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The Arctic winter 2010/11 was characterized by a persisting vortex with extremely cold temperatures in the lower stratosphere above northern Scandinavia leading to a strong activation of chlorine compounds (ClOx) like Cl, Cl2, ClO, ClOOCl, OClO, and HOCl which rapidly destroyed ozone when sunlight returned after winter solstice. MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and TELIS (Terahertz and submillimeter Limb Sounder) balloon measurements obtained in northern Sweden on 31 March 2011 inside the polar vortex have provided vertical profiles of inorganic and organic chlorine species as well as diurnal variations of ClO around sunrise over the whole altitude range in which chlorine is undergoing activation and deactivation. This flight was performed at the end of the winter during the last phase of ClOx deactivation. The complete inorganic and organic chlorine partitioning and budget in the stratosphere has been derived by combining MIPAS-B and TELIS simultaneously observed molecules. A total chlorine amount of 3.41 ± 0.30 ppbv is inferred from the measurements. This value is in line with previously carried out stratospheric observations confirming the slightly decreasing chlorine trend in the stratosphere. Observations are compared and discussed with the output of a multi-year simulation performed with the Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). The simulated stratospheric total chlorine amount is in accordance with the MIPAS-B/TELIS observation taking into account the fact that some chlorine source gases and very short lived species are not included in the model. [ABSTRACT FROM AUTHOR]

Arctic stratospheric ozone depletion is closely linked to the occurrence of low stratospheric temperatures. There are indications that cold winters in the Arctic stratosphere have been getting colder, raising the question if and to what extent a cooling of the Arctic stratosphere may continue into the future. We use meteorological reanalyses from the European Centre for Medium Range Weather Forecasts (ECMWF) ERA-Interim and NASA's Modern-Era Retrospective-Analysis for Research and Applications (MERRA) for the past 32 yr together with calculations of the chemistry-climate model (CCM) ECHAM/MESSy Atmospheric Chemistry (EMAC) and models from the Chemistry-Climate Model Validation (CCMVal) project to infer radiative and dynamical contributions to long-term Arctic stratospheric temperature changes. For the past three decades the reanalyses show a warming trend in winter and cooling trend in spring and summer, which agree well with trends from the Radiosonde Innovation Composite Homogeniza-tion (RICH) adjusted radiosonde data set. Changes in winter and spring are caused by a corresponding change of planetary wave activity with increases in winter and decreases in spring. During winter the increase of planetary wave activity is counteracted by a residual radiatively induced cooling. Stratospheric radiatively induced cooling is detected throughout all seasons, being highly significant in spring and summer. This means that for a given dynamical situation, according to ERA-Interim the annual mean temperature of the Arctic lower stratosphere has been cooling by -0.41 ± 0.ll K decade-1 at 50 hPa over the past 32yr. Calculations with state-of-the-art models from CCM Val and the EMAC model qualitatively reproduce the radiatively induced cooling for the past decades, but underestimate the amount of radiatively induced cooling deduced from reanalyses. There are indications that this discrepancy could be partly related to a possible underestimation of past Arctic ozone trends in the models. The models project a continued cooling of the Arctic stratosphere over the coming decades (2001-2049) that is for the annual mean about 40 % less than the modeled cooling for the past, due to the reduction of ozone depleting substances and the resulting ozone recovery. This projected cooling in turn could offset between 15 and 40 % of the Arctic ozone recovery. [ABSTRACT FROM AUTHOR]

Arctic stratospheric ozone depletion is closely linked to the occurrence of low stratospheric temperatures. There are indications that cold winters in the Arctic stratosphere have been getting colder, raising the question if and to what extent a cooling of the Arctic stratosphere may continue into the future. We use meteorological re-analyses from ERA-Interim for the past 32 yr together with calculations of the chemistry-climate model EMAC and CCM models from the CCMVal project to infer radiative and dynamical contributions to long-term Arctic stratospheric temperature changes. For the past three decades ERA-Interim shows a warming trend in winter and cooling trend in spring and summer. Changes in winter and spring are caused by a corresponding change of planetary wave activity with increases in winter and decreases in spring. During winter the increase of planetary wave activity is counteracted by a radiatively induced cooling. Stratospheric radiatively induced cooling is detected throughout all seasons being highly significant in spring and summer. This means that for a given dynamical situation, in ERA-Interim the annual mean temperature of the Arctic lower stratosphere has been cooling by -0.41±0.11 Kdecade-1 at 50 hPa over the past 32 yr. Calculations with state-of-the-art models from CCMVal and the EMAC model confirm the radiatively induced cooling for the past decades, but underestimate the amount of radiatively induced cooling deduced from ERA-Interim. EMAC predicts a continued annual radiatively induced cooling for the coming decades (2001-2049) of -0.15±0.06 Kdecade-1 where the projected increase of CO2 accounts for about 2/3 of the cooling effect. Expected decrease of stratospheric halogen loading and resulting ozone recovery in the future counteracts the cooling tendency due to increasing greenhouse gas concentrations and leads to a reduced future cooling trend compared to the past. CCMVal multi-model mean predicts a future annual mean radiatively induced cooling of -0.10±0.02 Kdecade-1 which is also smaller in the future than in the past. [ABSTRACT FROM AUTHOR]

The winter 2009/2010 was characterized by a strong Arctic vortex with extremely cold mid-winter temperatures in the lower stratosphere associated with an intense activation of reactive chlorine compounds (ClOx). In order to assess the capacities of state-of-the-art chemistry models to predict polar stratospheric chemistry, stratospheric limb emission spectra were recorded during a flight of the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 24 January 2010 inside the Arctic vortex. Several fast limb sequences of spectra (in time steps of about 10min) were measured from nighttime photochemical equilibrium to local noon allowing the retrieval of chlorine- and nitrogen-containing species which change quickly their concentration around the terminator between night and day. Mixing ratios of species like ClO, NO2, and N2O5 show significant changes around sunrise, which are temporally delayed due to shadowing of the lower stratosphere by upper tropospheric and polar stratospheric clouds. ClO variations were derived for the first time from MIPAS-B spectra. Daytime ClO values of up to 1.6 ppbv are visible in a broad chlorine activated layer below 26 km correlated with low values (close to zero) of its reservoir species ClONO2. Observations are compared and discussed with calculations performed with the 3-dimensional Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). Mixing ratios of the species ClO, NO2, and N2O5 are fairly well reproduced by the model during photochemical equilibrium. However, since the model assumes cloudless illumination, simulated concentration changes around sunrise start earlier but less quickly compared to the observed variation of the species concentration. [ABSTRACT FROM AUTHOR]

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). 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. [ABSTRACT FROM AUTHOR]

Time series of total column abundances of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) were determined from ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC) and located between 80.05° N and 77.82° S. These measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Trends of HCl, ClONO2, and HF are calculated from both measurement and model time series data, with a focus on the time range 2000-2009. Their precision is estimated with the bootstrap resampling method. The sensitivity of the trend results with respect to the fitting function, the time of year chosen and time series length is investigated, as well as a bias due to the irregular sampling of the measurements. For the two chlorine species, a decrease is expected during this period because the emission of their prominent anthropogenic source gases (solvents, chlorofluorocarbons (CFCs)) was restricted by the Montreal Protocol 1987 and its amendments and adjustments. As most of the restricted source gases also contain fluorine, the HF total column abundance was also influenced by the above-mentioned regulations in the time period considered. The measurements and model results investigated here agree qualitatively on a decrease of the chlorine species by around -1% yr-1. The models simulate an increase of HF of around +1% yr-1. This also agrees well with most of the measurements, but some of the FTIR series in the Northern Hemisphere show a stabilisation or even a decrease in the last few years. In general, for all three gases, the measured trends vary more strongly with latitude and hemisphere than the modelled trends. Relative to the FTIR measurements, the models tend to underestimate the decreasing chlorine trends and to overestimate the fluorine increase in the Northern Hemisphere. [ABSTRACT FROM AUTHOR]

Trends of hydrogen chloride (HCl), chlorine nitrate (ClONO2) and hydrogen fluoride (HF) column abundances above Kiruna (Northern Sweden, 67.84° N, 20.41° E) derived from nearly 14 years (1996--2009) of measurement and model data are presented. The measurements have been performed with a Bruker 120HR (later Bruker 125HR) Fourier transform infrared (FTIR) spectrometer and the model used was KASIMA (KArlsruhe SImulation model of the Middle Atmosphere). To calculate the long-term trends, a linear function combined with an annual cycle was fitted to the data using a least squares method. The precision of the resulting trends was estimated with the so-called bootstrap resampling method. The relative trends were calculated on the basis of the linear fit result on 1 January 2000, 12:00UTC. For hydrogen fluoride, both model and measurements show a positive trend that seems to decrease in the last few years. This suggests a stabilisation of the HF total column abundance. For the summer data (August to November), the FTIR trend of (+1.25±0.28)%/yr agrees within errors with the KASIMA one of (+1.55±0.11)%/yr. The trends determined for HCl and ClONO2 are significantly negative over the time period considered here. This corresponds to the expectations because the emission of their precursors (chlorofluorocarbons and hydrochlorofluorocarbons) has been restricted in the Montreal Protocol in 1987 and its amendments and adjustments. The relative trend for ClONO2 from the FTIR measurements amounts to (-3.28±0.56)%/yr and the one for HCl to (-0.81±0.23)%/yr. KASIMA simulates a weaker decrease: For ClONO2 , the result is (-0.90±0.10)%/yr and for HCl (-0.17±0.06)%/yr. Part of the difference between measurement and model data can be explained by sampling and the stronger annual cycle indicated by the measurements. There is a factor of about four between the trends of HCl and ClONO2 above Kiruna for both measurement and model data. The absolute values of ClONO2 and HF calculated by KASIMA agree quite well with the FTIR measurements while KASIMA tends to underestimate the HCl column abundances. [ABSTRACT FROM AUTHOR]

Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively. [ABSTRACT FROM AUTHOR]

Total column and stratospheric ozone levels at mid-latitudes often reveal strong fluctuations on time scales of days caused by dynamic processes. In some cases the total ozone column is distinctly reduced below climatological values. Here, a very low total ozone 5 episode around 19 January 2006 over Western Europe is investigated when the observed total ozone column over Uccle (BE), measured by a Brewer spectrophotometer, reached a daily minimum of 200 DU, the lowest recorded value at this station. In order to investigate the mechanisms leading to the ozone minimum, the present study used data from (i) six ozone sounding stations in Western and Middle Europe, 10 (ii) ECMWF meteorological fields, (iii) a simulation of the CLaMS model for January 2006, (iv) a multi-year run of the chemistry transport model KASIMA, and (v) a sixyear run of the climate chemistry model ECHAM5/MESSy1. The ozone decrease at different heights was quantified and it was determined to what extent different transport mechanisms, and instantaneous, in-situ chemical ozone depletion contributed to 15 the event. All three models reproduced well the evolution and formation of the event. The ozone column decrease between ⊝=300 and 750K was strongest at Uccle (BE) and De Bilt (NL) with 108 and 103 DU, respectively, and somewhat lower at Hohenpeissenberg (DE), Payerne (CH), Prague (CZ) and Lerwick (UK) with 85, 84, 83 and 74 DU, respectively. Our analysis demonstrated that mainly the displacement of the 20 ozone depleted polar vortex contributed to the ozone column decrease (between 55 and 82%), compared to the advection of ozone-poor low-latitude air in the UTLS region, connected with divergence of air out of the column caused by uplift of isentropes in the lower stratosphere. This dominance was significant only at Lerwick, De Bilt and Uccle. Severe low total ozone episodes seem to occur preferentially when the two mentioned transport mechanisms occur at the same time. Instantaneous, in-situ chemical ozone depletion accounted for only 2±1% of the overall total ozone decrease at the sounding stations. [ABSTRACT FROM AUTHOR]

We present an original multi-spectrum fitting procedure to retrieve volume mixing ratio (VMR) profiles of carbonyl fluoride (COF2) from ground-based high resolution Fourier transform infrared (FTIR) solar spectra. The multi-spectrum approach consists of simultaneously combining, during the retrievals, all spectra recorded consecutively during the same day and with the same resolution. Solar observations analyzed in this study with the SFIT-2 v3.91 fitting algorithm correspond to more than 2900 spectra recorded between January 2000 and December 2007 at high zenith angles, with a Fourier Transform Spectrometer operated at the high-altitude International Scientific Station of the Jungfraujoch (ISSJ, 46.5° N latitude, 8.0° E longitude, 3580m altitude), Switzerland. The goal of the retrieval strategy described here is to provide information about the vertical distribution of carbonyl fluoride. The microwindows used are located in the ν1 or in the ν4 COF2 infrared (IR) absorption bands. Averaging kernel and eigenvector analysis indicates that our FTIR retrieval is sensitive to COF2 inversion between 17 and 30 km, with the major contribution to the retrieved information always coming from the measurement. Moreover, there was no significant bias between COF2 partial columns, total columns or VMR profiles retrieved from the two bands. For each wavenumber region, a complete error budget including all identified sources has been carefully established. In addition, comparisons of FTIR COF2 17-30 km partial columns with KASIMA and SLIMCAT 3-D CTMs are also presented. If we do not notice any significant bias between FTIR and SLIMCAT time series, KASIMA COF2 17-30 km partial columns are lower of around 25%, probably due to incorrect lower boundary conditions. For each times series, linear trend estimation for the 2000-2007 time period as well as a seasonal variation study are also performed and critically discussed. We further demonstrate that all time series are able to reproduce the COF2 seasonal cycle, which main seasonal characteristics deduced from each data set agree quite well. [ABSTRACT FROM AUTHOR]

1-year data sets of monthly averaged nitrous oxide (N2O) and ozone (O3) derived from satellite measurements were used as a tool for the evaluation of atmospheric photochemical models. Two 1-year data sets, one derived from the Improved Limb Atmospheric Spectrometer (ILAS and ILAS-II) and one from the Odin Sub-Millimetre Radiometer (Odin/SMR) were employed. Here, these data sets are used for the evaluation of two Chemical Transport Models (CTMs), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) and the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as for one Chemistry-Climate Model (CCM), the atmospheric chemistry general circulation model ECHAM5/MESSy1 (E5M1) in the lower stratosphere with focus on the Northern Hemisphere. Since the Odin/SMR measurements cover the entire hemisphere, the evaluation is performed for the entire hemisphere as well as for the low latitudes, midlatitudes and high latitudes using the Odin/SMR 1-year data set as reference. To assess the impact of using different data sets for such an evaluation study we repeat the evaluation for the polar lower stratosphere using the ILAS/ILAS-II data set. Only small differences were found using ILAS/ILAS-II instead of Odin/SMR as a reference, thus, showing that the results are not influenced by the particular satellite data set used for the evaluation. The evaluation of CLaMS, KASIMA and E5M1 shows that all models are in good agreement with Odin/SMR and ILAS/ILAS-II. Differences are generally in the range of ±20%. Larger differences (up to -40%) are found in all models at 500±25 K for N2O mixing ratios greater than 200 ppb. Generally, the largest differences were found for the tropics and the lowest for the polar regions. However, an underestimation of polar winter ozone loss was found both in KASIMA and E5M1 both in the Northern and Southern Hemisphere. [ABSTRACT FROM AUTHOR]

In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km, where HOCl abundances are ruled by gas phase chemistry and at around 24 km, which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km, where in midlatitudinal and tropical atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed, polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. After deformation and displacement of the polar vortex in the course of a major warming, ClO rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. Comparison with a model run where no polar stratospheric clouds appeared during the observation period suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO and HOCl in the measurements is attributed to ongoing heterogeneous chemistry which is not reproduced by the model. In the following days, a decay of HOCl abundances was observed and on 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv. [ABSTRACT FROM AUTHOR]

In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18-24 km (475-625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run sug gests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO2 and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv. [ABSTRACT FROM AUTHOR]

This paper presents the spatiotemporal distribution of NOy species at altitudes between 14 and 31km as measured with the MIPAS-B instrument on the morning of 21 March 2003 in northern Scandinavia. At lower altitudes, temperature variations and the distribution of ClONO2 and the tracer N2O reveal the dynamics along the cross section through the edge of the late arctic polar vortex. At higher altitudes, continuous measurement before, during, and after sunrise provides information about photochemistry illustrating the evolution of the photochemically active gases NO2 and N2O5 around sunrise. The measured temporal evolution of NO2 and N2O5 is compared to box modelling that is run along backward calculated trajectories. With regard to NO2, there is a good agreement between the model and observations in terms of quantity but the photochemistry in the model is slightly too slow. The comparison of measured and modelled N2O5, however, reveals significant differences of the absolute quantities pointing at a too slow photochemistry in the model. [ABSTRACT FROM AUTHOR]

During the Arctic winter of 2000/01, ground-based FTIR and millimetre-wave measurements revealed significant amounts of ClO over Kiruna after the final warming in February 2001. In fact, column amounts of ClO were still increased in March 2001 when temperatures were about 20 K above the PSC (Polar Stratospheric Clouds) threshold. At these temperatures, chlorine activation due to heterogeneous processes on PSCs is not possible even in the presence of strong lee wave effects. In order to discuss possible reasons of this feature, time series of other chemical species will be presented and discussed, too. Measurements of HF and COF2 indicated that vortex air was still observed in mid-March 2001. Since the time series of HNO3 column amounts do not give any evidence of a denitrification later than 11 February, chlorine activation persisting for several weeks after the presence of PSCs due to denitrification is rather unlikely. The photolysis of ClONO2-rich air which had been formed at the end of February and beginning of March 2001 as well as chlorine activation due to the presence of an unusual aerosol layer are discussed as possible causes of the increased ClO column amounts after the final warming. [ABSTRACT FROM AUTHOR]