Technical Note: Quantification of interferences of wet chemical HONO measurements under simulated polar conditions

International audienceIn the present pilot study, an optimized LOPAP instrument for the detection of nitrous acid (HONO) in the atmosphere (DL 0.2 pptV) was tested at the high alpine research station "Jungfraujoch" at 3580 m altitude in the Swiss Alps under conditions comparable to polar regions. HONO concentrations in the range <0.5?50 pptV with an average of 7.5 pptV were observed at the "Jungfraujoch". The diurnal profiles obtained exhibited clear maxima at noon and minima with very low concentration during the night supporting the proposed photochemical production of HONO. In good agreement with recent measurements at the South Pole, it was demonstrated, that interferences of chemical HONO instruments can significantly influence the measurements and lead to considerable overestimations, especially for low pollution level. Accordingly, the correction of interferences is of paramount importance for those instruments, which sample HONO on aqueous or humid surfaces

Technical Note: Quantification of interferences of wet chemical HONO LOPAP measurements under simulated polar conditions

In the present pilot study, an optimized LOPAP instrument (LOng Path Absorption Photometer) for the detection of nitrous acid (HONO) in the atmosphere (DL 0.2 pptV) was tested at the high alpine research station Jungfraujoch at 3580 m altitude in the Swiss Alps under conditions comparable to polar regions. HONO concentrations in the range &amp;lt;0.5–50 pptV with an average of 7.5 pptV were observed at the Jungfraujoch. The diurnal profiles obtained exhibited clear maxima at noon and minima with very low concentration during the night supporting the proposed photochemical production of HONO. In good agreement with recent measurements at the South Pole, it was demonstrated, that interferences of chemical HONO instruments can significantly influence the measurements and lead to considerable overestimations, especially for low pollution level. Accordingly, the active correction of interferences is of paramount importance for the determination of reliable HONO data

Characterisation of the photolytic HONO-source in the atmosphere simulation chamber SAPHIR

HONO formation has been proposed as an important OH radical source in simulation chambers for more than two decades. Besides the heterogeneous HONO formation by the dark reaction of NO₂ and adsorbed water, a photolytic source has been proposed to explain the elevated reactivity in simulation chamber experiments. However, the mechanism of the photolytic process is not well understood so far. As expected, production of HONO and NO_x was also observed inside the new atmospheric simulation chamber SAPHIR under solar irradiation. This photolytic HONO and NO_x formation was studied with a sensitive HONO instrument under reproducible controlled conditions at atmospheric concentrations of other trace gases. It is shown that the photolytic HONO source in the SAPHIR chamber is not caused by NO₂ reactions and that it is the only direct NO_y source under illuminated conditions. In addition, the photolysis of nitrate which was recently postulated for the observed photolytic HONO formation on snow, ground, and glass surfaces, can be excluded in the chamber. A photolytic HONO source at the surface of the chamber is proposed which is strongly dependent on humidity, on light intensity, and on temperature. An empirical function describes these dependencies and reproduces the observed HONO formation rates to within 10%. It is shown that the photolysis of HONO represents the dominant radical source in the SAPHIR chamber for typical tropospheric O₃/H₂O concentrations. For these conditions, the HONO concentrations inside SAPHIR are similar to recent observations in ambient air

Dead Sea evaporation by eddy covariance measurements vs. aerodynamic, energy budget, Priestley–Taylor, and Penman estimates

The Dead Sea is a terminal lake, located in an arid environment. Evaporation is the key component of the Dead Sea water budget and accounts for the main loss of water. So far, lake evaporation has been determined by indirect methods only and not measured directly. Consequently, the governing factors of evaporation are unknown. For the first time, long-term eddy covariance measurements were performed at the western Dead Sea shore for a period of 1 year by implementing a new concept for onshore lake evaporation measurements. To account for lake evaporation during offshore wind conditions, a robust and reliable multiple regression model was developed using the identified governing factors wind velocity and water vapour pressure deficit. An overall regression coefficient of 0.8 is achieved. The measurements show that the diurnal evaporation cycle is governed by three local wind systems: a lake breeze during daytime, strong downslope winds in the evening, and strong northerly along-valley flows during the night. After sunset, the strong winds cause half-hourly evaporation rates which are up to 100 % higher than during daytime. The median daily evaporation is 4.3 mm d−1 in July and 1.1 mm d−1 in December. The annual evaporation of the water surface at the measurement location was 994±88 mm a−1 from March 2014 until March 2015. Furthermore, the performance of indirect evaporation approaches was tested and compared to the measurements. The aerodynamic approach is applicable for sub-daily and multi-day calculations and attains correlation coefficients between 0.85 and 0.99. For the application of the Bowen ratio energy budget method and the Priestley–Taylor method, measurements of the heat storage term are inevitable on timescales up to 1 month. Otherwise strong seasonal biases occur. The Penman equation was adapted to calculate realistic evaporation, by using an empirically gained linear function for the heat storage term, achieving correlation coefficients between 0.92 and 0.97. In summary, this study introduces a new approach to measure lake evaporation with a station located at the shoreline, which is also transferable to other lakes. It provides the first directly measured Dead Sea evaporation rates as well as applicable methods for evaporation calculation. The first one enables us to further close the Dead Sea water budget, and the latter one enables us to facilitate water management in the region

Modelling chemistry in the nocturnal boundary layer above tropical rainforest and a generalised effective nocturnal ozone deposition velocity for sub-ppbv NOx conditions

Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O3], but relatively low observed [NO2]. It is shown that a one-dimensional (1-D) column model with simple O3 -NOx chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NOx] conditions (NOx <1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NOx and O3. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ significantly if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following day’s peak ozone concentration. However under medium to high [NOx] conditions (NOx > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate constants

Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo)

Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations ( ≈ 3 ppbv h-1) versus ozone production from peroxy radicals measured ( ≈ 1 ppbv h-1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO] increases beyond 7 ppbv due to the model underprediction of RO2 under these conditions

Intercomparison of four different in-situ techniques for ambient formaldehyde measurements in urban air

International audienceResults from an intercomparison of several currently used in-situ techniques for the measurement of atmospheric formaldehyde (CH2O) are presented. The measurements were carried out at Bresso, an urban site in the periphery of Milan (Italy) as part of the FORMAT-I field campaign. Eight instruments were employed by six independent research groups using four different techniques: Differential Optical Absorption Spectroscopy (DOAS), Fourier Transform Infra Red (FTIR) interferometry, the fluorimetric Hantzsch reaction technique (five instruments) and a chromatographic technique employing C18-DNPH-cartridges (2,4-dinitrophenylhydrazine). White type multi-reflection systems were employed for the optical techniques in order to avoid spatial CH2O gradients and ensure the sampling of nearly the same air mass by all instruments. Between 23 and 31 July 2002, up to 13 ppbv of CH2O were observed. The concentrations lay well above the detection limits of all instruments. The formaldehyde concentrations determined with DOAS, FTIR and the Hantzsch instruments were found to agree within ±11%, with the exception of one Hantzsch instrument, which gave systematically higher values. The two hour integrated samples by DNPH yielded up to 25% lower concentrations than the data of the continuously measuring instruments averaged over the same time period. The consistency between the DOAS and the Hantzsch method was better than during previous intercomparisons in ambient air with slopes of the regression line not significantly differing from one. The differences between the individual Hantzsch instruments could be attributed in part to the calibration standards used. Possible systematic errors of the methods are discussed

Development of a gas chromatography - mass spectrometry method for the determination of carbon disulfide in the atmosphere

[EN] Carbon disulfide (CS2), a relevant reduced sulfur compound in air, is well-known for its malodor and its significant effect on global atmospheric chemistry. Therefore, a reliable method for determining CS2 in atmospheric samples has been developed based on solid-phase sampling and gas chromatography-mass spectrometry (GC-MS). Two types of solid-phase sampling supports (Orbo-32 and SKC) and the elution with organic solvents - hexane and toluene - were evaluated for low-volume outdoor sampling. Recovery studies and the standard addition method were carried out to demonstrate the proper determination of CS2 in the absence of the influence of interferences such as ozone, hydrogen sulfide or water - important atmospheric pollutants. The proposed methodology was validated by performing experiments in a high-volume smog chamber and by comparison with two reference optical methods, Fourier Transform Infrared (FTIR) and Differential Optical Absorption Spectroscopy (DOAS) installed in these facilities. Satisfactory analytical parameters were reported: fast analysis, a correct repeatability of 6±1% and reproducibility of 14±3%, and low detection limits of 0.3-0.9pgm-3. Finally, the method was successfully applied to industrial samples near a pulp factory area, where a high correlation between industrial emissions and reported carbon disulfide concentrations were observed. © 2011 Elsevier B.V.The research leading to these results received funding from the Centro de Investigacion del Medio Ambiente (CIMA), Consejeria de Medio Ambiente, Gobierno de Cantabria. The Instituto Universitario CEAM-UMH is partly supported by Generalitat Valenciana, Fundacion Bancaja, and the projects GRACCIE (Consolider-Ingenio 2010) and FEEDBACKS (Prometeo - Generalitat Valenciana). We also acknowledged the European Community's Seventh Framework Program under the grant agreement no. 228335 (Eurochamp2), the Spanish Ministry of Science and Innovation, through INNPLANTA project: PCT-440000-2010-003 and the EUPHORE staff for their support in the chamber experiments. The authors also thank J.T.B. for his contribution.Borrás García, EM.; Ródenas, M.; Dieguez, J.; Pérez-García, M.; Lomba, R.; Lavin, J.; Tortajada-Genaro, LA. (2012). Development of a gas chromatography - mass spectrometry method for the determination of carbon disulfide in the atmosphere. Microchemical Journal. 101:37-42. https://doi.org/10.1016/j.microc.2011.10.002S374210

Dephosphorylation of YB-1 is Required for Nuclear Localisation During G2 Phase of the Cell Cycle

Elevated levels of nuclear Y-box binding protein 1 (YB-1) are linked to poor prognosis in cancer. It has been proposed that entry into the nucleus requires specific proteasomal cleavage. However, evidence for cleavage is contradictory and high YB-1 levels are prognostic regardless of cellular location. Here, using confocal microscopy and mass spectrometry, we find no evidence of specific proteolytic cleavage. Doxorubicin treatment, and the resultant G2 arrest, leads to a significant increase in the number of cells where YB-1 is not found in the cytoplasm, suggesting that its cellular localisation is variable during the cell cycle. Live cell imaging reveals that the location of YB-1 is linked to progression through the cell cycle. Primarily perinuclear during G1 and S phases, YB-1 enters the nucleus as cells transition through late G2/M and exits at the completion of mitosis. Atomistic modelling and molecular dynamics simulations show that dephosphorylation of YB-1 at serine residues 102, 165 and 176 increases the accessibility of the nuclear localisation signal (NLS). We propose that this conformational change facilitates nuclear entry during late G2/M. Thus, the phosphorylation status of YB-1 determines its cellular location

On the interpretation of in situ HONO observations via photochemical steady state

A substantial body of recent literature has shown that boundary layer HONO levels are higher than can be explained by simple, established gas-phase chemistry, to an extent that implies that additional HONO sources represent a major, or the dominant, precursor to OH radicals in such environments. This conclusion may be reached by analysis of point observations of (for example) OH, NO and HONO, alongside photochemical parameters; however both NO and HONO have non-negligible atmospheric lifetimes, so these approaches may be problematic if substantial spatial heterogeneity exists. We report a new dataset of HONO, NOx and HOx observations recorded at an urban background location, which support the existence of additional HONO sources as determined elsewhere. We qualitatively evaluate the possible impacts of local heterogeneity using a series of idealised numerical model simulations, building upon the work of Lee et al. (J. Geophys. Res., 2013, DOI: 10.1002/2013JD020341). The simulations illustrate the time required for photostationary state approaches to yield accurate results following substantial perturbations in the HOx/NOx/NOy chemistry, and the scope for bias to an inferred HONO source from NOx and VOC emissions in either a positive or negative sense, depending upon the air mass age following emission. To assess the extent to which these impacts may be present in actual measurements, we present exploratory spatially resolved measurements of HONO and NOx abundance obtained using a mobile instrumented laboratory. Measurements of the spatial variability of HONO in urban, suburban and rural environments show pronounced changes in abundance are found in proximity to major roads within urban areas, indicating that photo-stationary steady state (PSS) analyses in such areas are likely to be problematic. The measurements also show areas of very homogeneous HONO and NOx abundance in rural, and some suburban, regions, where the PSS approach is likely to be valid. Implications for future exploration of HONO production mechanisms are discussed