How to most effectively expand the global surface ozone observing network

Surface ozone observations with modern instrumentation have been made around the world for more than 40 years. Some of these observations have been made as one-off activities with short-term, specific science objectives and some have been made as part of wider networks which have provided a foundational infrastructure of data collection, calibration, quality control, and dissemination. These observations provide a fundamental underpinning to our understanding of tropospheric chemistry, air quality policy, atmosphere-biosphere interactions, etc. brought together eight of these networks to provide a single data set of surface ozone observations. We investigate how representative this combined data set is of global surface ozone using the output from a global atmospheric chemistry model. We estimate that on an area basis, 25 % of the globe is observed (34 % land, 21 % ocean). Whereas Europe and North America have almost complete coverage, other continents, Africa, South America, Australia, and Asia (12-17 %) show significant gaps. Antarctica is surprisingly well observed (78 %). Little monitoring occurs over the oceans, with the tropical and southern oceans particularly poorly represented. The surface ozone over key biomes such as tropical forests and savanna is almost completely unmonitored. A chemical cluster analysis suggests that a significant number of observations are made of polluted air masses, but cleaner air masses whether over the land or ocean (especially again in the tropics) are significantly under-observed. The current network is unlikely to see the impact of the El Ninõ-Southern Oscillation (ENSO) but may be capable of detecting other planetary-scale signals. Model assessment and validation activities are hampered by a lack of observations in regions where the models differ substantially, as is the ability to monitor likely changes in surface ozone over the next century. Using our methodology we are able to suggest new sites which would help to close the gap in our ability to measure global surface ozone. An additional 20 surface ozone monitoring sites (a 20 % increase in the World Meteorological Organization Global Atmosphere Watch (WMO GAW) ozone sites or a 1 % increase in the total background network) located on 10 islands and in 10 continental regions would almost double the area observed. The cost of this addition to the network is small compared to other expenditure on atmospheric composition research infrastructure and would provide a significant long-term benefit to our understanding of the composition of the atmosphere, information which will also be available for consideration by air quality control managers and policy makers

Spectral analysis of atmospheric composition: application to surface ozone model-measurement comparisons

Models of atmospheric composition play an essential role in our scientific understanding of atmospheric processes and in providing policy strategies to deal with societally relevant problems such as climate change, air quality and ecosystem degradation. The fidelity of these models needs to be assessed against observations to ensure that errors in model formulations are found and that model limitations are understood. A range of approaches are necessary for these comparisons. Here, we apply a spectral analysis methodology for this comparison. We use the Lomb-Scargle Periodogram, a method similar to a Fourier transform, but better suited to dealing with the gapped datasets typical of observational data. We apply this methodology to long-term hourly ozone observations and the equivalent model (GEOS-Chem) output. We show that the spectrally transformed observational data shows a distinct power spectrum with regimes indicative of meteorological processes (weather, macroweather) and specific peaks observed at the daily and annual timescales together with corresponding harmonic peaks at half, third etc. of these frequencies. Model output shows corresponding features. A comparison between the amplitude and phase of these peaks introduces a new comparison methodology between model and measurements.We focus on the amplitude and phase of diurnal and seasonal cycles and present observational/model comparisons and discuss model performance. We find large biases notably for the seasonal cycle in the mid-latitude northern hemisphere where the amplitudes are generally overestimated by up to 16 ppb, and phases are too late on the order of 1–5 months. This spectral methodology can be applied to a range of model-measurement applications and is highly suitable for Multimodel Intercomparison Projects (MIPs)

Factors controlling variability in the oxidative capacity of the troposphere since the Last Glacial Maximum

The oxidative capacity of past atmospheres is highly uncertain. We present here a new climate–biosphere–chemistry modeling framework to determine oxidant levels in the present and past troposphere. We use the GEOS-Chem chemical transport model driven by meteorological fields from the NASA Goddard Institute of Space Studies (GISS) ModelE, with land cover and fire emissions from dynamic global vegetation models. We present time-slice simulations for the present day, late preindustrial era (AD 1770), and the Last Glacial Maximum (LGM, 19–23 ka), and we test the sensitivity of model results to uncertainty in lightning and fire emissions. We find that most preindustrial and paleo climate simulations yield reduced oxidant levels relative to the present day. Contrary to prior studies, tropospheric mean OH in our ensemble shows little change at the LGM relative to the preindustrial era (0.5 ± 12 %), despite large reductions in methane concentrations. We find a simple linear relationship between tropospheric mean ozone photolysis rates, water vapor, and total emissions of NO_x and reactive carbon that explains 72 % of the variability in global mean OH in 11 different simulations across the last glacial–interglacial time interval and the industrial era. Key parameters controlling the tropospheric oxidative capacity over glacial–interglacial periods include overhead stratospheric ozone, tropospheric water vapor, and lightning NO_x emissions. Variability in global mean OH since the LGM is insensitive to fire emissions. Our simulations are broadly consistent with ice-core records of Δ¹⁷O in sulfate and nitrate at the LGM, and CO, HCHO, and H₂O₂ in the preindustrial era. Our results imply that the glacial–interglacial changes in atmospheric methane observed in ice cores are predominantly driven by changes in its sources as opposed to its sink with OH

Updated ozone absorption cross section will reduce air quality compliance

Photometric ozone measurements rely upon an accurate value of the ozone absorption cross section at 253.65 nm. This has recently been reevaluated by Viallon et al. (2015) as 1.8 % smaller than the accepted value (Hearn, 1961) used for the preceding fifty years. Thus, ozone measurements that applied the older cross section systematically underestimate the amount of ozone in air. We correct the reported historical surface data from North America and Europe and find that this modest change in cross section has a significant impact on the number of locations that are out of compliance with air quality regulations if the air quality standards remain the same. We find 18, 23, and 20 % increases in the number of sites that are out of compliance with current US, Canadian, and European ozone air quality health standards for the year 2012. Should the new cross section value be applied, it would impact attainment of air quality standards and compliance with relevant clean air acts, unless the air quality target values themselves were also changed proportionately. We draw attention to how a small change in gas metrology has a global impact on attainment and compliance with legal air quality standards. We suggest that further laboratory work to evaluate the new cross section is needed and suggest three possible technical and policy responses should the new cross section be adopted

Controls on the movement and composition of firn air at the West Antarctic Ice Sheet Divide

We sampled interstitial air from the perennial snowpack (firn) at a site near the West Antarctic Ice Sheet Divide (WAIS-D) and analyzed the air samples for a wide variety of gas species and their isotopes. We find limited convective influence (1.4–5.2 m, depending on detection method) in the shallow firn, gravitational enrichment of heavy species throughout the diffusive column in general agreement with theoretical expectations, a ~10 m thick lock-in zone beginning at ~67 m, and a total firn thickness consistent with predictions of Kaspers et al. (2004). Our modeling work shows that the air has an age spread (spectral width) of 4.8 yr for CO<sub>2</sub> at the firn-ice transition. We also find that advection of firn air due to the 22 cm yr<sup>−1</sup> ice-equivalent accumulation rate has a minor impact on firn air composition, causing changes that are comparable to other modeling uncertainties and intrinsic sample variability. Furthermore, estimates of Δage (the gas age/ice age difference) at WAIS-D appear to be largely unaffected by bubble closure above the lock-in zone. Within the lock-in zone, small gas species and their isotopes show evidence of size-dependent fractionation due to permeation through the ice lattice with a size threshold of 0.36 nm, as at other sites. We also see an unequivocal and unprecedented signal of oxygen isotope fractionation within the lock-in zone, which we interpret as the mass-dependent expression of a size-dependent fractionation process

Gridded global surface ozone metrics for atmospheric chemistry model evaluation

The concentration of ozone at the Earth's surface is measured at many locations across the globe for the purposes of air quality monitoring and atmospheric chemistry research. We have brought together all publicly available surface ozone observations from online databases from the modern era to build a consistent data set for the evaluation of chemical transport and chemistry-climate (Earth System) models for projects such as the Chemistry-Climate Model Initiative and Aer-Chem-MIP. From a total data set of approximately 6600 sites and 500 million hourly observations from 1971-2015, approximately 2200 sites and 200 million hourly observations pass screening as high-quality sites in regionally representative locations that are appropriate for use in global model evaluation. There is generally good data volume since the start of air quality monitoring networks in 1990 through 2013. Ozone observations are biased heavily toward North America and Europe with sparse coverage over the rest of the globe. This data set is made available for the purposes of model evaluation as a set of gridded metrics intended to describe the distribution of ozone concentrations on monthly and annual timescales. Metrics include the moments of the distribution, percentiles, maximum daily 8-hour average (MDA8), sum of means over 35 ppb (daily maximum 8-h; SOMO35), accumulated ozone exposure above a threshold of 40 ppbv (AOT40), and metrics related to air quality regulatory thresholds. Gridded data sets are stored as netCDF-4 files and are available to download from the British Atmospheric Data Centre (doi:10.5285/08fbe63d-fa6d-4a7a-b952-5932e3ab0452). We provide recommendations to the ozone measurement community regarding improving metadata reporting to simplify ongoing and future efforts in working with ozone data from disparate networks in a consistent manner

Atmospheric Input and Seasonal Inventory of Dissolved Iron in the Sargasso Sea: Implications for Iron Dynamics in Surface Waters of the Subtropical Ocean

Constraining the role of dust deposition in regulating the concentration of the essential micronutrient iron in surface ocean waters requires knowledge of the flux of seawater-soluble iron in aerosols and the replacement time of dissolved iron (DFe) in the euphotic zone. Here we estimate these quantities using seasonally resolved DFe data from the Bermuda Atlantic Time-series Study region and weekly-scale measurements of iron in aerosols and rain from Bermuda during 2019. In response to seasonal changes in vertical mixing, primary production and dust deposition, surface DFe concentrations vary from ∼0.2 nM in early spring to \u3e1 nM in late summer, with DFe inventories ranging from ∼30 to ∼80 μmol/m2, respectively, over the upper 200 m. Assuming the upper ocean approximates steady state for DFe on an annual basis, our aerosol and rainwater data require a mean euphotic-zone residence time of ∼0.8–1.9 years for DFe with respect to aeolian input

Efficacy and safety of the anti-IL-12/23 p40 monoclonal antibody, ustekinumab, in patients with active psoriatic arthritis despite conventional non-biological and biological anti-tumour necrosis factor therapy: 6-month and 1-year results of the phase 3, multicentre, double-blind, placebo-controlled, randomised PSUMMIT 2 trial

Objective: Assess ustekinumab efficacy (week 24/week 52) and safety (week 16/week 24/week 60) in patients with active psoriatic arthritis (PsA) despite treatment with conventional and/or biological anti-tumour necrosis factor (TNF) agents. Methods: In this phase 3, multicentre, placebo-controlled trial, 312 adults with active PsA were randomised (stratified by site, weight (≤100 kg/>100 kg), methotrexate use) to ustekinumab 45 mg or 90 mg at week 0, week 4, q12 weeks or placebo at week 0, week 4, week 16 and crossover to ustekinumab 45 mg at week 24, week 28 and week 40. At week 16, patients with <5% improvement in tender/swollen joint counts entered blinded early escape (placebo→45 mg, 45 mg→90 mg, 90 mg→90 mg). The primary endpoint was ≥20% improvement in American College of Rheumatology (ACR20) criteria at week 24. Secondary endpoints included week 24 Health Assessment Questionnaire-Disability Index (HAQ-DI) improvement, ACR50, ACR70 and ≥75% improvement in Psoriasis Area and Severity Index (PASI75). Efficacy was assessed in all patients, anti-TNF-naïve (n=132) patients and anti-TNF-experienced (n=180) patients. Results: More ustekinumab-treated (43.8% combined) than placebo-treated (20.2%) patients achieved ACR20 at week 24 (p<0.001). Significant treatment differences were observed for week 24 HAQ-DI improvement (p<0.001), ACR50 (p≤0.05) and PASI75 (p<0.001); all benefits were sustained through week 52. Among patients previously treated with ≥1 TNF inhibitor, sustained ustekinumab efficacy was also observed (week 24 combined vs placebo: ACR20 35.6% vs 14.5%, PASI75 47.1% vs 2.0%, median HAQ-DI change −0.13 vs 0.0; week 52 ustekinumab-treated: ACR20 38.9%, PASI75 43.4%, median HAQ-DI change −0.13). No unexpected adverse events were observed through week 60. Conclusions: The interleukin-12/23 inhibitor ustekinumab (45/90 mg q12 weeks) yielded significant and sustained improvements in PsA signs/symptoms in a diverse population of patients with active PsA, including anti-TNF-experienced PsA patients