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Utilising polyphenylene oxide for high exposure solar UVA dosimetry

A personal UV dosimeter that can quantitatively assess high exposure solar UVA exposures has been developed. The chemical polyphenylene oxide has been previously reported on its ability to measure high UVB exposures. This current research has found that polyphenylene oxide, cast in thin film form, is responsive to both the UVA and UVB parts of the solar spectrum. Further to this, the UVB wavelengths were filtered out with the use of mylar. This combined system responded to the UVA wavelengths only and underwent a change in optical absorbance as a result of UVA exposure. Preliminary results indicate that this UVA dosimeter saturates steadily when exposed to sunlight and can measure exposures of more than 20 MJ/m2 of solar UVA radiation with an uncertainty level of no more than ±5%.
Measurement of black carbon at Syowa station, Antarctica: seasonal variation, transport processes and pathways

Measurement of black carbon (BC) was carried out at Syowa station Antarctica (69° S, 39° E) from February 2004 until January 2007. The BC concentration at Syowa ranged from below detection to 176 ng m−3 during the measurements. Higher BC concentrations were observed mostly under strong wind (blizzard) conditions due to the approach of a cyclone and blocking event. The BC-rich air masses traveled from the lower troposphere of the Atlantic and Indian Oceans to Syowa (Antarctic coast). During the summer (November–February), the BC concentration showed a diurnal variation together with surface wind speed and increased in the katabatic wind from the Antarctic continent. Considering the low BC source strength in the Antarctic continent, the higher BC concentration in the continental air (katabatic wind) might be caused by long range transport of BC via the free troposphere from mid- and low- latitudes. The seasonal variation of BC at Syowa had a maximum in August, while at the other coastal stations (Halley, Neumayer, and Ferraz) and the continental station (Amundsen-Scott), the maximum occurred in October. This difference may result from different transport pathways and scavenging of BC by precipitation during the transport from the source regions. During the austral summer, long-range transport of BC via the free troposphere is likely to make an important contribution to the ambient BC concentration. The BC transport flux indicated that BC injection into the Antarctic region strongly depended on the frequency of storm (blizzard) conditions. The seasonal variation of BC transport flux increased by 290 mg m−2 month−1 in winter–spring when blizzards frequently occurred, whereas the flux decreased to lower than 50 mg m−2 month−1 in the summer with infrequent blizzards.
Observations of shallow convective clouds generated by solar heating of dark smoke plumes

The SEVIRI instrument on the Meteosat Second Generation satellite with both fine spatial and temporal resolution allows to detect and follow the dynamics of fast developing meteorological events like spreading smoke plumes and the lifecycles of convective clouds. Smoke plumes have the ability to change the atmospheric heat content due to absorption and reduced reflection of solar radiation. By these means they can trigger formation of shallow convective clouds at their edge. A heavy smoke plume emerging from burning Lebanese oil tanks and spreading over adjacent deserts on 17 July 2006 has been observed as an example of such an effect. This study suggests a physical explanation of the observed convection along the edge of the smoke plume, namely the strong thermal contrast resulting from solar heating of the smoke layer.
SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds

The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure poL (atm) and enthalpy of vaporization Δ Hvap (kJ mol-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log10poL,i (T)=∑kνk,ibk(T) where νk,i is the number of groups of type k, and bk (T) is the contribution to log10poL,i (T) by each group of type k. A zeroeth group is included that uses b0 (T) with ν0,i=1 for all i. A total of 30 structural groups are considered: molecular carbon, alkyl hydroxyl, aromatic hydroxyl, alkyl ether, alkyl ring ether, aromatic ether, aldehyde, ketone, carboxylic acid, ester, nitrate, nitro, alkyl amine (primary, secondary, and tertiary), aromatic amine, amide (primary, secondary, and tertiary), peroxide, hydroperoxide, peroxy acid, C=C, carbonylperoxynitrate, nitro-phenol, nitro-ester, aromatic rings, non-aromatic rings, C=C–C=O in a non-aromatic ring, and carbon on the acid-side of an amide. The T dependence in each of the bk (T) is assumed to follow b(T)=B1/T+B2+B3T+B4ln T. Values of the B coefficients are fit using an initial basis set of 272 compounds for which experimentally based functions po L,i=fi (T) are available. The range of vapor pressure considered spans fourteen orders of magnitude. The ability of the initially fitted B coefficients to predict poL values is examined using a test set of 184 compounds and a T range that is as wide as 273.15 to 393.15 K for some compounds. σFIT is defined as the average over all points of the absolute value of the difference between experimental and predicted values of log10poL,i (T). After consideration of σFIT for the test set, the initial basis set and test set compounds are combined, and the B coefficients re-optimized. For all compounds and temperatures, σFIT=0.34: on average, poL,i (T) values are predicted to within a factor of 2. Because d(log10 poL,i (T))d(1/T) is related to the enthalpy of vaporization ΔHvap,i, the fitted B provide predictions of ΔHvap,i based on structure.
Evaluation of the atmospheric transport in a GCM using radon measurements: sensitivity to cumulus convection parameterization

The radioactive species radon (222Rn) has long been used as a test tracer for the numerical simulation of large scale transport processes. In this study, radon transport experiments are carried out using an atmospheric GCM with a finite-difference dynamical core, the van Leer type FFSL advection algorithm, and two state-of-the-art cumulus convection parameterization schemes. Measurements of surface concentration and vertical distribution of radon collected from the literature are used as references in model evaluation. The simulated radon concentrations using both convection schemes turn out to be consistent with earlier studies with many other models. Comparison with measurements indicates that at the locations where significant seasonal variations are observed in reality, the model can reproduce both the monthly mean surface radon concentration and the annual cycle quite well. At those sites where the seasonal variation is not large, the model is able to give a correct magnitude of the annual mean. In East Asia, where radon simulations are rarely reported in the literature, detailed analysis shows that our results compare reasonably well with the observations. The most evident changes caused by the use of a different convection scheme are found in the vertical distribution of the tracer. The scheme associated with weaker upward transport gives higher radon concentration up to about 6 km above the surface, and lower values in higher altitudes. In the lower part of the atmosphere results from this scheme does not agree as well with the measurements as the other scheme. Differences from 6 km to the model top are even larger, although we are not yet able to tell which simulation is better due to the lack of observations at such high altitudes.
Modeling cosmogenic radionuclides 10Be and 7Be during the Maunder Minimum using the ECHAM5-HAM General Circulation Model

All existing 10Be records from Greenland and Antarctica show increasing concentrations during the Maunder Minimum period (MM), 1645–1715, when solar activity was very low and the climate was colder (little ice age). In detail, however, the 10Be records deviate from each other. We investigate to what extent climatic changes influence the 10Be measured in ice by modeling this period using the ECHAM5-HAM general circulation model. Production calculations show that during the MM the mean global 10Be production was higher by 32% than at present due to lower solar activity. Our modeling shows that the zonally averaged modeled 10Be deposition flux deviates by only ~8% from the average increase of 32%, indicating that climatic effects are much smaller than the production change. Due to increased stratospheric production, the 10Be content in the downward fluxes is larger during MM, leading to larger 10Be deposition fluxes in the subtropics, where stratosphere-troposphere exchange (STE) is strongest. In polar regions the effect is small. In Greenland the deposition change depends on latitude and altitude. In Antarctica the change is larger in the east than in the west. We use the 10Be/7Be ratio to study changes in STE. We find larger change between 20° N–40° N during spring, pointing to a stronger STE in the Northern Hemisphere during MM. In the Southern Hemisphere the change is small. These findings indicate that climate changes do influence the 10Be deposition fluxes, but not enough to significantly disturb the production signal. Climate-induced changes remain small, especially in polar regions.
Utilising shade to optimize UV exposure for vitamin D

Numerous studies have stated that humans need to utilise full sun radiation, at certain times of the day, to assist the body in synthesising the required levels of vitamin D3. The time needed to be spent in the full sun depends on a number of factors, for example, age, skin type, latitude, solar zenith angle. Current Australian guidelines suggest exposure to approximately 1/6 to 1/3 of a minimum erythemal dose (MED), depending on age, would be appropriate to provide adequate vitamin D3 levels. The aim of the study was to determine the exposure times to diffuse solar UV to receive exposures of 1/6 and 1/3 MED for a changing solar zenith angle in order to assess the possible role that diffuse UV (scattered radiation) may play in vitamin D3 effective UV exposures (UVD3). Diffuse and global erythemal UV measurements were conducted at five minute intervals over a twelve month period for a solar zenith angle range of 4° to 80° at a latitude of 27.6° S. For a diffuse UV exposure of 1/3 MED, solar zenith angles smaller than approximately 50° can be utilised for exposure times of less than 10 min. Spectral measurements showed that, for a solar zenith angle of 40°, the UVA (315–400 nm) in the diffuse component of the solar UV is reduced by approximately 62% compared to the UVA in the global UV, whereas UVD3 wavelengths are only reduced by approximately 43%. At certain latitudes, diffuse UV under shade may play an important role in providing the human body with adequate levels of UVD3 (290–315 nm) radiation without experiencing the high levels of UVA observed in full sun.
Variability of the total ozone trend over Europe for the period 1950–2004 derived from reconstructed data

The total ozone data over Europe are available for only few ground-based stations in the pre-satellite era disallowing examination of the spatial trend variability over the whole continent. A need of having gridded ozone data for a trend analysis and input to radiative transfer models stimulated a reconstruction of the daily ozone values since January 1950. Description of the reconstruction model and its validation were a subject of our previous paper. The data base used was built within the objectives of the COST action 726 "Long-term changes and climatology of UV radiation over Europe". Here we focus on trend analyses. The long-term variability of total ozone is discussed using results of a flexible trend model applied to the reconstructed total ozone data for the period 1950–2004. The trend pattern, which comprises both anthropogenic and "natural" component, is not a priori assumed but it comes from a smooth curve fit to the zonal monthly means and monthly grid values. The ozone long-term changes are calculated separately for cold (October–next year April) and warm (May–September) seasons. The confidence intervals for the estimated ozone changes are derived by the block bootstrapping. The statistically significant negative trends are found almost over the whole Europe only in the period 1985–1994. Negative trends up to −3% per decade appeared over small areas in earlier periods when the anthropogenic forcing on the ozone layer was weak . The statistically positive trends are found only during warm seasons 1995–2004 over Svalbard archipelago. The reduction of ozone level in 2004 relative to that before the satellite era is not dramatic, i.e., up to ~−5% and ~−3.5% in the cold and warm subperiod, respectively. Present ozone level is still depleted over many popular resorts in southern Europe and northern Africa. For high latitude regions the trend overturning could be inferred in last decade (1995–2004) as the ozone depleted areas are not found there in 2004 in spite of substantial ozone depletion in the period 1985–1994.
The role of ammonia in sulfuric acid ion induced nucleation

We have developed a new multi-step strategy for quantum chemical calculations on atmospherically relevant cluster structures that makes calculation for large clusters affordable with a good accuracy-to-computational effort ratio. We have applied this strategy to evaluate the relevance of ternary ion induced nucleation; we have also performed calculations for neutral ternary nucleation for comparison. The results for neutral ternary nucleation agree with previous results, and confirm the important role of ammonia in enhancing the growth of sulfuric acid clusters. On the other hand, we have found that ammonia does not enhance the growth of ionic sulfuric acid clusters. The results also confirm that ion-induced nucleation is a barrierless process at high altitudes, but at ground level there exists a barrier due to the presence of a local minimum on the free energy surface.
Adjoint inversion modeling of Asian dust emission using lidar observations

A four-dimensional variational (4D-Var) data assimilation system for a regional dust model (RAMS/CFORS-4DVAR; RC4) is applied to an adjoint inversion of a heavy dust event over eastern Asia during 20 March–4 April 2007. The vertical profiles of the dust extinction coefficients derived from NIES Lidar network are directly assimilated, with validation using observation data. Two experiments assess impacts of observation site selection: Experiment A uses five Japanese observation sites located downwind of dust source regions; Experiment B uses these and two other sites near source regions. Assimilation improves the modeled dust extinction coefficients. Experiment A and Experiment B assimilation results are mutually consistent, indicating that observations of Experiment A distributed over Japan can provide comprehensive information related to dust emission inversion. Time series data of dust AOT calculated using modeled and Lidar dust extinction coefficients improve the model results. At Seoul, Matsue, and Toyama, assimilation reduces the root mean square differences of dust AOT by 35–40%. However, at Beijing and Tsukuba, the RMS differences degrade because of fewer observations during the heavy dust event. Vertical profiles of the dust layer observed by CALIPSO are compared with assimilation results. The dense dust layer was trapped at potential temperatures (θ) of 280–300 K and was higher toward the north; the model reproduces those characteristics well. Latitudinal distributions of modeled dust AOT along the CALIPSO orbit paths agree well with those of CALIPSO dust AOT, OMI AI, and MODIS coarse-mode AOT, capturing the latitude at which AOTs and AI have high values. Assimilation results show increased dust emissions over the Gobi Desert and Mongolia; especially for 29–30 March, emission flux is about 10 times greater. Strong dust uplift fluxes over the Gobi Desert and Mongolia cause the heavy dust event. Total optimized dust emissions are 57.9 Tg (Experiment A; 57.8% larger than before assimilation) and 56.3 Tg (Experiment B; 53.4% larger).