Global food loss and waste embodies unrecognized harms to air quality and biodiversity hotspots.

Global food loss and waste (FLW) undermines the resilience and sustainability of food systems and is closely tied to the United Nation's Sustainable Development Goals on climate, resource use and food security. Here we reveal strong yet under-discussed interconnections between FLW and two other Sustainable Development Goals of Human Health and Life on Land via the nitrogen cycle. We find that eliminating global FLW in 2015 would have reduced anthropogenic NH3 emissions associated with food production by 11.4 Tg (16%), decreased local PM2.5 concentrations by up to 5 µg m-3 and PM2.5-related years of life lost by 1.5 million years, and mitigated nitrogen critical load exceedances in global biodiversity hotspots by up to 19%. Halving FLW in 2030 will reduce years of life lost by 0.5-0.8 million years and nitrogen deposition by 4.7-6.0 Tg N per year (4%) (range for socioeconomic pathways). Complementary to near-term NH3 mitigation potential via technological measures, our study emphasizes incentivizing FLW reduction efforts from air quality and ecosystem health perspectives.

Photocatalytic chlorine atom production on mineral dust-sea spray aerosols over the North Atlantic.

Active chlorine in the atmosphere is poorly constrained and so is its role in the oxidation of the potent greenhouse gas methane, causing uncertainty in global methane budgets. We propose a photocatalytic mechanism for chlorine atom production that occurs when Sahara dust mixes with sea spray aerosol. The mechanism is validated by implementation in a global atmospheric model and thereby explaining the episodic, seasonal, and location-dependent 13C depletion in CO in air samples from Barbados [J.E. Mak, G. Kra, T. Sandomenico, P. Bergamaschi, J. Geophys. Res. Atmos. 108 (2003)], which remained unexplained for decades. The production of Cl can also explain the anomaly in the CO:ethane ratio found at Cape Verde [K. A. Read et al., J. Geophys. Res. Atmos. 114 (2009)], in addition to explaining the observation of elevated HOCl [M. J. Lawler et al., Atmos. Chem. Phys. 11, 7617-7628 (2011)]. Our model finds that 3.8 Tg(Cl) y-1 is produced over the North Atlantic, making it the dominant source of chlorine in the region; globally, chlorine production increases by 41%. The shift in the methane sink budget due to the increased role of Cl means that isotope-constrained top-down models fail to allocate 12 Tg y-1 (2% of total methane emissions) to 13C-depleted biological sources such as agriculture and wetlands. Since 2014, an increase in North African dust emissions has increased the 13C isotope of atmospheric CH4, thereby partially masking a much greater decline in this isotope, which has implications for the interpretation of the drivers behind the recent increase of methane in the atmosphere.

Global environmental implications of atmospheric methane removal through chlorine-mediated chemistry-climate interactions.

Atmospheric methane is both a potent greenhouse gas and photochemically active, with approximately equal anthropogenic and natural sources. The addition of chlorine to the atmosphere has been proposed to mitigate global warming through methane reduction by increasing its chemical loss. However, the potential environmental impacts of such climate mitigation remain unexplored. Here, sensitivity studies are conducted to evaluate the possible effects of increasing reactive chlorine emissions on the methane budget, atmospheric composition and radiative forcing. Because of non-linear chemistry, in order to achieve a reduction in methane burden (instead of an increase), the chlorine atom burden needs to be a minimum of three times the estimated present-day burden. If the methane removal target is set to 20%, 45%, or 70% less global methane by 2050 compared to the levels in the Representative Concentration Pathway 8.5 scenario (RCP8.5), our modeling results suggest that additional chlorine fluxes of 630, 1250, and 1880 Tg Cl/year, respectively, are needed. The results show that increasing chlorine emissions also induces significant changes in other important climate forcers. Remarkably, the tropospheric ozone decrease is large enough that the magnitude of radiative forcing decrease is similar to that of methane. Adding 630, 1250, and 1880 Tg Cl/year to the RCP8.5 scenario, chosen to have the most consistent current-day trends of methane, will decrease the surface temperature by 0.2, 0.4, and 0.6 °C by 2050, respectively. The quantity and method in which the chlorine is added, its interactions with climate pathways, and the potential environmental impacts on air quality and ocean acidity, must be carefully considered before any action is taken.

Periodicity of Two-Dimensional Bonding of Main Group Elements.

In the periodic table the position of each atom follows the 'aufbau' principle of the individual electron shells. The resulting intrinsic periodicity of atomic properties determines the overall behavior of atoms in two-dimensional (2D) bonding and structure formation. Insight into the type and strength of bonding is the key in the discovery of innovative 2D materials. The primary features of 2D bonding and the ensuing monolayer structures of the main-group II-VI elements result from the number of valence electrons and the change of atom size, which determine the type of hybridization. The results reveal the tight connection between strength of bonding and bond length in 2D networks. The predictive power of the periodic table reveals general rules of bonding, the bonding-structure relationship, and allows an assessment of published data of 2D materials.

Nitrification, denitrification, and competition for soil N: Evaluation of two Earth System Models against observations.

Earth System Models (ESMs) have implemented nitrogen (N) cycles to account for N limitation on terrestrial carbon uptake. However, representing inputs, losses, and recycling of N in ESMs is challenging. Here, we use global rates and ratios of key soil N fluxes, including nitrification, denitrification, mineralization, leaching, immobilization, and plant uptake (both NH4 + and NO3 - ), from the literature to evaluate the N cycles in the land model components of two ESMs. The two land models evaluated here, E3SM Land Model version 1 (ELMv1)-ECA and CLM5.0, originated from a common model but have diverged in their representation of plant-microbe competition for soil N. The models predict similar global rates of gross primary productivity (GPP) but have approximately two-fold to three-fold differences in their underlying global mineralization, immobilization, plant N uptake, nitrification, and denitrification fluxes. Both models dramatically underestimate the immobilization of NO3 - by soil bacteria compared with literature values and predict dominance of plant uptake by a single form of mineral nitrogen (NO3 - for ELM, with regional exceptions, and NH4 + for CLM5.0). CLM5.0 strongly underestimates the global ratio of gross nitrification:gross mineralization and both models are likely to substantially underestimate the ratio of nitrification:denitrification. Few experimental data exist to evaluate this last ratio, in part because nitrification and denitrification are quantified using different techniques and because denitrification fluxes are difficult to measure at all. More observational constraints on soil nitrogen fluxes such as nitrification and denitrification, as well as greater scrutiny of the functional impact of introducing separate NH4 + and NO3 - pools into ESMs, could help to improve confidence in present and future simulations of N limitation on the carbon cycle.

Nitrification and denitrification in the Community Land Model compared with observations at Hubbard Brook Forest.

Models of terrestrial system dynamics often include nitrogen (N) cycles to better represent N limitations on terrestrial carbon (C) uptake, but simulating the fate of N in ecosystems has proven challenging. Here, key soil N fluxes and flux ratios from the Community Land Model version 5.0 (CLM5.0) are compared with an extensive set of observations from the Hubbard Brook Forest Long-Term Ecological Research site in New Hampshire. Simulated fluxes include microbial immobilization and plant uptake, which compete with nitrification and denitrification, respectively, for available soil ammonium (NH4 + ) and nitrate (NO3 - ). In its default configuration, CLM5.0 predicts that both plant uptake and immobilization are strongly dominated by NH4 + over NO3 - , and that the model ratio of nitrification:denitrification is ~1:1. In contrast, Hubbard Brook observations suggest that NO3 - plays a more significant role in plant uptake and that nitrification could exceed denitrification by an order of magnitude. Modifications to the standard CLM5.0 at Hubbard Brook indicate that a simultaneous increase in the competitiveness of nitrifying microbes for NH4 + and reduction in the competitiveness of denitrifying bacteria for NO3 - are needed to bring soil N flux ratios into better agreement with observations. Such adjustments, combined with evaluation against observations, may help to improve confidence in present and future simulations of N limitation on the C cycle, although C fluxes, such as gross primary productivity and net primary productivity, are less sensitive to the model modifications than soil N fluxes.

Bonding, structure, and mechanical stability of 2D materials: the predictive power of the periodic table.

This tutorial review describes the ongoing effort to convert main-group elements of the periodic table and their combinations into stable 2D materials, which is sometimes called modern 'alchemy'. Theory is successfully approaching this goal, whereas experimental verification is lagging far behind in the synergistic interplay between theory and experiment. The data collected here gives a clear picture of the bonding, structure, and mechanical performance of the main-group elements and their binary compounds. This ranges from group II elements, with two valence electrons, to group VI elements with six valence electrons, which form not only 1D structures but also, owing to their variable oxidation states, low-symmetry 2D networks. Outside of these main groups reviewed here, predominantly ionic bonding may be observed, for example in group II-VII compounds. Besides high-symmetry graphene with its shortest and strongest bonds and outstanding mechanical properties, low-symmetry 2D structures such as various borophene and tellurene phases with intriguing properties are receiving increasing attention. The comprehensive discussion of data also includes bonding and structure of few-layer assemblies, because the electronic properties, e.g., the band gap, of these heterostructures vary with interlayer layer separation and interaction energy. The available data allows the identification of general relationships between bonding, structure, and mechanical stability. This enables the extraction of periodic trends and fundamental rules governing the 2D world, which help to clear up deviating results and to estimate unknown properties. For example, the observed change of the bond length by a factor of two alters the cohesive energy by a factor of four and the extremely sensitive Young's modulus and ultimate strength by more than a factor of 60. Since the stiffness and strength decrease with increasing atom size on going down the columns of the periodic table, it is important to look for suitable allotropes of elements and binaries in the upper rows of the periodic table when mechanical stability and robustness are issues. On the other hand, the heavy compounds are of particular interest because of their low-symmetry structures with exotic electronic properties.

Thickness of elemental and binary single atomic monolayers.

The thickness of monolayers is a fundamental property of two-dimensional (2D) materials that has not found the necessary attention. It plays a crucial role in their mechanical behavior, the determination of related physical properties such as heat transfer, and especially the properties of multilayer systems. Measurements of the thickness of free-standing monolayers are widely lacking and notoriously too large. Consistent thicknesses have been reported for single layers of graphene, boronitrene, and SiC derived from interlayer spacing measured by X-ray diffraction in multilayer systems, first-principles calculations of the interlayer spacing, and tabulated van der Waals (vdW) diameters. Furthermore, the electron density-based volume model agrees with the geometric slab model for graphene and boronitrene. For other single-atom monolayers DFT calculations and molecular dynamics (MD) simulations deliver interlayer distances that are often much smaller than the vdW diameter, owing to further electrostatic and (weak) covalent interlayer interaction. Monolayers strongly bonded to a surface also show this effect. If only weak vdW forces exist, the vdW diameter delivers a reasonable thickness not only for free-standing monolayers but also for few-layer systems and adsorbed monolayers. Adding the usually known corrugation effect of buckled or puckered monolayers to the vdW diameter delivers an upper limit of the monolayer thickness. The study presents a reference database of thickness values for elemental and binary group-IV and group-V monolayers, as well as binary III-V and IV-VI compounds.

Predictive modeling of intrinsic strengths for several groups of chemically related monolayers by a reference model.

The linear correlation between the ratios of linear and nonlinear intrinsic mechanical properties allows the prediction of largely unknown nonlinear fracture properties of brittle two-dimensional (2D) solids using a reference model. It is demonstrated that from accurately known Young's moduli unknown theoretical strengths can be derived. The predictive power of the reference model for the systematic evaluation of the fundamental mechanical behavior of whole groups of compounds with chemically-related configurations is shown. This is revealed for graphene-like atomic monolayers, various derivatives of graphene, transition-metal dichalcogenide (TMDC), and transition-metal monochalcogenide (TMMC) molecular monolayers of the fast growing family of 2D solids. The estimated unknown intrinsic strengths represent the upper limits for the mechanical performance of 2D compounds and can be used to judge the actual deviations between real monolayers and their ideal counterparts. A detailed comparison of the reference model with existing experiments and density functional theory (DFT) calculations confirmed that the ratios of Young's moduli and intrinsic strengths reach a factor of ∼6 for strongly bonded TMMCs, the bulk value of ∼9 for graphene-like monolayers, ∼11 for graphene derivatives, whereas for transition-metal dichalcogenide (TMDC) monolayers the ratio is ∼13.5. With its minimal requirement of mechanical input data and its versatility the reference model provides a unique tool to predict unknown nonlinear mechanical properties.

Relationships between the elastic and fracture properties of boronitrene and molybdenum disulfide and those of graphene.

A consistent set of 2D elastic and fracture properties of hexagonal boron nitride (h-BN) monolayers (boronitrene) and molybdenum disulfide (MoS2) nanosheets is derived. Reported literature values for Young's moduli and fracture strengths, based on experiments and DFT calculations, were used to estimate the line or edge energy with a local 2D bond-breaking model. Consistent information was obtained for intrinsic fracture properties. The basic mechanical properties of boronitrene are roughly 25% lower than the corresponding graphene values. This is consistent with the tensile bond force model, and the lower ionic-covalent bonding energy of sp2-hybridized B-N bonds in comparison with sp2-hybridized carbon bonds. While the intrinsic stiffness and strength of MoS2 correlate with the strength of its constituent chemical bonds, DFT calculations of the line or edge energy scale with roughly two times the Mo-S bonding energy, whereas the 2D bond-breaking model yields a correlation similar to that found for h-BN. Additional failure properties such as the fracture toughness and strain energy release rate were determined. Together with the intrinsic strengths a Griffith plot of the effective strength of defective h-BN and MoS2 versus the square root of half the defect size of single defects such as (multi)vacancies and micro-cracks exhibits a slope similar to that of the graphene plot.

Laser-based linear and nonlinear guided elastic waves at surfaces (2D) and wedges (1D).

The characteristic features and applications of linear and nonlinear guided elastic waves propagating along surfaces (2D) and wedges (1D) are discussed. Laser-based excitation, detection, or contact-free analysis of these guided waves with pump-probe methods are reviewed. Determination of material parameters by broadband surface acoustic waves (SAWs) and other applications in nondestructive evaluation (NDE) are considered. The realization of nonlinear SAWs in the form of solitary waves and as shock waves, used for the determination of the fracture strength, is described. The unique properties of dispersion-free wedge waves (WWs) propagating along homogeneous wedges and of dispersive wedge waves observed in the presence of wedge modifications such as tip truncation or coatings are outlined. Theoretical and experimental results on nonlinear wedge waves in isotropic and anisotropic solids are presented.

Solitary surface acoustic waves and bulk solitons in nanosecond and picosecond laser ultrasonics.

Recent achievements of nonlinear acoustics concerning the realization of solitons and solitary waves in crystals and their surfaces attained by nanosecond and picosecond laser ultrasonics are discussed and compared. The corresponding pump-probe setups are described, which allow an all-optical contact-free excitation and detection of short strain pulses in the broad frequency range between 10 MHz and about 300 GHz. The formation of solitons in the propagating longitudinal strain pulses is investigated for nonlinear media with intrinsic lattice-based dispersion. The excitation of solitary surface acoustic waves is realized by a geometric film-based dispersion effect. Future developments and potential applications of nonlinear nanosecond and picosecond ultrasonics are discussed.

Intercontinental impacts of ozone pollution on human mortality.

Ozone exposure is associated with negative health impacts, including premature mortality. Observations and modeling studies demonstrate that emissions from one continent influence ozone air quality over other continents. We estimate the premature mortalities avoided from surface ozone decreases obtained via combined 20% reductions of anthropogenic nitrogen oxide, nonmethane volatile organic compound, and carbon monoxide emissions in North America (NA), EastAsia (EA), South Asia (SA), and Europe (EU). We use estimates of ozone responses to these emission changes from several atmospheric chemical transportmodels combined with a health impactfunction. Foreign emission reductions contribute approximately 30%, 30%, 20%, and >50% of the mortalities avoided by reducing precursor emissions in all regions together in NA, EA, SA and EU, respectively. Reducing emissions in NA and EU avoids more mortalities outside the source region than within, owing in part to larger populations in foreign regions. Lowering the global methane abundance by 20% reduces mortality mostin SA,followed by EU, EA, and NA. For some source-receptor pairs, there is greater uncertainty in our estimated avoided mortalities associated with the modeled ozone responses to emission changes than with the health impact function parameters.

Nonlinear surface acoustic waves: silicon strength in phonon-focusing directions.

The anisotropy of the elastic properties of single-crystal silicon manifests itself in features of both the linear and nonlinear surface acoustic wave (SAW) propagation. Directions showing the phonon-focusing effect and strong nonlinearity were employed in contact-free and notch-free laser-based fracture experiments, yielding the intrinsic strength of silicon. The critical tensile stress values vary between 2.5 GPa and 7 GPa for the different crystallographic planes and directions of SAW propagation investigated.

Nonlinear surface acoustic waves: realization of solitary pulses and fracture.

A laser-based technique for the contact-free generation and detection of strongly nonlinear surface acoustic wave (SAW) pulses with amplitudes limited by the materials strength has been developed. The effects of nonlinear propagation of short elastic surface pulses with finite strength in isotropic solids, such as fused quartz, anisotropic solids, such as silicon, and dispersive media were investigated. Solitary surface wave propagation was observed in layered structures for normal and anomalous dispersion. In addition, a SAW-based method for evaluating the critical fracture stress of anisotropic brittle solids, such as single crystal silicon, is introduced.

Quantitative characterization of crosstalk effects for friction force microscopy with scan-by-probe SPMs.

If the photodetector and cantilever of an atomic force microscope (AFM) are not properly adjusted, crosstalk effects will appear. These effects disturb measurements of the absolute vertical and horizontal cantilever deflections, which are involved in friction force microscopy (FFM). A straightforward procedure is proposed to study quantitatively crosstalk effects observed in scan-by-probe SPMs. The advantage of this simple, fast, and accurate procedure is that no hardware change or upgrade is needed. The results indicate that crosstalk effects depend not only on the alignment of the detector but also on the cantilever properties, position, and detection conditions. The measurements may provide information on the origin of the crosstalk effect. After determination of its magnitude, simple correction formulas can be applied to correct the crosstalk effects and then the single-load wedge method, using a commercially available grating, can be employed for accurate calibration of the lateral force.

Ammonia detection by using quantum-cascade laser photoacoustic spectroscopy.

A pulsed quantum-cascade distributed-feedback laser, temperature tunable from -41 degrees C to +31.6 degrees C, and a resonant differential photoacoustic detector are used to measure trace-gas concentrations to as low as 66 parts per 10(9) by volume (ppbv) ammonia at a low laser power of 2 mW. Good agreement between the experimental spectrum and the simulated HITRAN spectrum of NH3 is found in the spectral range between 1046 and 1052 cm(-1). A detection limit of 30 ppbv ammonia at a signal-to-noise ratio of 1 was obtained with the quantum-cascade laser (QCL) photoacoustic (PA) setup. Concentration changes of approximately 50 ppbv were detectable with this compact and versatile QCL-based PA detection system. The performance of the PA detector, characterized by the product of the incident laser power and the minimum detectable absorption coefficient, was 4.7 x 10-9 W cm(-1).

Sensitive wavelength-modulated photoacoustic spectroscopy with a pulsed optical parametric oscillator.

With a laser-excited acoustic wave as the carrier wave and by modulation of the light wavelength of a multikilohertz-repetition-rate optical parametric oscillator at a lower frequency than the acoustic frequency, we demonstrate a wavelength-amplitude double-modulation technique and achieve an enhancement factor of 35 in sensitivity in photoacoustic trace gas detection with the technique.

Industrial emissions cause extreme urban ozone diurnal variability.

Simulations with a regional chemical transport model show that anthropogenic emissions of volatile organic compounds and nitrogen oxides (NO(x) = NO + NO(2)) lead to a dramatic diurnal variation of surface ozone (O(3)) in Houston, Texas. During the daytime, photochemical oxidation of volatile organic compounds catalyzed by NO(x) results in episodes of elevated ambient O(3) levels significantly exceeding the National Ambient Air Quality Standard. The O(3) production rate in Houston is significantly higher than those found in other cities over the United States. At night, a surface NO(x) maximum occurs because of continuous NO emission from industrial sources, and, consequently, an extensive urban-scale "hole" of surface ozone (<10 parts per billion by volume in the entire Houston area) is formed as a result of O(3) removal by NO. The results suggest that consideration of regulatory control of O(3) precursor emissions from the industrial sources is essential to formulate ozone abatement strategies in this region.

Dialysis access-associated steal syndrome: the intraoperative use of duplex ultrasound scan.

Dialysis access-associated steal syndrome (DASS) is an uncommon but serious complication after the creation of an arteriovenous shunt for hemodialysis and is related to an excess perfusion of the fistula. Several surgical options have been described for DASS correction. To achieve an adequate distribution of the blood flow towards the fistula and the hand, intraoperative duplex ultrasound scan monitoring was used in this preliminary communication to control the surgical reduction of volume flow through the fistula. The shunt flow was not estimated with direct insonation of the shunt but calculated from the difference of the bilateral subclavian artery volume flow rates. This new technique has several advantages over a direct shunt evaluation that are discussed in this report. Three patients with DASS are described in whom the technique was successfully applied and led to a normalization of the hand perfusion and to the maintenance of a long-term patency of the fistula.