Items

Advanced search

Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.
Persistence of ozone anomalies in the Arctic stratospheric vortex in autumn

Dynamical processes during the formation phase of the Arctic stratospheric vortex in autumn (from September to December) can introduce considerable interannual variability in the amount of ozone that is incorporated into the vortex. Chemistry in autumn tends to remove part of this variability because ozone relaxes towards equilibrium. As a quantitative measure of how important dynamical variability during vortex formation is for the winter ozone abundances above the Arctic we analyze which fraction of an ozone anomaly induced during vortex formation persists until early winter (3 January). The work is based on the Lagrangian Chemistry Transport Model ATLAS. In a case study, model runs for the winter 1999–2000 are used to assess the fate of an ozone anomaly artificially introduced during the vortex formation phase on 16 September. In addition, runs with reduced resolution explore the sensitivity of the results to interannual changes in transport, mixing, temperatures and NOx. The runs provide information about the persistence of the induced ozone anomaly as a function of time, potential temperature and latitude. The induced ozone anomaly survives longer inside the polar vortex than outside the vortex. Half of the initial perturbation survives until 3 January at 550 K inside the polar vortex, with a rapid fall off towards higher levels, mainly due to NOx induced chemistry. Above 750 K the signal falls to values below 0.5%. Hence, dynamically induced ozone variability from the early vortex formation phase cannot significantly contribute to early winter variability above 750 K. At lower levels increasingly larger fractions of the initial perturbation survive, reaching 90% at 450 K. In this vertical range dynamical processes during the vortex formation phase are crucial for the ozone abundance in early winter.
Renewed methane increase for five years (2007–2011) observed by solar FTIR spectrometry

Trends of column-averaged methane for the time period (1996, Sep 2011) are derived from the mid-infrared (mid-IR) solar FTIR time series at the Zugspitze (47.42° N, 10.98° E, 2964 m a.s.l.) and Garmisch (47.48° N, 11.06° E, 743 m a.s.l.). Trend analysis comprises a fit to the de-seasonalized time series along with bootstrap resampling for quantifying trend uncertainties. We find a positive trend during [1996, 1998] of 9.0 [3.2, 14.7] ppb yr−1 for Zugspitze (95% confidence interval), an insignificant growth during [1999, mid 2006] of 0.8 [−0.1, 1.7] ppb yr−1 (Zugspitze), and a significant renewed increase during [mid 2006, Sep 2011] of 5.1 [4.2, 6.0] ppb yr−1 for Garmisch, which is in agreement with 4.8 [3.8, 5.9] ppb yr−1 for Zugspitze. The agreement of methane trends at the two closely neighboring FTIR sites Zugspitze and Garmisch within the uncertainties indicates a good station-to-station consistency as a basis for future trend analyses by the ground-based mid-IR FTIR network on the global scale. Furthermore, the Zugspitze FTIR trend for the time interval [Jul 2006, Jun 2009] is found to agree with the trend derived from SCIAMACHY (WFM-DOAS v2.0.2) data within the 95% confidence intervals. In case a 1000-km pixel selection radius around the Zugspitze is used, the confidence interval is narrower for the FTIR trend (6.9 [4.2, 9.5] ppb yr−1) compared to SCIAMACHY (7.1 [5.1, 8.6] ppb yr−1). If, however, a loosened pixel selection is used (≈1000-km half-width latitudinal band), the SCIAMACHY trend significance interval is narrower (6.8 [5.1, 8.6] ppb yr−1) compared to Zugspitze FTIR (5.7 [3.0, 8.3] ppb yr−1). While earlier studies using surface network data revealed changes of 8.0 ± 0.6 ppb in 2007, 6.4 ± 0.6 ppb in 2008, and 4.7 ± 0.6 ppb in 2009 (Dlugokencky et al., 2011), our updated result proves that the renewed methane increase meanwhile has been persisting for >5 years [mid 2006, Sep 2011]. This is either the longest and largest positive trend anomaly since the beginning of systematic observations more than 25 years ago or the onset of a new period of strongly increasing CH4 levels in the atmosphere. Several scenarios have been developed to explain the persistent increase observed, mainly invoking an increase in emissions from natural wetlands, an increase in fossil fuel-related emissions or a decrease in OH concentrations. However, more work is needed to fully attribute this increase to a particular source or sink.
Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH) had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals resulted in a very distinct fractionation factor of α34 = 1.085±0.013. The fractionation factors measured in this study will be particularly useful in combination with field and modelling studies to understand the role of surface oxidation on clay minerals and aqueous oxidation by mineral dust and its leachate in global and regional sulfur cycles.
Comment on "Tropospheric temperature response to stratospheric ozone recovery in the 21st century" by Hu et al. (2011)

Stratospheric ozone recovery is expected to figure prominently in twenty-first century climate change. In a recent paper, Hu et al. (2011) argue that one impact of ozone recovery will be to enhance the warming of the surface-troposphere system produced by increases in well-mixed greenhouse gases. Furthermore, this enhanced warming would be strongest in the Northern Hemisphere, which is surprising since previous studies have consistently shown the effects of stratospheric ozone changes to be most pronounced in the Southern Hemisphere. Hu et al. (2011) base their claims largely on differences in the simulated temperature change between two groups of CMIP3 (Coupled Model Intercomparison Project 3) climate models, one group which included stratospheric ozone recovery in its twenty-first century simulations and a second group which did not. Both groups of models were forced with the same increases in well-mixed greenhouse gases according to the A1B emissions scenario. In the current work, we compare the surface temperature responses of the same two groups of models in a different experiment in which atmospheric CO2 was increased by 1% per year until doubling. We find remarkably similar differences in the simulated surface temperature change between the two sets of models as Hu et al. (2011) found for the A1B experiment, suggesting that the enhanced warming which they attribute to stratospheric ozone recovery is actually a reflection of different responses of the two model groups to greenhouse gas forcing.
Highly time-resolved chemical characterization of atmospheric fine particles during 2010 Shanghai World Expo

Shanghai, with a population of over 20 million, is the largest mega-city in China. Rapidly increasing industrial and metropolitan emissions have deteriorated its air quality in the past decades, with fine particle pollution as one of the major issues. However, systematic characterization of atmospheric fine particles with advanced measurement techniques has been very scarce in Shanghai. During 2010 Shanghai World Expo, we deployed a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a single particle soot photometer (SP2) in urban Shanghai between 15 May and 10 June 2010 to measure fine particles with a high time resolution. The 4-min resolution PM1 mass concentration ranged from 5.5 to 155 μg m−3, with an average of 29.2 μg m−3. On average, sulfate and organic matter (OM) were the most abundant PM1 components, accounting for 33.3 and 28.7% of the total mass, respectively, while the fraction of nitrate showed an increasing trend with the increasing PM1 loading, indicating the photochemical nature of high fine particle pollution in Shanghai. Taking advantage of HR-ToF-AMS and SP2, OM was found to have an average OM/OC ratio (organic matter mass/organic carbon mass) of 1.55 and black carbon (BC) had an average number fraction of internally mixed BC of 41.2%. Positive matrix factorization (PMF) analysis on the high resolution organic mass spectral dataset identified a hydrocarbon-like (HOA), a semi-volatile oxygenated (SV-OOA), and a low-volatility oxygenated (LV-OOA) organic aerosol component, which on average accounted for 24.0, 46.8, and 29.2% of the total organic mass, respectively. The diurnal patterns of them with interesting time delay possibly implied a photochemical oxidizing process from HOA (and/or its concurrently emitted gaseous organic pollutants) to SV-OOA to LV-OOA. Back trajectory analysis indicated that the northwesterly continental air mass represented the most severe pollutant regional transport condition with the highest nitrate and SV-OOA fractions. In addition, the results in Shanghai were compared with similar measurements performed recently in other mega-cities in the world.
Iodine monoxide in the north subtropical free troposphere

Iodine monoxide (IO) differential slant column densities (DSCD) have been retrieved from a new multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument deployed at the Izaña subtropical observatory as part of the Network for the Detection of Atmospheric Composition Change (NDACC) programme. The station is located at 2370 m a.s.l., well above the trade wind inversion that limits the top of the marine boundary layer, and hence is representative of the free troposphere. We report daily observations from May to August 2010 at different viewing angles. During this period, the spectral signature of IO was unequivocally detected on every day of measurement. A mean IO DSCD of 1.52×1013 molecules cm−2 was observed at the 5° instrument elevation angle (IEA) on clear days using a single zenith reference for the reported period, with a day-to-day variability of 33% at one standard deviation. Based on the simulation of the DSCDs using radiative transfer calculations with five different hypothesized IO profiles, the IO mixing ratio is estimated to range between 0.2 and 0.4 pptv in the free troposphere. Episodes of Saharan dust outbreaks were also observed, with large increases in the DSCDs at higher IEA, suggesting an enhancement of IO inside the dust cloud.
A parameterization of low visibilities for hazy days in the North China Plain

Visibility degradation is a pervasive and urgent environmental problem in China. The occurrence of low visibility events is frequent in the North China Plain, where the aerosol loading is quite high and aerosols are strongly hygroscopic. A parameterization of light extinction (Kex) for low visibilities on hazy days is proposed in this paper, based on visibility, relative humidity (RH), aerosol hygroscopic growth factors and particle number size distributions measured during the Haze in China (HaChi) Project. Observational results show that a high aerosol volume concentration is responsible for low visibility at RH <90%; while for RH >90%, decrease of visibility is mainly influenced by the increase of RH. The parameterization of Kex is developed on the basis of aerosol volume concentrations and RH, taking into accounts the sensitivity of visibility to the two factors and the availability of corresponding data. The extinction coefficients calculated with the parameterization schemes agree well with the directly measured values.
Global stratospheric hydrogen peroxide distribution from MIPAS-Envisat full resolution spectra compared to KASIMA model results

MIPAS-ENVISAT full resolution spectra were analyzed to obtain a global distribution of hydrogen peroxide (H2O2) in the stratosphere. H2O2 acts as reservoir gas for the HOx family (= H+OH+HO2) and thus, observations of H2O2 provide a better understanding of the HOx chemistry in the atmosphere. A retrieval approach based on constrained least squares fitting was developed and applied to small dedicated spectral analysis windows with maximum H2O2 information and minimum contribution of interfering gases. Due to a low signal to noise ratio in the measured spectra single profiles cannot be used for scientific interpretation and about 100 profiles have to be averaged temporally or spatially. Our retrievals of H2O2 from MIPAS measurements provide meaningful results between approximately 20 and 60 km. A possible impact by the high uncertainty of the reaction rate constant for HO2 + HO2→H2O2 + O2 in our 3D-CTM KASIMA is discussed. We find best agreement between model and observations for applying rate constants according to Christensen et al. (2002) however, a mismatch in vertical profile shape remains. The observations were compared to the model results of KASIMA focusing on low to mid latitudes. Good agreement in spatial distribution and in temporal evolution was found. Highest vmr of H2O2 in the stratosphere were observed and modeled in low latitudes shortly after equinox at about 30 km. The modelled diurnal cycle with lowest vmr shortly after sunrise and highest vmr in the afternoon is confirmed by the MIPAS observations.
The impact of circulation patterns on regional transport pathways and air quality over Beijing and its surroundings

This study investigated the air pollution characteristics of synoptic-scale circulation in the Beijing megacity, and provided quantitative evaluation of the impacts of circulation patterns on air quality during the 2008 Beijing Summer Olympics. Nine weather circulation types (CTs) were objectively identified over the North China region during 2000–2009, using obliquely rotated T-mode principal component analysis (PCA). The resulting CTs were examined in relation to the local meteorology, regional transport pathways, and air quality parameters, respectively. The FLEXPART-WRF model was used to calculate 48-h backward plume trajectories for each CT. Each CT was characterized with distinct local meteorology and air mass origin. CT 1 (high pressure to the west with a strong pressure gradient) was characterized by a northwestern air mass origin, with the smallest local and southeasterly air mass sources, and CT 6 (high pressure to the northwest) had air mass sources mostly from the north and east. On the contrary, CTs 5, 8, and 9 (weak pressure field, high pressure to the east, and low pressure to the northwest, respectively) were characterized by southern and southeastern trajectories, which indicated a greater influence of high pollutant emission sources. In turn, poor air quality in Beijing (high loadings of PM10, BC, SO2, NO2, NOx, O3, AOD, and low visibility) was associated with these CTs. Good air quality in Beijing was associated with CTs 1 and 6. The average visibilities (with ±1σ) in Beijing for CTs 1 and 6 during 2000–2009 were 18.5 ± 8.3 km and 14.3 ± 8.5 km, respectively. In contrast, low visibility values of 6.0 ± 3.5 km, 6.6 ± 3.7 km, and 6.7 ± 3.6 km were found in CTs 5, 8, and 9, respectively. The mean concentrations of PM10 for CTs 1, 6, 5, 8, and 9 during 2005–2009 were 90.3 ± 76.3 μg m−3, 111.7 ± 89.6 μg m−3, 173.4 ± 105.8 μg m−3, 158.4 ± 90.0 μg m−3, and 151.2 ± 93.1 μg m−3, respectively. Analysis of the relationship between circulation pattern and air quality during the emission control period suggests that CTs are the primary drivers of day-to-day variations in pollutant concentrations over Beijing and its vicinity. During the Olympics period, the frequency of CT 6 was twice that of the mean in August from 2000 to 2009. This CT had northerly transport pathways and favorable meteorological conditions (e.g. frequent precipitation) for clean air during the Olympics. Assuming that relationships between CTs and air quality parameters in the same season are fixed in different years, the relative contributions of synoptic circulation to decreases in PM10, BC, SO2, NO2, NOx, CO, and horizontal light extinction during the Olympics were estimated as 19 ± 14%, 18 ± 13%, 41 ± 36%, 12 ± 7%, 10 ± 5%, 19 ± 11%, and 54 ± 25%, respectively.