Peroxy radicals in the summer free troposphere: seasonality and potential for heterogeneous loss

The sum of peroxy radicals (HO2+ΣiRiO2) and supporting trace gases were measured on the Jungfraujoch (3580 m a.s.l.) during the late summer of 2005. The period was marked by extended times of heavy snow which led to reduction in the observed peroxy radicals during the snowy periods that was greater than the concomitant reduction in j(O1D). In the limit a first order loss rate of 0.0063 s−1 can be derived for the peroxy radical loss in the snowy conditions that could be potentially ascribed to a heterogenous loss process. On snow free days photolysis of HCHO is shown to be a significant peroxy radical source. The seasonal trends of the peroxy radical concentrations have been mapped from the winter to summer transition in line with previous experiments. Net ozone production in late summer at the Jungfraujoch was net neutral to marginally ozone destructive. A value of 28±4 pptv is calculated for the ozone compensation point for the snow free days.ISSN:1680-7375ISSN:1680-736

Comparisons between SCIAMACHY atmospheric CO₂ retrieved using (FSI) WFM-DOAS to ground based FTIR data and the TM3 chemistry transport model

International audienceAtmospheric CO2 concentrations, retrieved from spectral measurements made in the near infrared (NIR) by the SCIAMACHY instrument, using Full Spectral Initiation Weighting Function Modified Differential Optical Absorption Spectroscopy (FSI WFM-DOAS), are compared to ground based Fourier Transform Infrared (FTIR) data and to the output from a global chemistry-transport model. Analysis of the FSI WFM-DOAS retrievals with respect to the ground based FTIR instrument, located at Egbert, Canada, show good agreement with an average negative bias of approximately ?4.0% with a standard deviation of ~3.0%. This bias which exhibits an apparent seasonal trend, is of unknown origin, though slight differences between the averaging kernels of the instruments and the limited temporal coverage of the FTIR data may be the cause. The relative scatter of the retrieved vertical column densities is comparable to the spread of the FTIR measurements themselves. Normalizing the CO2 columns using the surface pressure does not affect the magnitude of this bias although it slightly increases the scatter of the FSI data. Comparisons of the FSI retrievals to the TM3 global chemistry-transport model, performed over four selected Northern Hemisphere scenes show good agreement. The correlation, between the time series of the SCIAMACHY and model monthly scene averages, are ~0.7 or greater, demonstrating the ability of SCIAMACHY to detect seasonal changes in the CO2 distribution. The amplitude of the seasonal cycle, peak to peak, observed by SCIAMACHY however, is overestimated by a factor of 2?3, which cannot be explained. The yearly means detected by SCIAMACHY are within 2% of those of the model with the mean difference between the CO2 distributions also approximately 2.0%. Additionally, analysis of the retrieved CO2 distributions reveals structure not evident in the model fields which correlates well with land classification type. From these comparisons, the overall precision and bias of the CO2 columns retrieved by the FSI algorithm are estimated to be close to 1.0% and <4.0% respectively

The TOMCAT global chemical transport model v1.6: description of chemical mechanism and model evaluation

This paper documents the tropospheric chemical mechanism scheme used in the TOMCAT 3-D chemical transport model. The current scheme includes a more detailed representation of hydrocarbon chemistry than previously included in the model, with the inclusion of the emission and oxidation of ethene, propene, butane, toluene and monoterpenes. The model is evaluated against a range of surface, balloon, aircraft and satellite measurements. The model is generally able to capture the main spatial and seasonal features of high and low concentrations of carbon monoxide (CO), ozone (O3), volatile organic compounds (VOCs) and reactive nitrogen. However, model biases are found in some species, some of which are common to chemistry models and some that are specific to TOMCAT and warrant further investigation. The most notable of these biases are (1) a negative bias in Northern Hemisphere (NH) winter and spring CO and a positive bias in Southern Hemisphere (SH) CO throughout the year, (2) a positive bias in NH O3 in summer and a negative bias at high latitudes during SH winter and (3) a negative bias in NH winter C2 and C3 alkanes and alkenes. TOMCAT global mean tropospheric hydroxyl radical (OH) concentrations are higher than estimates inferred from observations of methyl chloroform but similar to, or lower than, multi-model mean concentrations reported in recent model intercomparison studies. TOMCAT shows peak OH concentrations in the tropical lower troposphere, unlike other models which show peak concentrations in the tropical upper troposphere. This is likely to affect the lifetime and transport of important trace gases and warrants further investigation

Everyday executive function and adaptive skills in children and adolescents with Autism Spectrum Disorder: Cross-sectional developmental trajectories

Background and aims: The development of Executive Function (EF) in Autism Spectrum Disorder (ASD) has been investigated using mainly performance-based EF measures. Less is known about the development of everyday EF skills. The present study aimed to identify the developmental patterns of everyday EF of children and adolescents with ASD compared to neurotypical controls. The association between EF and adaptive skills was also investigated. Methods: The present study used a cross-sectional developmental trajectory approach and data were collected from 57 children and adolescents with ASD, matched to 63 controls of the same age (7-15 years). Results: Results showed age-related performance declines in most everyday EF domains (e.g. inhibition, working memory, planning) in ASD, whereas for EF emotional control and shift, non-significant differences emerged across age in ASD. Everyday EF predicted adaptive skills over and above age and IQ, in participants overall. Conclusions and Implications: These results suggest that several everyday EF problems increase in adolescence in ASD and that these everyday EF developmental patterns deviate to a great extent from those of typical development. Shedding more light on the developmental course of all types of EF processes as well as their association with crucial social outcomes in ASD could contribute to a better theoretical understanding of the heterogeneity of the neurocognitive development in ASD

Peroxy radicals in the summer free troposphere: seasonality and potential for heterogeneous loss

The sum of peroxy radicals (HO&lt;sub&gt;2&lt;/sub&gt;+&amp;Sigma;&lt;sub&gt;&lt;i&gt;i&lt;/i&gt;&lt;/sub&gt;R&lt;sub&gt;&lt;i&gt;i&lt;/i&gt;&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;) and supporting trace gases were measured on the Jungfraujoch (3580 m a.s.l.) during the late summer of 2005. The period was marked by extended times of heavy snow which led to reduction in the observed peroxy radicals during the snowy periods that was greater than the concomitant reduction in &lt;i&gt;j&lt;/i&gt;(O&lt;sup&gt;1&lt;/sup&gt;D). In the limit a first order loss rate of 0.0063 s&lt;sup&gt;&amp;minus;1&lt;/sup&gt; can be derived for the peroxy radical loss in the snowy conditions that could be potentially ascribed to a heterogenous loss process. On snow free days photolysis of HCHO is shown to be a significant peroxy radical source. The seasonal trends of the peroxy radical concentrations have been mapped from the winter to summer transition in line with previous experiments. Net ozone production in late summer at the Jungfraujoch was net neutral to marginally ozone destructive. A value of 28&amp;plusmn;4 pptv is calculated for the ozone compensation point for the snow free days

Intercomparison of aircraft instruments on board the <i>C-130</i> and <i>Falcon 20</i> over southern Germany during EXPORT 2000

International audienceIn the summer 2000 Export aircraft campaign (European eXport of Precursors and Ozone by long-Range Transport), two comprehensively instrumented research aircraft measuring a variety of chemical species flew wing tip to wing tip for a period of one and a quarter hours. During this interval a comparison was undertaken of the measurements of nitrogen oxide (NO), odd nitrogen species (NOy), carbon monoxide (CO) and ozone (O3). The comparison was performed at two different flight levels, which provided a 10-fold variation in the concentrations of both NO (10 to 1000 parts per trillion by volume (pptv)) and NOy (200 to over 2500 pptv). Large peaks of NO and NOy observed from the Falcon 20, which were at first thought to be from the exhaust of the C-130, were also detected on the 4 channel NOx,y instrument aboard the C-130. These peaks were a good indication that both aircraft were in the same air mass and that the Falcon 20 was not in the exhaust plume of the C-130. Correlations and statistical analysis are presented between the instruments used on the two separate aircraft platforms. These were found to be in good agreement giving a high degree of correlation for the ambient air studied. Any deviations from the correlations are accounted for in the estimated inaccuracies of the instruments. These results help to establish that the instruments aboard the separate aircraft are reliably able to measure the corresponding chemical species in the range of conditions sampled and that data collected by both aircraft can be co-ordinated for purposes of interpretation

Seasonal dependence of peroxy radical concentrations at a northern hemisphere marine boundary layer site during summer and winter: evidence for photochemical activity in winter

International audiencePeroxy radicals (HO2+?RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer than winter (1.51±0.5 ppbv h?1 and 1.11±0.47 ppbv h?1 respectively) but summer shows more variability of (meteorological) conditions than winter. The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 min in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and the ability of winter to make oxidant. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state

Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter

Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state

Large and increasing methane emissions from eastern Amazonia derived from satellite data, 2010–2018

We use a global inverse model, satellite data and flask measurements to estimate methane (CH4) emissions from South America, Brazil and the basin of the Amazon River for the period 2010–2018. We find that emissions from Brazil have risen during this period, most quickly in the eastern Amazon basin, and that this is concurrent with increasing surface temperatures in this region. Brazilian CH4 emissions rose from 49.8 ± 5.4 Tg yr−1 in 2010–2013 to 55.6 ± 5.2 Tg yr−1 in 2014–2017, with the wet season of December–March having the largest positive trend in emissions. Amazon basin emissions grew from 41.7 ± 5.3 to 49.3 ± 5.1 Tg yr−1 during the same period. We derive no significant trend in regional emissions from fossil fuels during this period. We find that our posterior distribution of emissions within South America is significantly and consistently changed from our prior estimates, with the strongest emission sources being in the far north of the continent and to the south and south-east of the Amazon basin, at the mouth of the Amazon River and nearby marsh, swamp and mangrove regions. We derive particularly large emissions during the wet season of 2013/14, when flooding was prevalent over larger regions than normal within the Amazon basin. We compare our posterior CH4 mole fractions, derived from posterior fluxes, to independent observations of CH4 mole fraction taken at five lower- to mid-tropospheric vertical profiling sites over the Amazon and find that our posterior fluxes outperform prior fluxes at all locations. In particular the large emissions from the eastern Amazon basin are shown to be in good agreement with independent observations made at Santarém, a location which has long displayed higher mole fractions of atmospheric CH4 in contrast with other basin locations. We show that a bottom-up wetland flux model can match neither the variation in annual fluxes nor the positive trend in emissions produced by the inversion. Our results show that the Amazon alone was responsible for 24 ± 18 % of the total global increase in CH4 flux during the study period, and it may contribute further in future due to its sensitivity to temperature changes