at the Mn L(3) edge, which reflects the Mn magnetic order parameter. First-principles calculations provide a microscopic understanding of these results and show that a spin-dependent hybridization of O 2p and Mn 3d states results in a purely electronic contribution to the ferroelectric polarization, which can exist in the absence of lattice distortions.

High-resolution x-ray scattering from epitaxial thin films of Y/Nb on Al2O3.

During the 1990s, Roger Cowley had a strong interest in the crystal and magnetic structures of rare-earth superlattices as a means to understand the rich and exotic magnetic properties of the rare-earth metals. High-quality samples can be grown by molecular beam epitaxy on sapphire substrates by first depositing a thin epitaxial layer of niobium, then a layer of yttrium or lutetium as a seed. High-resolution x-ray scattering is an excellent probe to characterise the crystal quality and was used to study the structure of the niobium layer. However, relatively little attention was paid to the seed layer. This article summarises some of the x-ray experiments performed by the Cowley group to study the structure of epitaxial [Formula: see text] niobium on [Formula: see text] sapphire, and extends the work to report some results on the structure of thin [Formula: see text] yttrium seed layers. The structure of the yttrium films is shown to have a strong dependence on the thickness of the niobium buffer, with the buffer needing to be thicker than a critical value of ∼80 [Formula: see text] for the formation of misfit dislocations at the Nb/Al2O3 interface before highly coherent Y films can be grown. Yttrium films grown on Nb buffers thinner than ∼500 [Formula: see text] show a similar two-peak line shape in [Formula: see text] scans through their specular Bragg peaks to that seen in the specular Nb Bragg peaks, with a resolution-limited feature on a broader diffuse peak. The resolution-limited feature depends on the thickness of the yttrium film, becoming weaker and having a stronger decay with increasing [Formula: see text] as the film thickness increases, while the width of the yttrium broad peak evolves as the square root of the width of the niobium Bragg peak. The data are discussed within the context of theories describing the scattering from films with misfit dislocations.

Nature of the magnetic order and origin of induced ferroelectricity in TbMnO3.

The magnetic structures which endow TbMnO(3) with its multiferroic properties have been reassessed on the basis of a comprehensive soft x-ray resonant scattering (XRS) study. The selectivity of XRS facilitated separation of the various contributions (Mn L(2) edge, Mn 3d moments; Tb M(4) edge, Tb 4f moments), while its variation with azimuth provided information on the moment direction of distinct Fourier components. When the data are combined with a detailed group theory analysis, a new picture emerges of the ferroelectric transition at 28 K. Instead of being driven by the transition from a collinear to a noncollinear magnetic structure, as has previously been supposed, it is shown to occur between two noncollinear structures.

Porphyrinoid rotaxanes: building a mechanical picket fence.

Building on recent progress in the synthesis of functional porphyrins for a range of applications using the Cu-mediated azide-alkyne cycloaddition (CuAAC) reaction, we describe the active template CuAAC synthesis of interlocked triazole functionalised porphyrinoids in excellent yield. By synthesising interlocked analogues of previously studied porphyrin-corrole conjugates, we demonstrate that this approach gives access to rotaxanes in which the detailed electronic properties of the axle component are unchanged but whose steric properties are transformed by the mechanical "picket fence" provided by the threaded rings. Our results suggest that interlocked functionalised porphyrins, readily available using the AT-CuAAC approach, are sterically hindered scaffolds for the development of new catalysts and materials.

Barley yellow rust in North America.

Yellow rust of barley is an invasive disease that was found in the past 10 years in North America. The causal agent, Puccinia striiformis f. sp. hordei, was introduced into Colombia, South America, from Europe in 1975. It spread to all major barley-producing areas in South America by 1982. In 1988 it was found in Mexico and in 1991 in Texas. Since then it has been found in all major barley-producing areas of the American West. Originally described as race (R) 24, barley yellow rust in North America is now known to be a very heterogeneous population. Resistance has been identified, evaluated, and is being introduced into commercial malting and other barley cultivars. Cultural and chemical controls are effective and available. An integrated approach using general field resistance and other tactics is described for sustainable management of barley yellow rust.

Spin-orbit-driven magnetic structure and excitation in the 5d pyrochlore Cd2Os2O7.

Much consideration has been given to the role of spin-orbit coupling (SOC) in 5d oxides, particularly on the formation of novel electronic states and manifested metal-insulator transitions (MITs). SOC plays a dominant role in 5d(5) iridates (Ir(4+)), undergoing MITs both concurrent (pyrochlores) and separated (perovskites) from the onset of magnetic order. However, the role of SOC for other 5d configurations is less clear. For example, 5d(3) (Os(5+)) systems are expected to have an orbital singlet with reduced effective SOC. The pyrochlore Cd2Os2O7 nonetheless exhibits a MIT entwined with magnetic order phenomenologically similar to pyrochlore iridates. Here, we resolve the magnetic structure in Cd2Os2O7 with neutron diffraction and then via resonant inelastic X-ray scattering determine the salient electronic and magnetic energy scales controlling the MIT. In particular, SOC plays a subtle role in creating the electronic ground state but drives the magnetic order and emergence of a multiple spin-flip magnetic excitation.

Crystallization and preliminary X-ray diffraction studies on cytosolic (class 1) aldehyde dehydrogenase from sheep liver.

The cytosolic (Class 1) aldehyde dehydrogenase (AlDH) from sheep liver has been crystallized in a form suitable for X-ray diffraction studies. The crystals, grown by vapour diffusion using 6.5 to 7.5% methoxypolyethylene glycol 5000 as precipitant, at pH 6.5, are orthorhombic with cell dimensions a = 80.7, b = 92.5, c = 151.6 A, space-group P2(1)2(1)2(1), and one dimer in the asymmetric unit. The crystals diffract to at least 2.8 A resolution. Although unmodified AlDH crystallized readily, a key factor in obtaining diffraction-quality crystals was the covalent attachment of an active site reporter group, provided by 3,4-dihydro-3-methyl-6-nitro-2H-1,3-benzoxazin-2-one.

Probing single magnon excitations in Sr2IrO4 using O K-edge resonant inelastic x-ray scattering.

Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

Simultaneous analysis of surface marker expression and cell cycle progression in human peripheral blood mononuclear cells.

One method for examining cell cycle kinetics by flow cytometry uses continuous DNA labeling with bromodeoxyuridine (BrdU), a thymidine analogue. Upon incorporation into DNA, BrdU causes stoichiometric quenching of the DNA fluorochrome Hoechst 33258. After counterstaining with a secondary DNA fluorochrome (e.g., ethidium bromide), the analyst can distinguish cells in different phases of the cell cycle over a number of mitotic cycles with flow cytometry. In this report, we describe a modification of the flow cytometric BrdU-Hoechst assay that allows combined analysis of cell proliferation and immunophenotyping at the single cell level. To demonstrate an application of this method, human peripheral blood mononuclear cells were stimulated with tetanus toxoid or interleukin-2 for up to 6 days in the presence of BrdU, harvested, and immunostained for the cell surface markers CD3, CD4, CD8, CD14, CD19, and the cytokine receptor, CCR5. We used four-color flow cytometry analyses to simultaneously measure cell proliferation and surface marker expression, for the purpose of immunophenotyping and identifying specific cell subsets responding to antigen stimulation. Our successful application of this method suggests that it may be used to study immune responses at the molecular and cellular level and to identify mechanisms of immune system modulation.