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Hands-on learning in a laboratory is an integral part of the undergraduate experience for chemistry students. However, with the onset of the COVID-19 pandemic, an opportunity for this approach was not possible. The pandemic has been forcing instructors to explore the remote setting instead of the laboratory. There are several commercially available kits for remote laboratory instruction in general chemistry, organic chemistry, and biochemistry. Kits provide students with a majority of necessary items to conduct scientific experiments in their homes. Unfortunately, there are no commercially available kit options for laboratory exercises in an instrumental analysis course. Here, we describe a homemade kit that focuses on two important pillars of instrumental analysis: spectroscopy and chromatography. The total cost of the kit is about 700 USD; this amount can be reduced significantly if a "do-it-yourself" spectrometer is employed instead of a commercial model. Details about kit contents and experiments performed are described.

Energy Theater is a dynamic, full-body activity that engages all students in representing the flow of energy in various phenomena, such as a light bulb burning steadily or a refrigerator cooling food. In Energy Theater, each participant acts as a unit of energy that has one form at a time. Regions on the floor correspond to objects in a physical scenario, and participants move from one region to another to demonstrate the flow of energy among objects. (See Figs. 1 , 3 , and 4 .) The goal of Energy Theater is for students to track energy transfers and transformations in real-world energy scenarios while employing the principle of energy conservation and disambiguating matter and energy. Unlike most representations of energy, which are static before-and-after accounting schemes for energy changes, Energy Theater is a dynamic representation that provides a natural stepping stone toward the more advanced ideas of energy density, energy current, and a continuity equation relating them. The fact that conservation of energy is embedded in the representation encourages students to "find the energy" in situations where it may be imperceptible. The rules of Energy Theater are listed in Fig. 2 .

Inspired in part by Chemistry Collaborations, Workshops, and Community of Scholars workshops, the Chemistry and Art course offered at Ithaca College is team-taught by a chemist and an art historian, underscoring the complementary nature of the two disciplines. The course, populated primarily by nonscience majors, highlights the importance of using both historical knowledge and empirical measurements to address particular questions about a work of art. The course culminates in a collaborative student research project in which students must select a nonaccessioned art object, generate a series of questions about the object, and subsequently use available scientific tools to attempt to address these questions. Undergraduates are exposed to a variety of techniques used in the analysis of art objects, including visible and infrared spectroscopy, gas chromatography and mass spectrometry, X-ray fluorescence spectroscopy, and microscopy. The Chemistry and Art course at Ithaca College will be discussed, and two case studies from the collaborative student research projects will be summarized.

Abstract Aluminum, due to its high abundance, very attractive theoretical capacity, low cost, low (de−) lithiation potential, light weight, and effective suppression of dendrite growth, is considered as a promising anode candidate for lithium‐ion batteries (LIBs). However, its practical application is hindered due to multiple detrimental challenges, including the formation of an amorphous surface oxide layer, pulverization, and insufficient lithium diffusion kinetics in the α‐phase. These outstanding intrinsic challenges need to be addressed to facilitate the commercial production of Al‐based batteries. The native passivation layer, Al2O3, plays a critical role in the nucleation and reversibility of lithiating aluminum and is thoroughly investigated in this study using high precision electrochemical micro calorimetry. The enthalpy of crystallization of β‐LiAl is found to be 40.5 kJ mol−1, which is in a strong agreement with the value obtained by calculation using Nernst equation (40.04 kJ mol−1). Surface treatment of the active material by the addition of 25 nm of alumina increases the nucleation energy barrier by 83 % over the native oxide layer. After the initial nucleation, the added alumina does not negatively impact the reversibility at 0.1 C rate, suggesting the removal of alumina is not necessary for improving the cyclability of aluminum anode based lithium‐ion batteries. Moreover, the coulombic efficiencies are also found to be slightly higher in the alumina treated samples compared to the untreated ones.

The safety of titanium dioxide (TiO2), widely used in foods and personal care products, has been of ongoing concern. Significant toxicity of TiO2 has been reported, suggesting a risk to human health. To evaluate its potential epigenotoxicity, the effect of exposure to a TiO2 product to which humans could be exposed on DNA methylation, a primary epigenetic mechanism, was investigated using two human cell lines (Caco-2 (colorectal) and HepG2 (liver)) relevant to human exposure. Global methylation was determined by enzyme-linked immunosorbent assay-based immunochemical analysis. Gene promoter methylation was evaluated using EpiTect Methyl II Signature PCR System Array technology. Expression of DNA methyltransferases, MBD2, and URHF1 was quantified by qRT-PCR. A decrease in global DNA methylation was observed in both cell lines. Across the cell lines, seven genes (BNIP3, DNAJC15, GADD45G, GDF15, INSIG1, SCARA3, and TP53) were identified in which promoters were methylated. Changes in promoter methylation were associated with gene expression. Results also revealed aberrant expression of regulatory genes, DNA methyltransferases, MBD2, and UHRF1. Findings from the study clearly demonstrate the impact of TiO2 exposure on DNA methylation in two cell types, supporting the potential involvement of this epigenetic mechanism in its biological responses. Hence, epigenetic studies are critical for complete assessment of potential risk from exposure.

Past work has shown that traffic patterns in the USA and resulting NOx emissions vary by day of week, with NOx emissions typically being higher on weekdays than weekends. This pattern of emissions leads to different levels of ozone on weekends versus weekdays and can be leveraged to understand how local ozone formation changes in response to NOx emission perturbations in different urban areas. Specifically, areas with lower NOx but higher ozone on the weekends (the weekend effect) can be characterized as NOx-saturated and areas with both lower NOx and ozone on weekends (the weekday effect) can be characterized as NOx-limited. In this analysis, we assess maximum daily 8 h average (MDA8) ozone weekend–weekday differences across 51 USA nonattainment areas using 18 years of observed and modeled data from 2002–2019, using the following two metrics: mean MDA8 ozone and percentage of days with MDA8 ozone > 70 ppb (parts per billion). In addition, we quantify the modeled and observed trends in these weekend–weekday differences across this period of substantial NOx emission reductions in the USA. The model assessment is carried out using U.S. Environmental Protection Agency (EPA)'s Air QUAlity TimE Series Project (EQUATES) Community Multiscale Air Quality (CMAQ) model dataset. We identify three types of MDA8 ozone trends occurring across the USA, namely transitioning chemical regime, disappearing weekday effect, and no trend. The transitioning chemical regime trend occurs in a subset of large urban areas that were NOx-saturated (i.e., volatile organic compound (VOC)-limited) at the beginning of the analysis period but transitioned to mixed chemical regimes or NOx-limited conditions by the end of the analysis period. Nine areas have strong transitioning chemical regime trends using both modeled and observed data and with both metrics indicating strong agreement that they are shifting to more NOx-limited conditions: Milwaukee, Houston, Phoenix, Denver, the Northern Wasatch Front, the Southern Wasatch Front, Las Vegas, Los Angeles – San Bernardino County, Los Angeles – South Coast, and San Diego. The disappearing weekday effect was identified for multiple rural and agricultural areas of California which were NOx-limited for the entire analysis period but appear to become less influenced by local day-of-week emission patterns in more recent years. Finally, we discuss a variety of reasons why there are no trends in certain areas including complex impacts of heterogeneous source mixes and stochastic impacts of meteorology. Overall, this assessment finds that the EQUATES modeling simulations indicate more NOx-saturated conditions than the observations but do a good job of capturing year-to-year changes in weekend–weekday MDA8 ozone patterns.

Future African aerosol emissions, and therefore air pollution levels and health outcomes, are uncertain and understudied. Understanding the future health impacts of pollutant emissions from this region is crucial. Here, this research gap is addressed by studying the range in the future health impacts of aerosol emissions from Africa in the Shared Socioeconomic Pathway (SSP) scenarios, using the UK Earth System Model version 1 (UKESM1), along with human health concentration–response functions. The effects of Africa following a high-pollution aerosol pathway are studied relative to a low-pollution control, with experiments varying aerosol emissions from industry and biomass burning. Using present-day demographics, annual deaths within Africa attributable to ambient particulate matter are estimated to be lower by 150 000 (5th–95th confidence interval of 67 000–234 000) under stronger African aerosol mitigation by 2090, while those attributable to O3 are lower by 15 000 (5th–95th confidence interval of 9000–21 000). The particulate matter health benefits are realised predominantly within Africa, with the O3-driven benefits being more widespread – though still concentrated in Africa – due to the longer atmospheric lifetime of O3. These results demonstrate the important health co-benefits from future emission mitigation in Africa.

Solar climate intervention using stratospheric aerosol injection (SAI) has been proposed as a method which could offset some of the adverse effects of global warming. The Assessing Responses and Impacts of Solar climate intervention on the Earth system with Stratospheric Aerosol Injection (ARISE-SAI) set of simulations is based on a moderate-greenhouse-gas-emission scenario and employs injection of sulfur dioxide at four off-equatorial locations using a control algorithm which maintains the global-mean surface temperature at 1.5 K above pre-industrial conditions (ARISE-SAI-1.5), as well as the latitudinal gradient and inter-hemispheric difference in surface temperature. This is the first comparison between two models (CESM2 and UKESM1) applying the same multi-target SAI strategy. CESM2 is successful in reaching its temperature targets, but UKESM1 has considerable residual Arctic warming. This occurs because the pattern of temperature change in a climate with SAI is determined by both the structure of the climate forcing (mainly greenhouse gases and stratospheric aerosols) and the climate models' feedbacks, the latter of which favour a strong Arctic amplification of warming in UKESM1. Therefore, research constraining the level of future Arctic warming would also inform any hypothetical SAI deployment strategy which aims to maintain the inter-hemispheric and Equator-to-pole near-surface temperature differences. Furthermore, despite broad agreement in the precipitation response in the extratropics, precipitation changes over tropical land show important inter-model differences, even under greenhouse gas forcing only. In general, this ensemble comparison is the first step in comparing policy-relevant scenarios of SAI and will help in the design of an experimental protocol which both reduces some known negative side effects of SAI and is simple enough to encourage more climate models to participate.

Superhydrophobic materials are often inspired by nature, whereas metamaterials are engineered to have properties not usually occurring naturally. In both, the key to their unique properties is structure. Here, it is shown that a negative Poisson's ratio (auxetic) mechanical metamaterial can transform into a unique superhydrophobic material. When stretched, its surface has the counterintuitive property that it also expands in the orthogonal lateral direction. The change in the solid surface fraction as strain is applied is modeled, and it is shown that it decreases as the space between solid elements of the auxetic lattice expands. This results in a unique dependence of the superhydrophobicity on strain. Experimental models are constructed to illustrate the relationship between different states of strain and superhydrophobicity as the lattice transitions from an auxetic to a conventional structure. The findings offer a new approach to designing superhydrophobic materials for self‐cleaning surfaces, droplet transportation, droplet encapsulation, and oil–water separation.

In June 2019 the Raikoke volcano, located in the Kuril Islands northeast of the Japanese archipelago, erupted explosively and emitted approximately 1.5 Tg ± 0.2 Tg of SO2 and 0.4–1.8 Tg of ash into the upper troposphere and lower stratosphere. Volcanic ash is usually neglected in modelling stratospheric climate changes since larger particles have generally been considered to be short-lived particles in terms of their stratospheric lifetime. However, recent studies have shown that the coagulation of mixed particles with ash and sulfate is necessary to model the evolution of aerosol size distribution more accurately. We perform simulations using a nudged version of the UK Earth System Model (UKESM1) that includes a detailed two-moment aerosol microphysical scheme for modelling the oxidation of sulfur dioxide (SO2) to sulfate aerosol and the detailed evolution of aerosol microphysics in the stratosphere. We compare the model with a wide range of observational data. The current observational network, including satellites, surface-based lidars, and high-altitude sun photometers means that smaller-scale eruptions such as Raikoke provide unprecedented detail of the evolution of volcanic plumes and processes, but there are significant differences in the evolution of the plume detected using the various satellite retrievals. These differences stem from fundamental differences in detection methods between, e.g. lidar and limb-sounding measurement techniques and the associated differences in detection limits and the geographical areas where robust retrievals are possible. This study highlights that, despite the problems in developing robust and consistent observational constraints, the balance of evidence suggests that including ash in the model emission scheme provides a more accurate simulation of the evolution of the volcanic plume within UKESM1.

The potential future trend in African aerosol emissions is uncertain, with a large range found in future scenarios used to drive climate projections. The future climate impact of these emissions is therefore uncertain. Using the Shared Socioeconomic Pathway (SSP) scenarios, transient future experiments were performed with the UK Earth System Model (UKESM1) to investigate the effect of African emissions following the high emission SSP370 scenario as the rest of the world follows the more sustainable SSP119, relative to a global SSP119 control. This isolates the effect of Africa following a relatively more polluted future emissions pathway. Compared to SSP119, SSP370 projects higher non-biomass-burning (non-BB) aerosol emissions, but lower biomass burning emissions, over Africa. Increased shortwave (SW) absorption by black carbon aerosol leads to a global warming, but the reduction in the local incident surface radiation close to the emissions is larger, causing a local cooling effect. The local cooling persists even when including the higher African CO2 emissions under SSP370 than SSP119. The global warming is significantly higher by 0.07 K when including the non-BB aerosol increases and higher still (0.22 K) when including all aerosols and CO2. Precipitation also exhibits complex changes. Northward shifts in the Inter-tropical Convergence Zone (ITCZ) occur under relatively warm Northern Hemisphere land, and local rainfall is enhanced due to mid-tropospheric instability from black carbon absorption. These results highlight the importance of future African aerosol emissions for regional and global climate and the spatial complexity of this climate influence.

Deep generative neural networks are increasingly exploited for drug discovery, but often the majority of generated molecules are predicted to be inactive. Here, an optimized protocol for generative models with reinforcement learning is derived and applied to design potent epidermal growth factor inhibitors.

The successful use of a microband electrode printed on a silicon internal reflection element to perform time resolved infrared spectroscopy is described. Decreasing the critical dimension of the microband electrode to several hundred micrometers provides a sub-microsecond time constant in a Kretschmann configured spectroelectrochemical cell. The high brilliance of synchrotron sourced infrared radiation has been combined with a specially designed horizontal attenuated total reflectance (ATR) microscope to focus the infrared beam on the microband electrode. The first use of a sub-microsecond time constant working electrode for ATR surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) is reported. Measurements show that the advantage afforded by the high brilliance of the synchrotron source is at least partially offset by increased noise from the experimental floor. The test system was the potential induced desorption of an adsorbed monolayer of 4-methoxypyridine (MOP) as measured using step-scan interferometry. Based on diffusion considerations alone, the expected time scale of the process was less than 10 microseconds but was experimentally measured to be three orders of magnitude slower. A defect-mediated dissolution of the condensed film is speculated to be the underlying cause of the unexpected slow kinetics. Key words: ATR-SEIRAS, microband electrode, electrochemical time constant, step-scan interferometry, synchrotron infrared radiation. Nous decrivons l'emploi d'une electrode a microbande imprimee sur un element de reflexion interne en silicium que nous avons appliquee a la spectroscopie infrarouge a resolution temporelle. La reduction de la dimension critique de l'electrode a microbande a quelques centaines de micrometres donne lieu a une constante de temps de l'ordre de l'inframi-croseconde dans une cellule spectroelectrochimique de configuration Kretschmann. La forte brillance du rayonnement synchrotron infrarouge a ete conjuguee a un microscope en reflexion totale attenuee (RTA) horizontal specialement concu pour concentrer le faisceau infrarouge sur l'electrode a microbande. Nous faisons etat de la premiere utilisation d'une electrode de travail a constante de temps dans l'inframicroseconde destinee a la spectroscopie d'absorption infrarouge exaltee de surface en RTA (ATR-SEIRAS ou Attenuated Total Reflectance-Surface Enhanced InfraRed Absorption Spectroscopy). Selon les resultats que nous avons obtenus, l'avantage qu'offre la forte brillance de la source synchrotron est annule, du moins partiellement, par l'augmentation du bruit provenant du plancher de l'environnement experimental. L'eventuelle desorption d'une monocouche de 4methoxypyridine (MOP) adsorbee, mesuree par interferometrie a balayage progressif, constituait le systeme de mise a l'epreuve. Sur la base de considerations centrees uniquement sur la diffusion, le processus aurait du se produire sur une echelle de temps inferieure a 10 microsecondes, mais les mesures experimentales ont revele qu'il etait plus lent de trois ordres de grandeur. Nous posons l'hypothese selon laquelle une dissolution du film condense regie par la presence de defauts pourrait etre la cause sous-jacente de la cinetique etonnamment lente. [Traduit par la Redaction] Mots-cles : ATR-SEIRAS, electrode a microbande, constante de temps electrochimique, interferometrie a balayage progressif, rayonnement synchrotron infrarouge., Introduction The electrochemical RC cell constant, the product of the electrolyte resistance and the capacitance of the working electrode, determines the minimum time required for an electrified interface to respond [...]

The aim of the present study was to assess the relationship between a comprehensive physical testing battery and golf performance, as quantified through a variety of previously determined usable metrics from launch monitor data. Twenty-six high-level, amateur golfers undertook a series of physical assessments, including anthropometry measurements, isometric mid-thigh pull (IMTP), isometric bench press, countermovement jump (CMJ), seated medicine ball throws for distance, and seated thoracic rotation tests. In addition, golf shot data were recorded in an indoor biomechanics laboratory, with a driver and 6-iron to quantify clubhead speed (CHS), ball speed, carry distance, and smash factor. Pearson’s r associative analyses showed that the strongest relationships with the golf shot data were with the isometric bench press for the upper body (r values up to 0.76) and countermovement jump for the lower body (r values up to 0.82). In addition, the median split analysis of the physical performance data revealed that players who were able to exhibit greater maximal and explosive strength capabilities in the IMTP, isometric bench press, and CMJ assessments had a significantly greater CHS (g range = 1.09–1.28; p < 0.05), ball speed (g range = 1.18–1.41; p < 0.05), carry distance (g range = 1.06–1.53; p < 0.05), and smash factor (g range = 0.81–1.17; p < 0.05). These data underscore the importance of superior physical capacity for golfers, especially for maximal force production in both the lower and upper body, as well as explosive force production for the lower body.

Volcanic ash advisories are produced by specialised forecasters who combine several sources of observational data and volcanic ash dispersion model outputs based on their subjective expertise. These advisories are used by the aviation industry to make decisions about where it is safe to fly. However, both observations and dispersion model simulations are subject to various sources of uncertainties that are not represented in operational forecasts. Quantification and communication of these uncertainties are fundamental for making more informed decisions. Here, we develop a data assimilation method that combines satellite retrievals and volcanic ash transport and dispersion model (VATDM) output, considering uncertainties in both data sources. The methodology is applied to a case study of the 2019 Raikoke eruption. To represent uncertainty in the VATDM output, 1000 simulations are performed by simultaneously perturbing the eruption source parameters, meteorology, and internal model parameters (known as the prior ensemble). The ensemble members are filtered, based on their level of agreement with the ash column loading, and their uncertainty, of the Himawari–8 satellite retrievals, to produce a constrained posterior ensemble. For the Raikoke eruption, filtering the ensemble skews the values of mass eruption rate towards the lower values within the wider parameters ranges initially used in the prior ensemble (mean reduces from 1 to 0.1 Tg h−1). Furthermore, including satellite observations from subsequent times increasingly constrains the posterior ensemble. These results suggest that the prior ensemble leads to an overestimate of both the magnitude and uncertainty in ash column loadings. Based on the prior ensemble, flight operations would have been severely disrupted over the Pacific Ocean. Using the constrained posterior ensemble, the regions where the risk is overestimated are reduced, potentially resulting in fewer flight disruptions. The data assimilation methodology developed in this paper is easily generalisable to other short duration eruptions and to other VATDMs and retrievals of ash from other satellites.

Abstract This is the first study investigating the nuclear factor (erythroid‐derived 2)‐like 2 (NRF2) activity of compounds containing a new scaffold, tetrahydrobenzo[b]thiophene. Eighteen compounds were synthesised and confirmed their NRF2 activation through NQO1 enzymatic activity and mRNA expression of NQO1 and HO‐1 in Hepa‐1c1c7 cells. The compounds disrupted the interaction between Kelch‐like ECH‐associated protein 1 (KEAP1) and NRF2 via interfering with the KEAP1’s Kelch domain. The compounds exhibited anti‐inflammatory activity in Escherichia coli Lipopolysaccharide (LPSEc)‐stimulated RAW 264.7 cells. The anti‐inflammatory activity of the compounds was associated with their ability to activate NRF2. The compounds reversed the elevated levels of pro‐inflammatory cytokines (IL‐1β, IL‐6, TNF‐α, and IFN‐γ) and inflammatory mediators (PGE2, COX‐2, and NF‐κB). The compounds were metabolically stable in human, rat, and mouse liver microsomes and showed optimum half‐life (T1/2) and intrinsic clearance (Clint). The binding mode of the compounds and physicochemical properties were predicted via in silico studies.

Observations from the Orbiting Carbon Observatory 2 (OCO-2) satellite have been used to estimate CO2 fluxes in many regions of the globe and provide new insight into the global carbon cycle. The objective of this study is to infer the relationships between patterns in OCO-2 observations and environmental drivers (e.g., temperature, precipitation) and therefore inform a process understanding of carbon fluxes using OCO-2. We use a multiple regression and inverse model, and the regression coefficients quantify the relationships between observations from OCO-2 and environmental driver datasets within individual years for 2015–2018 and within seven global biomes. We subsequently compare these inferences to the relationships estimated from 15 terrestrial biosphere models (TBMs) that participated in the TRENDY model inter-comparison. Using OCO-2, we are able to quantify only a limited number of relationships between patterns in atmospheric CO2 observations and patterns in environmental driver datasets (i.e., 10 out of the 42 relationships examined). We further find that the ensemble of TBMs exhibits a large spread in the relationships with these key environmental driver datasets. The largest uncertainty in the models is in the relationship with precipitation, particularly in the tropics, with smaller uncertainties for temperature and photosynthetically active radiation (PAR). Using observations from OCO-2, we find that precipitation is associated with increased CO2 uptake in all tropical biomes, a result that agrees with half of the TBMs. By contrast, the relationships that we infer from OCO-2 for temperature and PAR are similar to the ensemble mean of the TBMs, though the results differ from many individual TBMs. These results point to the limitations of current space-based observations for inferring environmental relationships but also indicate the potential to help inform key relationships that are very uncertain in state-of-the-art TBMs.

Interactions between aerosols and gases in the atmosphere have been the focus of an increasing number of studies in recent years. Here, we focus on aerosol effects on tropospheric ozone that involve meteorological feedbacks induced by aerosol–radiation interactions. Specifically, we study the effects that involve aerosol influences on the transport of gaseous pollutants and on atmospheric moisture, both of which can impact ozone chemistry. For this purpose, we use the UK Earth System Model (UKESM1), with which we performed sensitivity simulations including and excluding the aerosol direct radiative effect (ADE) on atmospheric chemistry, and focused our analysis on an area with a high aerosol presence, namely China. By comparing the simulations, we found that ADE reduced shortwave radiation by 11 % in China and consequently led to lower turbulent kinetic energy, weaker horizontal winds and a shallower boundary layer (with a maximum of 102.28 m reduction in north China). On the one hand, the suppressed boundary layer limited the export and diffusion of pollutants and increased the concentration of CO, SO2, NO, NO2, PM2.5 and PM10 in the aerosol-rich regions. The NO/NO2 ratio generally increased and led to more ozone depletion. On the other hand, the boundary layer top acted as a barrier that trapped moisture at lower altitudes and reduced the moisture at higher altitudes (the specific humidity was reduced by 1.69 % at 1493 m on average in China). Due to reduced water vapour, fewer clouds were formed and more sunlight reached the surface, so the photolytical production of ozone increased. Under the combined effect of the two meteorology feedback methods, the annual average ozone concentration in China declined by 2.01 ppb (6.2 %), which was found to bring the model into closer agreement with surface ozone measurements from different parts of China.

We apply airborne measurements across three seasons (summer, winter and spring 2017–2018) in a multi-inversion framework to quantify methane emissions from the US Corn Belt and Upper Midwest, a key agricultural and wetland source region. Combing our seasonal results with prior fall values we find that wetlands are the largest regional methane source (32 %, 20 [16–23] Gg/d), while livestock (enteric/manure; 25 %, 15 [14–17] Gg/d) are the largest anthropogenic source. Natural gas/petroleum, waste/landfills, and coal mines collectively make up the remainder. Optimized fluxes improve model agreement with independent datasets within and beyond the study timeframe. Inversions reveal coherent and seasonally dependent spatial errors in the WetCHARTs ensemble mean wetland emissions, with an underestimate for the Prairie Pothole region but an overestimate for Great Lakes coastal wetlands. Wetland extent and emission temperature dependence have the largest influence on prediction accuracy; better representation of coupled soil temperature–hydrology effects is therefore needed. Our optimized regional livestock emissions agree well with the Gridded EPA estimates during spring (to within 7 %) but are ∼ 25 % higher during summer and winter. Spatial analysis further shows good top-down and bottom-up agreement for beef facilities (with mainly enteric emissions) but larger (∼ 30 %) seasonal discrepancies for dairies and hog farms (with > 40 % manure emissions). Findings thus support bottom-up enteric emission estimates but suggest errors for manure; we propose that the latter reflects inadequate treatment of management factors including field application. Overall, our results confirm the importance of intensive animal agriculture for regional methane emissions, implying substantial mitigation opportunities through improved management.

There is much about the action of bismuth within heterogeneous catalysis that still require a deeper understanding. We observed that, when Bi was added to AuPd bimetallic nanoparticles (NPs) supported on activated carbon, Bi affected the activity and significantly alters the selectivity in two model liquid phase reactions, namely the oxidation of cinnamyl alcohol and the hydrogenation of cinnamaldehyde. A combination of transmission electron microscopy and X-ray absorption spectroscopy provided a detailed characterization of trimetallic AuPdBi systems. We propose that the introduction of bismuth on AuPd NPs results in a partial blockage of most active sites, limiting the occurrence of consecutive reactions.

We present top-down constraints on global monthly N2O emissions for 2011 from a multi-inversion approach and an ensemble of surface observations. The inversions employ the GEOS-Chem adjoint and an array of aggregation strategies to test how well current observations can constrain the spatial distribution of global N2O emissions. The strategies include (1) a standard 4D-Var inversion at native model resolution (4° × 5°), (2) an inversion for six continental and three ocean regions, and (3) a fast 4D-Var inversion based on a novel dimension reduction technique employing randomized singular value decomposition (SVD). The optimized global flux ranges from 15.9 Tg N yr−1 (SVD-based inversion) to 17.5–17.7 Tg N yr−1 (continental-scale, standard 4D-Var inversions), with the former better capturing the extratropical N2O background measured during the HIAPER Pole-to-Pole Observations (HIPPO) airborne campaigns. We find that the tropics provide a greater contribution to the global N2O flux than is predicted by the prior bottom-up inventories, likely due to underestimated agricultural and oceanic emissions. We infer an overestimate of natural soil emissions in the extratropics and find that predicted emissions are seasonally biased in northern midlatitudes. Here, optimized fluxes exhibit a springtime peak consistent with the timing of spring fertilizer and manure application, soil thawing, and elevated soil moisture. Finally, the inversions reveal a major emission underestimate in the US Corn Belt in the bottom-up inventory used here. We extensively test the impact of initial conditions on the analysis and recommend formally optimizing the initial N2O distribution to avoid biasing the inferred fluxes. We find that the SVD-based approach provides a powerful framework for deriving emission information from N2O observations: by defining the optimal resolution of the solution based on the information content of the inversion, it provides spatial information that is lost when aggregating to political or geographic regions, while also providing more temporal information than a standard 4D-Var inversion.

Cautions chemists to be wary of ferromagnetic samples (especially magnetized samples), stray electromagnetic radiation, dusty environments, and changing weather conditions. These and other conditions may alter readings obtained from electronic analytical balances. (JN)

Describes exercises used for the first two weeks of general chemistry when class rolls are fluctuating. Includes learning objectives, linear graphs, nonlinear graphs, scatter graphs, and precision of measurement. Exercises are designed to introduce students to the metric system, balances, significant digits, graphing, and computerized data analysis. (CW)

There have been efforts to develop physiologically based pharmacokinetic (PBPK) models for nanomaterials (NMs). Since NMs have quite different kinetic behaviors, the applicability of the approaches and techniques that are utilized in current PBPK models for NMs is warranted. Most PBPK models simulate a size-independent endocytosis from tissues or blood. In the lungs, dosimetry and the air-liquid interface (ALI) models have sometimes been used to estimate NM deposition and translocation into the circulatory system. In the gastrointestinal (GI) tract, kinetics data are needed for mechanistic understanding of NM behavior as well as their absorption through GI mucus and their subsequent hepatobiliary excretion into feces. Following absorption, permeability (Pt) and partition coefficients (PCs) are needed to simulate partitioning from the circulatory system into various organs. Furthermore, mechanistic modelling of organ- and species-specific NM corona formation is in its infancy. More recently, some PBPK models have included the mononuclear phagocyte system (MPS). Most notably, dissolution, a key elimination process for NMs, is only empirically added in some PBPK models. Nevertheless, despite the many challenges still present, there have been great advances in the development and application of PBPK models for hazard assessment and risk assessment of NMs.

We employ new global space-based measurements of atmospheric methanol from the Tropospheric Emission Spectrometer (TES) with the adjoint of the GEOS-Chem chemical transport model to quantify terrestrial emissions of methanol to the atmosphere. Biogenic methanol emissions in the model are based on version 2.1 of the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1), using leaf area data from NASA's Moderate Resolution Imaging Spectroradiometer (MODIS) and GEOS-5 assimilated meteorological fields. We first carry out a pseudo observation test to validate the overall approach, and find that the TES sampling density is sufficient to accurately quantify regional- to continental-scale methanol emissions using this method. A global inversion of two years of TES data yields an optimized annual global surface flux of 122 Tg yr−1 (including biogenic, pyrogenic, and anthropogenic sources), an increase of 60% from the a priori global flux of 76 Tg yr−1. Global terrestrial methanol emissions are thus nearly 25% those of isoprene (~540 Tg yr−1), and are comparable to the combined emissions of all anthropogenic volatile organic compounds (~100–200 Tg yr−1). Our a posteriori terrestrial methanol source leads to a strong improvement of the simulation relative to an ensemble of airborne observations, and corroborates two other recent top-down estimates (114–120 Tg yr−1) derived using in situ and space-based measurements. Inversions testing the sensitivity of optimized fluxes to model errors in OH, dry deposition, and oceanic uptake of methanol, as well as to the assumed a priori constraint, lead to global fluxes ranging from 118 to 126 Tg yr−1. The TES data imply a relatively modest revision of model emissions over most of the tropics, but a significant upward revision in midlatitudes, particularly over Europe and North America. We interpret the inversion results in terms of specific source types using the methanol : CO correlations measured by TES, and find that biogenic emissions are overestimated relative to biomass burning and anthropogenic emissions in central Africa and southeastern China, while they are underestimated in regions such as Brazil and the US. Based on our optimized emissions, methanol accounts for > 25% of the photochemical source of CO and HCHO over many parts of the northern extratropics during springtime, and contributes ~6% of the global secondary source of those compounds annually.