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A new selenized yeast reference material (SELM-1) produced by the Institute for National Measurement Standards, National Research Council of Canada (INMS, NRC) certified for total selenium (2,059±64 mg kg-¹), methionine (Met, 5,758±277 mg kg-¹) and selenomethionine (SeMet, 3,431±157 mg kg-¹) content is described. The ±value represents an expanded uncertainty with a coverage factor of 2. SeMet and Met amount contents were established following a methanesulfonic acid digestion of the yeast using GC-MS and LC-MS quantitation. Isotope dilution (ID) calibration was used for both compounds, using ¹³C-labelled SeMet and Met. Total Se was determined after complete microwave acid digestion based on ID ICP-MS using a ⁸²Se spike or ICP-OES spectrometry using external calibration. An international intercomparison exercise was piloted by NRC to assess the state-of-the-art of measurement of selenomethione in SELM-1. Determination of total Se and methionine was also attempted. Seven laboratories submitted results (2 National Metrology Institutes (NMIs) and 5 university/government laboratories). For SeMet, ten independent mean values were generated. Various acid digestion and enzymatic procedures followed by LC ICP-MS, LC AFS or GC-MS quantitation were used. Four values were based on species-specific ID calibration, one on non-species-specific ID with the remainder using standard addition (SA) or external calibration (EC). For total selenium, laboratories employed various acid digestion procedures followed by ICP-MS, AFS or GC-MS quantitation. Four laboratories employed ID calibration, the remaining used SA or EC. A total of seven independent results were submitted. Results for methionine were reported by only three laboratories, all of which used various acid digestion protocols combined with determination by GC-MS and LC UV. The majority of participants submitted values within the certified range for SeMet and total Se, whereas the intercomparison was judged unsuccessful for Met because only two external laboratories provided values, both of which were outside the certified range.

The Community Earth System Model version 2 (CESM2) includes a detailed representation of chemistry throughout the atmosphere in the Community Atmosphere Model with chemistry and Whole Atmosphere Community Climate Model configurations. These model configurations use the Model for Ozone and Related chemical Tracers (MOZART) family of chemical mechanisms, covering the troposphere, stratosphere, mesosphere, and lower thermosphere. The new MOZART tropospheric chemistry scheme (T1) has a number of updates over the previous version (MOZART‐4) in CESM, including improvements to the oxidation of isoprene and terpenes, organic nitrate speciation, and aromatic speciation and oxidation and thus improved representation of ozone and secondary organic aerosol precursors. An evaluation of the present‐day simulations of CESM2 being provided for Climate Model Intercomparison Project round 6 (CMIP6) is presented. These simulations, using the anthropogenic and biomass burning emissions from the inventories specified for CMIP6, as well as online calculation of emissions of biogenic compounds, lightning NO, dust, and sea salt, indicate an underestimate of anthropogenic emissions of a variety of compounds, including carbon monoxide and hydrocarbons. The simulation of surface ozone in the southeast United States is improved over previous model versions, largely due to the improved representation of reactive nitrogen and organic nitrate compounds resulting in a lower ozone production rate than in CESM1 but still overestimates observations in summer. The simulation of tropospheric ozone agrees well with ozonesonde observations in many parts of the globe. The comparison of NOx and PAN to aircraft observations indicates the model simulates the nitrogen budget well. Plain Language Summary The set of chemical reactions for tropospheric chemistry used in the Community Earth System Model version 2 (CESM2) has been updated significantly over CESM1 in the Community Atmosphere Model with chemistry (CAM‐chem) and Whole Atmosphere Community Climate Model (WACCM) configurations. The emissions used for the CESM2 simulations are documented here, with anthropogenic and biomass burning emissions based on the specified inventories for Climate Model Intercomparison Project 6 (CMIP6), and emissions of biogenic compounds, lightning NO, dust, and sea salt are calculated online and dependent on the simulated meteorology. Evaluation of the CAM‐chem and WACCM configurations of CESM2 with observations indicate an underestimate of anthropogenic emissions of a variety of compounds, including carbon monoxide and hydrocarbons. The updated chemistry leads to an improvement in the simulation of tropospheric ozone. Key Points This paper fully documents the significant updates to the chemistry mechanisms in version 2 of the Community Earth System Model The new tropospheric chemistry scheme improves representation of isoprene oxidation as well as other ozone precursors over earlier versions The simulation of tropospheric ozone is improved in comparison to observations

Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2 %, COA: 15.0 ± 3.4 %, OOA: 41.5 ± 5.7 %, BBOA: 29.3 ± 5.0 %). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2 %.

The recently developed time-of-flight aerosol chemical speciation monitor with a capture vaporizer and a PM2.5 aerodynamic lens (TOF-ACSM-CV-PM2.5) aims to improve the collection efficiency and chemical characterization of aerosol particles with a diameter smaller than 2.5 µm. In this study, comprehensive cross-comparisons were performed between real-time online measurements and offline filter analysis with 24 h collection time. The goal was to evaluate the capabilities of the TOF-ACSM-CV-PM2.5 lens, as well as the accuracy of the TOF-ACSM-CV-PM2.5. The experiments were conducted at Cabauw Experimental Site for Atmospheric Research (CESAR) during the RITA-2021 campaign. The non-refractory fine particulate matter (PM1.0 and PM2.5) was measured by two collocated TOF-ACSM-CV-PM2.5 instruments by placing them behind a PM2.5 and PM1.0 inlet, respectively. A comparison between the ACSMs and PM2.5 and PM1.0 filter samples showed a much better accuracy than ±30 % less given in the previous reports, with average differences less than ±10 % for all inorganic chemical species. In addition, the ACSMs were compared to the Monitoring Instrument for Aerosol and Gas (MARGA) (slope between 0.78 and 0.97 for inorganic compounds, R2≥ 0.93) and a mobility particle size spectrometer (MPSS), measuring the particle size distribution from around 10 to 800 nm (slope was around 1.00, R2= 0.91). The intercomparison of the online measurements and the comparison between the online and offline measurements indicated a low bias (< 10 % for inorganic compounds) and demonstrated the high accuracy and stability of the TOF-ACSM-CV-PM2.5 lens for the atmospheric observations of particle matter. The two ACSMs exhibited an excellent agreement, with differences less than 7 %, which allowed a quantitative estimate of PM1.0 vs. PM2.5 chemical composition. The result showed that the PM1.0 accounted for about 70 %–80 % of the PM2.5 on average. The NO3 mass fraction increased, but the organic carbon (OC) mass fraction decreased from PM1.0 to PM2.5, indicating the size dependence on chemical composition.

Chemical mechanisms are critical to chemical transport models for air quality research and policy analysis. Several mechanisms are available and intercomparison, especially using metrics which reduce sensitivity to modeling scenario, is important for interpreting results and assessing uncertainties. Here, we investigate Ozone Production Efficiency (OPE) as a comparison metric under conditions where nitrogen oxides (NOX) are limited. OPE is the net number of ozone molecules produced per NOX molecule lost and can be computed in simulations using chemical process analysis (CPA). We compute OPE (OPE-CPA) for four chemical mechanisms (CB6r5, CB7r1, SAPRC07, RACM2) and find a similar response to varying anthropogenic emissions of volatile organic compounds (VOC) and NOX. RACM2 consistently produces the largest OPE-CPA and differences between mechanisms are greatest at high VOC / NOX ratios. The high RACM2 OPE-CPA is partially due to a slower OH+NO2 rate and potentially to its treatment of NOX recycling. OPE-CPA is generally consistent with aircraft OPE measurements downwind of Houston but direct comparison is difficult due to uncertainties in deposition and VOC speciation. More recent OPE measurements are required to determine whether trends over time are consistent. OPE-CPA responds nonlinearly to NOX and increases at low NOX even as ozone production decreases. Using OPE to predict ozone response to NOX emissions reductions is therefore an oversimplification that will tend to overstate ozone reductions. OPE-CPA is a viable metric to compare mechanisms, however, additional work would be helpful to define standardized conditions for comparisons.

The Beijing Climate Center Earth System Model version 1 (BCC-ESM1) is the first version of a fully coupled Earth system model with interactive atmospheric chemistry and aerosols developed by the Beijing Climate Center, China Meteorological Administration. Major aerosol species (including sulfate, organic carbon, black carbon, dust, and sea salt) and greenhouse gases are interactively simulated with a whole panoply of processes controlling emission, transport, gas-phase chemical reactions, secondary aerosol formation, gravitational settling, dry deposition, and wet scavenging by clouds and precipitation. Effects of aerosols on radiation, cloud, and precipitation are fully treated. The performance of BCC-ESM1 in simulating aerosols and their optical properties is comprehensively evaluated as required by the Aerosol Chemistry Model Intercomparison Project (AerChemMIP), covering the preindustrial mean state and time evolution from 1850 to 2014. The simulated aerosols from BCC-ESM1 are quite coherent with Coupled Model Intercomparison Project Phase 5 (CMIP5)-recommended data, in situ measurements from surface networks (such as IMPROVE in the US and EMEP in Europe), and aircraft observations. A comparison of modeled aerosol optical depth (AOD) at 550 nm with satellite observations retrieved from the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Multi-angle Imaging SpectroRadiometer (MISR) and surface AOD observations from the AErosol RObotic NETwork (AERONET) shows reasonable agreement between simulated and observed AOD. However, BCC-ESM1 shows weaker upward transport of aerosols from the surface to the middle and upper troposphere, likely reflecting the deficiency of representing deep convective transport of chemical species in BCC-ESM1. With an overall good agreement between BCC-ESM1 simulated and observed aerosol properties, it demonstrates a success of the implementation of interactive aerosol and atmospheric chemistry in BCC-ESM1.

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall – early-winter period (November–December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.

Water-soluble inorganic ions such as ammonium, nitrate and sulfate are major components of fine aerosols in the atmosphere and are widely used in the estimation of aerosol acidity. However, different experimental practices and instrumentation may lead to uncertainties in ion concentrations. Here, an intercomparison experiment was conducted in 10 different laboratories (labs) to investigate the consistency of inorganic ion concentrations and resultant aerosol acidity estimates using the same set of aerosol filter samples. The results mostly exhibited good agreement for major ions Cl−, SO42-, NO3-, NH4+ and K+. However, F−, Mg2+ and Ca2+ were observed with more variations across the different labs. The Aerosol Chemical Speciation Monitor (ACSM) data of nonrefractory SO42-, NO3- and NH4+ generally correlated very well with the filter-analysis-based data in our study, but the absolute concentrations differ by up to 42 %. Cl− from the two methods are correlated, but the concentration differ by more than a factor of 3. The analyses of certified reference materials (CRMs) generally showed a good detection accuracy (DA) of all ions in all the labs, the majority of which ranged between 90 % and 110 %. The DA was also used to correct the ion concentrations to showcase the importance of using CRMs for calibration check and quality control. Better agreements were found for Cl−, SO42-, NO3-, NH4+ and K+ across the labs after their concentrations were corrected with DA; the coefficient of variation (CV) of Cl−, SO42-, NO3-, NH4+ and K+ decreased by 1.7 %, 3.4 %, 3.4 %, 1.2 % and 2.6 %, respectively, after DA correction. We found that the ratio of anion to cation equivalent concentrations (AE / CE) and ion balance (anions–cations) are not good indicators for aerosol acidity estimates, as the results in different labs did not agree well with each other. In situ aerosol pH calculated from the ISORROPIA II thermodynamic equilibrium model with measured ion and ammonia concentrations showed a similar trend and good agreement across the 10 labs. Our results indicate that although there are important uncertainties in aerosol ion concentration measurements, the estimated aerosol pH from the ISORROPIA II model is more consistent.

Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) is capable of detecting a wide range of organic oxidation products in the particle phase in real time with minimal fragmentation. Quantification can sometimes be hindered by a lack of available commercial standards for aerosol constituents, however. Good correlations between the EESI-TOF and other aerosol speciation techniques have been reported, though no attempts have yet been made to parameterize the EESI-TOF response factor for different chemical species. Here, we report the first parameterization of the EESI-TOF response factor for secondary organic aerosol (SOA) at the near-molecular level based on its elemental composition. SOA was formed by ozonolysis of monoterpene or OH oxidation of aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as seed particles. A Vocus proton-transfer reaction mass spectrometer (Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used to determine the gas-phase molecular composition and the particle-phase bulk chemical composition, respectively. The EESI response factors towards bulk SOA coating and the inorganic seed particle core were constrained by intercomparison with the AMS. The highest bulk EESI response factor was observed for SOA produced from 1,3,5-trimethylbenzene, followed by those produced from d-limonene and o-cresol, consistent with previous findings. The near-molecular EESI response factors were derived from intercomparisons with Vocus-PTR measurements and were found to vary from 103 to 106 ion counts s−1 ppb−1, mostly within ±1 order of magnitude of their geometric mean of 104.6 ion counts s−1 ppb−1. For aromatic SOA components, the EESI response factors correlated with molecular weight and oxygen content and inversely correlated with volatility. The near-molecular response factors mostly agreed within a factor of 20 for isomers observed across the aromatics and biogenic systems. Parameterization of the near-molecular response factors based on the measured elemental formulae could reproduce the empirically determined response factor for a single volatile organic compound (VOC) system to within a factor of 5 for the configuration of our mass spectrometers. The results demonstrate that standard-free quantification using the EESI-TOF is possible.

It is now recognized and confirmed that the ozone layer shields the biosphere from dangerous solar UV radiation and is also important for the global atmosphere and climate. The observed massive ozone depletion forced the introduction of limitations on the production of halogen-containing ozone-depleting substances (hODSs) by the Montreal Protocol and its amendments and adjustments (MPA). Previous research has demonstrated the success of the Montreal Protocol and increased public awareness of its necessity. In this study, we evaluate the benefits of the Montreal Protocol on climate and ozone evolution using the Earth system model (ESM) SOCOLv4.0 (modeling tools for studies of SOlar Climate Ozone Links) which includes dynamic modules for the ocean, sea ice, interactive ozone, and stratospheric aerosol. Here, we analyze the results of the numerical experiments performed with and without limitations on the ozone-depleting substance (ODS) emissions. In the experiments, we have used CMIP6 (Coupled Model Intercomparison Project) SSP2-4.5 and SSP5-8.5 (Shared Socioeconomic Pathway) scenarios for future forcing behavior. We confirm previous results regarding catastrophic ozone layer depletion and substantial climate warming in the case without MPA limitations. We show that the climate effects of MPA consist of additional global-mean warming by up to 2.5 K in 2100 caused by the direct radiative effect of the hODSs, which is comparable to large climate warming obtained with the SSP5-8.5 scenario. For the first time, we reveal the dramatic effects of MPA on chemical species and cloud cover. The response of surface temperature, precipitation, and sea-ice fields was demonstrated for the first time with the model that has interactive tropospheric and stratospheric chemistry. We have found some differences in the climate response compared to the model with prescribed ozone, which should be further addressed. Our research updates and complements previous modeling studies on the quantifying of MPA benefits for the terrestrial atmosphere and climate.