The impact of bath gas composition on the calibration of photoacoustic spectrometers with ozone at discrete visible wavelengths spanning the Chappuis band

This is the author accepted manuscript. The final version is available from EGU via the DOI in this record.For data related to this paper, please contact Michael I. Cotterell (or Justin M. LangridgePhotoacoustic spectroscopy is a sensitive in situ technique for measuring the absorption coefficient for gas and aerosol samples. Photoacoustic spectrometer (PAS) instruments require accurate calibration by comparing the measured photoacoustic response with a known level of absorption for a calibrant. Ozone is a common calibrant of PAS instruments, yet recent work by Bluvshtein et al. (2017) has cast uncertainty on the validity of ozone as a calibrant at a wavelength of 405 nm. Moreover, Fischer and Smith (2018) demonstrate that a low O2 mass fraction in the bath gas can bias the measured PAS calibration coefficient to lower values for wavelengths in the range 532–780 nm. In this contribution, we present PAS sensitivity measurements at wavelengths of 405, 514 and 658 nm using ozone-based calibrations with variation in the relative concentrations of O2 and N2 bath gases. We find excellent agreement with the results of Fischer and Smith at the 658 nm wavelength. However, the PAS sensitivity decreases significantly as the bath gas composition tends to pure oxygen for wavelengths of 405 and 514 nm, which cannot be rationalised using arguments presented in previous studies. To address this, we develop a model to describe the variation in PAS sensitivity with both wavelength and bath gas composition that considers Chappuis band photodynamics and recognises that the photoexcitation of O3 leads rapidly to the photodissociation products O(3P) and O2(X, v > 0). We show that the rates of two processes are required to model the PAS sensitivity correctly. The first process involves the formation of vibrationally excited O3(X˜) through the reaction of the nascent O(3P) with bath gas O2. The second process involves the quenching of vibrational energy from the nascent O2(X, v > 0) to translational modes of the bath gas. Both of these processes proceed at different rates in collisions with N2 or O2 bath gas species. Importantly, we show that the PAS sensitivity is optimised for our PAS instruments when the ozone-based calibration is performed in a bath gas with a similar composition to ambient air and conclude that our methods for measuring aerosol absorption using an ozone-calibrated PAS are accurate and without detectable bias. We emphasise that the dependence of PAS sensitivity on bath gas composition is wavelength-dependent, and we recommend strongly that researchers characterise the optimal bath gas composition for their particular instrument.Analytical Chemistry Trust FundResearch Council on Norwa

On the accuracy of aerosol photoacoustic spectrometer calibrations using absorption by ozone

This is the final version of the article. Available from EGU via the DOI in this record.In recent years, photoacoustic spectroscopy has emerged as an invaluable tool for the accurate measurement of light absorption by atmospheric aerosol. Photoacoustic instruments require calibration, which can be achieved by measuring the photoacoustic signal generated by known quantities of gaseous ozone. Recent work has questioned the validity of this approach at short visible wavelengths (404 nm), indicating systematic calibration errors of the order of a factor of 2. We revisit this result and test the validity of the ozone calibration method using a suite of multipass photoacoustic cells operating at wavelengths 405, 514 and 658 nm. Using aerosolised nigrosin with mobility-selected diameters in the range 250-425 nm, we demonstrate excellent agreement between measured and modelled ensemble absorption cross sections at all wavelengths, thus demonstrating the validity of the ozone-based calibration method for aerosol photoacoustic spectroscopy at visible wavelengths.This work was funded by the Met Office. In addition, Nicholas W. Davies was supported by a NERC/Met Office Industrial Case studentship (ref 640052003). Michael I. Cotterell was supported by a Tom West Analytical Chemistry Trust Fund Fellowship. Michael I. Cotterell and Jim M. Haywood were supported by the CLARIFY-2017 Natural Environment Research Council funded proposal (NE/L013797/1)

Optimizing the Performance of Aerosol Photoacoustic Cells using a Finite Element Model. Part 2: Application to a Two-Resonator Cell

This is the author accepted manuscript. The final version is available from Taylor & Francis via the DOI in this recordData availability: For data related to this paper, please contact Michael I. Cotterell ([email protected]).Photoacoustic spectroscopy (PAS) measures aerosol absorption in a non-contact manner, providing accurate absorption measurements that are needed to improve aerosol optical property representations in climate models. Central to PAS is resonant amplification of the acoustic pressure wave generated from laser-heated aerosol transferring heat to surrounding gas by a photoacoustic cell. Although this cell amplifies pressure sources from aerosol absorption (signal), it also amplifies noise and background sources. It is important to maximise the cell signal-to-background ratio (SBR) for sensitive absorption measurements. Many researchers have adopted the two-resonator cell design described by Lack et al. (2006). We show that the uncertainty in PAS measurements of aerosol absorption using this two-resonator cell is significantly degraded by its large sensitivity to background contributions from laser scattering and absorption at the cell windows. In Part 1, we described the use of a finite element method (FEM) to predict cell acoustic properties, validated this framework by comparing model predictions to measurements, and used FEM to test various strategies applied commonly to single-resonator cell optimisation. In this second part, we apply FEM to understand the excitation of resonant modes of the two-resonator cell, with comparison measurements demonstrating accurate predictions of acoustic response. We perform geometry optimisation studies to maximise the SBR and demonstrate that the laser-window interaction background is reduced to undetectable levels for an optimal cell. This optimised two-resonator cell will improve the sensitivity and accuracy of future aerosol absorption measurements.Defence Science and Technology Laboratory (DSTL)Royal Society of ChemistryAnalytical Chemistry Trust FundNatural Environment Research Council (NERC

Sensitivity and accuracy of refractive index retrievals from measured extinction and absorption cross sections for mobility-selected internally mixed light absorbing aerosols

This is the final version. Available on open access from Taylor & Francis via the DOI in this record. Data availability: For data related to this article, please contact Michael I. Cotterell ([email protected]).Aerosol refractive index (RI) is related to particle composition and density, is used in optical spectroscopy studies to probe aerosol physiochemical properties during chemical reactions and gas-particle partitioning, and is important in atmospheric physics. Indeed, aerosol radiative forcing calculations require accurate descriptions of the real (n) and imaginary (k) RI components and their dependence on wavelength, humidity and particle mixing state. Using cavity ring-down spectroscopy (CRDS) and photoacoustic spectroscopy (PAS) to measure the extinction and absorption cross sections for mobility-selected aerosols is recognized as a good approach to retrieving n and k accurately. However, little work has assessed rigorously the sensitivity and accuracy of the retrieved values from this approach. This work investigates RI retrievals from CRDS- and PAS-measured optical properties for mobility-selected aerosols composed of ammonium sulfate (non-absorbing), nigrosin (strongly light absorbing) or a mixture of these two species. Importantly, we assess the sensitivity in our RI retrievals and then apply a Monte Carlo error propagation analysis to quantify the retrieval accuracy. Our Monte Carlo analysis is the first to account for the full range of uncertainties involved in RI retrievals from optical measurements on mobility-selected aerosol. We also report the first experimental validation of predictive RI mixing rules for non-aqueous internally mixed light absorbing aerosols by comparing mixing rule predictions with measurements for aerosol composed of internal mixtures of ammonium sulfate and nigrosin. The commonplace volume fraction mixing rule fails to predict refractive indices accurately and mixing rules with a physical basis must be used.Natural Environment Research Council (NERC

Photoacoustic Studies of Energy Transfer from Ozone Photoproducts to Bath Gases following Chappuis Band Photoexcitation

This is the final version. Available from the Royal Society of Chemistry via the DOI in this record.Photoacoustic spectroscopy (PAS) is a sensitive technique for the detection of trace gases and aerosols and measurements of their absorption coefficients. The accuracy of such measurements is often governed by the fidelity of the PAS instrument calibration. Gas samples laden with O3 of a known or independently measured absorption coefficient are a convenient and commonplace route to calibration of PAS instruments operating at visible wavelengths (λ), yet the accuracy of such calibrations remains unclear. Importantly, the photoacoustic detection of O3 in the Chappuis band (λ ∼ 400–700 nm) depends strongly on the timescales for energy transfer from the nascent photoproducts O(3P) and O2(X, v > 0) to translational motion of bath gas species. Significant uncertainties remain concerning the dependence of these timescales on both the sample pressure and the bath gas composition. Here, we demonstrate accurate characterisation of microphone response function dependencies on pressure using a speaker transducer to excite resonant acoustic modes of our photoacoustic cells. These corrections enable measurements of photoacoustic response amplitudes (also referred to as PAS sensitivities) and phase shifts with variation in static pressure and bath gas composition, at discrete visible wavelengths spanning the Chappuis band. We develop and fit a photochemical relaxation model to these measurements to retrieve the associated variations in the aforementioned relaxation timescales for O(3P) and O2(X, v > 0). These timescales enable a full assessment of the accuracy of PAS calibrations using O3-laden gas samples, dependent on the sample pressure, bath gas composition and PAS laser modulation frequency.Natural Environment Research Council (NERC)Natural Environment Research Council (NERC

Observation of absorbing aerosols above clouds over the south-east Atlantic Ocean from the geostationary satellite SEVIRI – Part 1: Method description and sensitivity

This is the final version. Available on open access from EGU via the DOI in this recordData availability: The data used for this study are available from the corresponding author, FP, upon reasonable request.High-temporal-resolution observations from satellites have a great potential for studying the impact of biomass burning aerosols and clouds over the south-east Atlantic Ocean (SEAO). This paper presents a method developed to simultaneously retrieve aerosol and cloud properties in aerosol above-cloud conditions from the geostationary instrument Meteosat Second Generation/Spinning Enhanced Visible and Infrared Imager (MSG/SEVIRI). The above-cloud aerosol optical thickness (AOT), the cloud optical thickness (COT) and the cloud droplet effective radius (CER) are derived from the spectral contrast and the magnitude of the signal measured in three channels in the visible to shortwave infrared region. The impact of the absorption from atmospheric gases on the satellite signal is corrected by applying transmittances calculated using the water vapour profiles from a Met Office forecast model. The sensitivity analysis shows that a 10 % error on the humidity profile leads to an 18.5 % bias on the above-cloud AOT, which highlights the importance of an accurate atmospheric correction scheme. In situ measurements from the CLARIFY-2017 airborne field campaign are used to constrain the aerosol size distribution and refractive index that is assumed for the aforementioned retrieval algorithm. The sensitivities in the retrieved AOT, COT and CER to the aerosol model assumptions are assessed. Between 09:00 and 15:00 UTC, an uncertainty of 40 % is estimated on the above-cloud AOT, which is dominated by the sensitivity of the retrieval to the single-scattering albedo. The absorption AOT is less sensitive to the aerosol assumptions with an uncertainty generally lower than 17 % between 09:00 and 15:00 UTC. Outside of that time range, as the scattering angle decreases, the sensitivity of the AOT and the absorption AOT to the aerosol model increases. The retrieved cloud properties are only weakly sensitive to the aerosol model assumptions throughout the day, with biases lower than 6 % on the COT and 3 % on the CER. The stability of the retrieval over time is analysed. For observations outside of the backscattering glory region, the time series of the aerosol and cloud properties are physically consistent, which confirms the ability of the retrieval to monitor the temporal evolution of aerosol above-cloud events over the SEAO.Research Council of NorwayNetB

Vertical variability of the properties of highly aged biomass burning aerosol transported over the southeast Atlantic during CLARIFY-2017

This is the final version. Available from European Geosciences Union via the DOI in this record. Airborne measurements are available from the Centre for Environmental Data Analysis (https://catalogue.ceda.ac.uk/uuid/38ab7089781a4560b067dd6c20af3769, Facility for Airborne Atmospheric Measurements et al., 2017).Seasonal biomass burning (BB) from June to October in central and southern Africa leads to absorbing aerosols being transported over the South Atlantic Ocean every year and contributes significantly to the regional climate forcing. The vertical distribution of submicron aerosols and their properties were characterized over the remote southeast Atlantic, using airborne in situ measurements made during the CLoud-Aerosol-Radiation Interactions and Forcing for Year 2017 (CLARIFY-2017) campaign. BB aerosols emitted from flaming-controlled fires were intensively observed in the region surrounding Ascension Island, in the marine boundary layer (MBL) and free troposphere (FT) up to 5 km. We show that the aerosols had undergone a significant ageing process during 7 d transit from source, as indicated by the highly oxidized organic aerosol. The highly aged BB aerosols in the far-field CLARIFY region were also especially rich in black carbon (BC), with relatively low single-scattering albedos (SSAs), compared with those from other BB transported regions. The column-weighted dry SSAs during CLARIFY were observed to be 0.85, 0.84 and 0.83 at 405, 550 and 658 nm respectively. We also found significant vertical variation in the dry SSA, as a function of relative chemical composition and size. The lowest SSA in the column was generally in the low FT layer around 2000 m altitude (averages: 0.82, 0.81 and 0.79 at 405, 550 and 658 nm). This finding is important since it means that BB aerosols across the southeast Atlantic region are more absorbing than currently represented in climate models, implying that the radiative forcing from BB may be more strongly positive than previously thought. Furthermore, in the FT, average SSAs at 405, 550 and 658 nm increased to 0.87, 0.86 and 0.85 with altitude up to 5 km. This was associated with an enhanced inorganic nitrate mass fraction and aerosol size, likely resulting from increased partitioning of ammonium nitrate to the existing particles at higher altitude with lower temperature and higher relative humidity. After entrainment into the boundary layer (BL), aerosols were generally smaller in dry size than in the FT and had a larger fraction of scattering material with resultant higher average dry SSA, mostly due to marine emissions and aerosol removal by drizzle. In the BL, the SSA decreased from the surface to the BL top, with the highest SSA in the column observed near the surface. Our results provide unique observational constraints on aerosol parameterizations used in modelling regional radiation interactions over this important region. We recommend that future work should consider the impact of this vertical variability on climate models.Natural Environment Research Council (NERC

Absorption closure in highly aged biomass burning smoke

This is the final version. Available from Copernicus Publications via the DOI in this record. Data availability. Airborne measurements are available from the Centre for Environmental Data Analysis (https://catalogue.ceda.ac.uk/uuid/38ab7089781a4560b067dd6c20af3769, Facility for Airborne Atmospheric Measurements et al., 2017).The optical properties of black carbon (BC) are a major source of uncertainty in regional and global climate studies. In the past, detailed investigation of BC absorption has been hampered by systematic biases in the measurement instrumentation. We present airborne measurements of aerosol absorption and black carbon microphysical properties in highly aged biomass burning plumes measured 4-8 d from their source over the southeast Atlantic Ocean during CLARIFY-2017, using a suite of novel photoacoustic spectrometers to measure aerosol absorption at 405, 514, and 655 nm and a single-particle soot photometer to measure the BC mass concentration, size, and mixing state. These measurements are of sufficient quality and detail to provide constraint on optical schemes used in climate models for the first time in biomass burning plumes far from their source-an aerosol environment that is one of the most important climatically. The average absorption Ångström exponents (AAE) were 1.38 over the wavelength range from 405 to 514 nm and 0.88 over the range from 514 to 655 nm, suggesting that brown carbon (BrC) contributed to 11±2 % of absorption at 405 nm. The effective organic aerosol (OA) mass absorption coefficient (MAC) was 0:31±0:09 m2 g-1 at 405 nm. The BC particles were universally thickly coated, and almost no externally mixed BC particles were detected. The average MAC of BC was 20 ± 4, 15 ± 3, and 12 ± 2 m2g-1 at wavelengths of 405, 514, and 655 nm respectively, with equivalent absorption enhancements of around 1:85 ± 0:45 at all three wavelengths, suggesting that the thick coatings acted as a lens that enhanced light absorption by the BC. We compared the measured MAC and AAE values with those calculated using several optical models and absorption parameterisations that took the measured BC mass and mixing state as inputs. Homogeneous grey-sphere Mie models were only able to replicate MAC for some low (real and imaginary) values of the complex BC refractive index (mBC) at the shortest wavelength, but they would have to use unrealistically low values of mBC to accurately replicate the AAE. A core-shell Mie model was able to generate good agreement for MAC in the green-red end of the visible spectrum for most values of mBC. However, there are no possible values of mBC that produce MAC values that agree with our observations at all three wavelengths, due to a wavelengthdependent underestimation of the MAC of the underlying BC core. Four semiempirical parameterisations from the literature were also tested, linking the BC mixing state to either the MAC or absorption enhancement. Two of these schemes produced results that agreed within a few percent with the measured MAC at all three wavelengths, and the AAE agreed well when discounting the effects of BrC. Our results uniquely demonstrate the validity of absorption parameterisations, as well as the failings of Mie calculations, in this highly aged environment. We recommend that future work should conduct similar analyses in environments where BC has different properties; future studies should also investigate the impact of implementing these types of schemes within climate models as well as the impact of developing equivalent schemes for light scattering by soot particles at visible wavelengths.Natural Environment Research Council (NERC

Observation of absorbing aerosols above clouds over the South-East Atlantic Ocean from the geostationary satellite SEVIRI – Part 2: Comparison with MODIS and aircraft measurements from the CLARIFY-2017 field campaign

This is the final version. Available on open access from Copernicus Publications via the DOI in this recordData availability: The SEVIRI data used for this study are available from the corresponding author, Fanny Peers, upon reasonable request. MODIS above-cloud data products are available from Kerry G. Meyer ([email protected]) upon request. The FAAM aircraft data are available at the Centre for Environmental Data Analysis from http://data.ceda.ac.uk/badc/faam/data/ (CEDA, 2021).To evaluate the SEVIRI retrieval for aerosols above clouds presented in Part 1 of the companion paper, the algorithm is applied over the south-east Atlantic Ocean during the CLARIFY-2017 field campaign period. The first step of our analysis compares the retrieved aerosol and cloud properties against equivalent products from the MODIS MOD06ACAERO retrieval (Meyer et al., 2015). While the correlation between the two satellite retrievals of the above-cloud aerosol optical thickness (AOT) is good (R = 0.78), the AOT retrieved by SEVIRI is 20.3 % smaller than that obtained from the MODIS retrieval. This difference in AOT is attributed mainly to the more absorbing aerosol model assumed for the SEVIRI retrieval compared to MODIS. The underlying cloud optical thickness (COT) derived from the two satellites is in good agreement (R = 0.90). The cloud droplet effective radius (CER) retrieved by SEVIRI is consistently smaller than MODIS by 2.2 µm, which is mainly caused by the use of different spectral bands of the satellite instruments. In the second part of our analysis, we compare the forecast water vapour profiles used for the SEVIRI atmospheric correction as well as the aforementioned aerosol and cloud products with in situ measurements made from the Facility for Airborne Atmospheric Measurements (FAAM) aircraft platform during the CLARIFY-2017 campaign. Around Ascension Island, the column water vapour used to correct the SEVIRI signal is overestimated by 3.1 mm in the forecast compared to that measured by dropsondes. However, the evidence suggests that the accuracy of the atmospheric correction improves closer to the African coast. Consistency is observed between the SEVIRI above-cloud AOT and in situ measurements (from cavity ring-down spectroscopy instruments) when the measured single-scattering albedo is close to that assumed in the retrieval algorithm. On the other hand, the satellite retrieval overestimates the AOT when the assumed aerosol model is not absorbing enough. Consistency is also found between the cloud properties retrieved by SEVIRI and the CER measured by a cloud droplet probe and the liquid water path derived from a microwave radiometer. Despite the instrumental limitations of the geostationary satellite, the consistency obtained between SEVIRI, MODIS and the aircraft measurements demonstrates the ability of the retrieval in providing additional information on the temporal evolution of the aerosol properties above clouds.Natural Environment Research Council (NERC)Research Council of Norwa

Overview: The CLoud-Aerosol-Radiation Interaction and Forcing: Year-2017 (CLARIFY-2017) measurement campaign

The representation of clouds, aerosols and cloud-aerosol-radiation impacts remain some of the largest uncertainties in climate change, limiting our ability to accurately reconstruct and predict future climate. The south-east Atlantic is a region where high atmospheric aerosol loadings and semi-permanent stratocumulus clouds are co-located, providing a natural laboratory for studying the full range of aerosol-radiation and aerosol-cloud interactions and their perturbations of the Earth’s radiation budget. While satellite measurements have provided some useful insights into aerosol-radiation and aerosol cloud interactions over the region, these observations do not have the spatial and temporal resolution, nor the required level of precision to allow for a process level assessment. Detailed measurements from high spatial and temporal resolution airborne atmospheric measurements in the region are very sparse, limiting their use in assessing the performance of aerosol modelling in numerical weather prediction and climate models. CLARIFY-2017 was a major consortium programme consisting of 5 principal UK universities with project partners from the UK Met Office and European and USA-based universities and research centres involved in the complementary ORACLES, LASIC and AEROCLO-sA projects. The aims of CLARIFY-2017 were four-fold; (1) to improve the representation and reduce uncertainty in model estimates of the direct, semi-direct and indirect radiative effect of absorbing biomass burning aerosols; (2) improve our knowledge and representation of the processes determining stratocumulus cloud microphysical and radiative properties and their transition to cumulus regimes; (3) challenge, validate and improve satellite retrievals of cloud and aerosol properties and their radiative impacts; (4) improve numerical models of cloud and aerosol and their impacts on radiation, weather and climate. This paper describes the modelling and measurement strategies central to the CLARIFY-2017 deployment of the FAAM BAe146 instrumented aircraft campaign, summarises the flight objectives and flight patterns, and highlights some key results from our initial analyses