Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

Fractal aspects of integrated concentration fluctuations

Time series of vertically integrated concentrations (VIC) across neutrally buoyant plumes are used to study the fractal and multifractal characteristics of passive scalar fluctuations in turbulent flow fields. Here, the multifractal analysis is based on a novel definition of the singularity spectrum-F() of the time records. Approximations for quantities such as the fractal dimension and the spectral exponent are derived as functions ofF() and are compared with the experimental results. Among other things, we show that VIC records are characterized by two typical subdomains. One domain, which is related to integrated concentration fluctuations, is a subfractal process; whereas the second one, which is directly related to the concentration fluctuations, is a fractal process.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

Measurements of stratospheric HO2 and NO2 by matrix isolation and ESR spectroscopy

Vertical profiles of stratospheric HO₂ and NO₂ concentrations were determined using matrix isolation and ESR. Up to 10 different samples per flight were collected in situ by a balloon borne cryosampler. Free radicals and trace constituents which are condensable at 68 K are trapped in a polycristalline H₂O or D₂O matrix. After collection, the samples are stored at a temperature below 83 K until they are analysed in the laboratory by X-band ESR spectroscopy at 4 K. The HO₂ and NO₂ were identified and calibrated by comparison with standard samples collected in the laboratory under typical stratospheric sampling conditions. From several flights over Southern France (44°N) we obtained two profiles of the stratospheric NO₂ mixing ratio. One, from 21 October 1982, agrees well with previous measurements. The other, from 8 October 1981, is lower by one order of magnitude. The few HO₂ data obtained around 35 km altitude agree with previous measurements. An isolated measurement at 17 km altitude is one order of magnitude higher than the model predicted HO₂ concentration.     

A cospectral correction model for measurement of turbulent NO2 flux

A correction model for eddy correlation flux measurements is developed and applied to nitrogen dioxide flux measurements obtained from a SOLENT sonic anemometer and a Scintrex Luminox LMA-3 analyser for NO₂. Four field campaigns were carried out near the village of Merenschwand in Central Switzerland from which two were selected for further analysis in this paper. The need for the correction of measured eddy covariance fluxes arises due to the damping loss of the NO₂ analyser at high frequencies. This damping loss is described by an analogy to inductance in an electronical alternating current circuit. The independent variables in the correction model are:z (measuring height above zero-plane displacement), (mean horizontal wind speed), (Monin-Obukhov stability parameter),f (natural frequency) and inductanceL. The value for inductanceL can be derived from spectral and cospectral analysis. The theoretical cospectrum of an ideal measurement is taken from Kaimalet al. (1972) and extended with a damping term in order to describe the real measurements of the cospectrum. The inductanceL of the LMA-3 with a 0.6 cm teflon aspiration tube of 5 m length lies in the order of 0.30 to 0.35 for the dataset from Merenschwand. With this inductance, a correction factor of 1.17 in August/September 1992 and of 1.18 in May 1993 was determined for the NO₂ flux maxima during daytime. The range of the correction factor is 1.05 to 1.31 for the mean daily cycles of both datasets.     

Characteristics of the Lyman-alpha humidiometer and measurements of turbulent humidity fluctuations over the ocean

The characteristics of a Lyman-alpha humidiometer have been carefully examined in an air-conditioned test chamber. The results confirm that when carefully used, this humidiometer is suitable for measurements of turbulent humidity fluctuations. Measurements with a Lyman-alpha humidiometer were carried out in the surface boundary layer over the ocean. The relation between turbulent intensity ( _a = a ^ov2) and the friction humidity (a _*) can be expressed as _a = l.6a _*. The spectrum of turbulent humidity for wind speeds larger than 3 m s ^–1 conforms to the similarity law in the surface boundary layer. The spectrum has two characteristic normalized frequencies, namely, a higher peak and a secondary peak (or a shoulder).     

Estimation of probable maximum precipitation for a 2-day duration: Part 2 — north Indian region

Summary In a previous study the authors have estimated the probable maximum precipitation (PMP) for a 2-day duration using Hershfield's formulaX _PMP =X _n +k _{m n} for stations in the southern Indian region. In this paper, the study is extended to estimate the PMP for stations in the north Indian region, north of 20°N. Maximum annual 2-day rainfall data for an 80-year period, from 1901, were obtained for 286 stations in the region. A mathematical relationship between the frequency factor (k _m ) and the mean annual extreme rainfall (X _n ) was developed to bek _m = 18.15 exp (–0.0448X _n ). This equation was used to obtaink _m for different values ofX _n and, subsequently, to estimate 2-day PMP values for the 286 stations. Using these PMP estimates, a generalised chart was prepared, showing the spatial distribution of 2-day PMP. It was found that 2-day PMP over the north Indian region varied from 60 cm to 130 cm, and the average ratio of the 2-day PMP to the highest observed 2-day rainfall was found to be 1.91. The results show that there have been instances when almost 2-day point PMP have occurred at some of the stations in the region. These results indicate that the statistically estimated PMP rainall are not therefore, mere theoretical estimates, but they can occur under optimum meteorological conditions.With 4 Figures     

Nitrogen compound emission from biomass burning in tropical African savanna FOS/DECAFE 1991 experiment (Lamto,Ivory Coast)

Gaseous nitrogen compounds (NO _x , NO _y , NH₃, N₂O) were measured at ground level in smoke plumes of prescribed savanna fires in Lamto, in the southern Ivory Coast, during the FOS/DECAFE experiment in January 1991. During the flaming phase, the linear regression between [NO _x ] and [CO₂] (differences in concentration between smoke plumes and atmosheric background) results volumic emission ratio [NO _x ]/[CO₂]=1.37×10^–3 with only slight differences between heading and backing fires. Nearly 90% of the nitrogen oxides are emitted as NO. Average emission ratios of other compounds are: 1.91, 0.047, and 0.145×10^–3 for NO _y , NH₃ and N₂O, respectively. The emission ratios obtained during this field experiment are compred with corresponding values measured during former experiments with the same plant species in combustion chambers. An accurate determination of both the biomass actually burned and of the plant nitrogen content, allows an assessment of emission fluxes of N-compounds from Guinean savanna burns. Preliminary results dealing with the influence of fire on biogenic emissions from soils are also reported.     

Study of Ozone and NO2 over Gadanki – a rural site in South India

We have studied long-term changes in tropospheric NO₂ over South India using ground-based observations, and GOME and OMI satellite data. We have found that unlike urban regions, the region between Eastern and Western Ghat mountain ranges experiences statistically significant decreasing trend. There are few ground-based observatories to verify satellite based trends for rural regions. However, using a past study and recent measurements we show a statistically significant decrease in NO_X and O₃ mixing ratio over a rural location (Gadanki; 13.48° N, 79.18° E) in South India. In the ground-based records of surface NO_X, the concentration during 2010–11 is found to be lower by 0.9 ppbv which is nearly 60 % of the values observed during 1994–95. Small but statistically significant decrease in noon-time peak ozone concentration is also observed. Noon-time peak ozone concentration has decreased from 34?±?13 ppbv during 1993–96 to 30?±?15 ppbv during 2010–11. NO_X mixing ratios are very low over Gadanki. In spite of low NO_X values (0.5 to 2 ppbv during 2010–11), ozone mixing ratios are not significantly low compared to many cities with high NO_X. The monthly mean ozone mixing ratio varies from 9 ppbv to 37 ppbv with high values during Spring and low values during late Summer. Using a box-model, we show that presence of VOCs is also very important in addition to NO_X in determining ozone levels in rural environment and to explain its seasonal cycle.     

Application of an infrared carbon dioxide and humidity instrument to studies of turbulent transport

A calibration equation and some results of the field performance of an infrared instrument, which is designed to measure simultaneous fluctuations of atmospheric carbon dioxide and water vapor, are described. Field observations show that the instrument is suitable for simultaneous measurement of turbulent fluxes of carbon dioxide and water vapor in conjunction with a sonic anemometer. Measured values of carbon dioxide and water vapor fluxes show diurnal variations characterized by crop activity with respect to assimilation, respiration and evapotranspiration. Carbon dioxide is transferred downward during the daytime and upward at night, while latent heat and sensible heat are transferred in the opposite sense. The non-dimensional gradient of carbon dioxide is expressed in the following form under weak unstable conditions: _c = (1 – 16 _v )^-1/2. Here, _v is the Monin-Obukhov stability parameter including the humidity effect. This relation was originally proposed for temperature and humidity. Thus, the results indicate that the turbulent mechanisms of carbon dioxide fluctuations are similar to those of other scalar entities. This is strongly supported by the high correlation coefficient found between fluctuations of carbon dioxide and temperature or humidity in the air layer over crop fields.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

Short term variability of atmospheric turbidity and optical turbulence in a desert environment

Summary Variability of atmospheric turbidity calculated from direct beam solar radiation measurements and the transverse coherence length,r ₀, derived from differential image motion of stellar sources show pronounced fluctuations on the order of a few minutes under convectively unstable conditions in a desert environment. The quiescent periods, neutral events, when local near surface adiabatic conditions occur show substantial reductions in the fluctuations of the same quantities. Image motion results for nighttime (stable) conditions display slowing varying patterns with reduced short term (few minutes) variations.The measurements were taken using a suite of instrumentation probing the same volume of atmosphere. The instrumentation used includes a pyrheliometer, Atmospheric Turbulence Measurement and Observation System (ATMOS), a sodar, a scintillometer, and tower- mounted sensors. A time-height display of sodar data calibrated for the refractive index structure parameter,C _n ² , coupled with scintillometer measurements show the diurnal evolution of the boundary layer responding to the local heating-cooling cycle and drainage flows from the surrounding mountains. Several atmospheric features are seen and discussed in these results as they affect the nature of the patterns of turbidity andr ₀. Of particular interests are the development of convection, changes in the capping inversion, thermal plume structures, neutral events, and wave-turbulence interactions. Sinusoidal oscillations, identified as internal gravity waves, are seen in the nighttime laminated structures.With 10 Figures     

A determination of the CH4, NO x and CO2 emissions from the Prudhoe Bay,Alaska oil development

In this paper we quantify the CH₄, CO₂ and NO _x emissions during routine operations at a major oil and gas production facility, Prudhoe Bay, Alaska, using the concentrations of combustion by products measured at the NOAA-CMDL observatory at Barrow, Alaska and fuel consumption data from Prudhoe Bay. During the 1989 and 1990 measurement campaigns, 10 periods (called events) were unambiguously identified where surface winds carry the Prudhoe Bay emissions to Barrow (approximately 300 km). The events ranged in duration from 8–48 h and bring ambient air masses containing substantially elevated concentrations of CH₄, CO₂ and NO _y to Barrow. Using the slope of the observed CH₄ vs CO₂ concentrations during the events and the CO₂ emissions based on reported fuel consumption data, we calculate annual CH₄ emissions of (24+/–8)×10³ metric tons from the facility. In a similar manner, the annual NO _x emissions are calculated to be (12+/–4)×10³ metric tons, which is in agreement with an independently determined value. The calculated CH₄ emissions represent the amount released during routine operations including leakage. However this quantity would not include CH₄ released during non-routine operations, such as from venting or gas flaring.     

Laboratory spectroscopic studies of atmospherically important radicals using fourier transform spectroscopy

This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm^-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the ₃ band of NO₃, at ca. 1500 cm^-1, were obtained with up to 0.005 cm^-1 resolution using the reaction between NO₂ and O₃ to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O₃, and the (1-0) vibration-rotation band in the region 829–880 cm^-1 was recorded at a resolution of 0.02 cm^-1. We were unable to observe infrared absorption of HO₂ with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N₂O₅, HNO₃, ClONO₂, FNO₂, Cl₂O, HO₂NO₂, and probably FO₂.The ability to monitor concentrations of the NO₃ radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO₂ reacts with O₃. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO₃–N₂O₅–H₂O system might be a viable source of HNO₃ in the atmosphere.     

Incorporation of internal fluctuations in a meandering plume model of concentration fluctuations

A meandering plume model that explicitly incorporates the effects of small-scale structure in the instantaneous plume has been formulated. The model requires the specification of two physically based input parameters; namely, the meander ratio,M, which is dependent on the ratio of the meandering plume dispersion to the instantaneous relative plume dispersion and, a relative in-plume fluctuation measure,k, that is related inversely to the fluctuation intensity in relative coordinates. Simple analytical expressions for crosswind profiles of the higher moments (including the important shape parameters such as fluctuation intensity, skewness, and kurtosis) and for the concentration pdf have been derived from the model. The model has been tested against some field data sets, indicating that it can reproduce many key aspects of the observed behavior of concentration fluctuations, particularly with respect to modeling the change in shape of the concentration pdf in the crosswind direction.List of Symbols C Mean concentration in absolute coordinates - C _r Mean concentration in relative coordinates - C₀ Centerline mean concentration in absolute coordinates - C _r,0 Centerline mean concentration in relative coordinates - f Probability density function of concentration in absolute coordinates - f _c Probability density function of plume centroid position - f _r Probability density function of concentration in relative coordinates - i Absolute concentration fluctuation intensity (standard deviation to mean ratio) - i _r Relative concentration fluctuation intensity (standard deviation to mean ratio) - k Relative in-plume fluctuation measure:k=1/i _r ² - K Concentration fluctuation kurtosis - M Meander ratio of meandering plume variance to relative plume variance - S Concentration fluctuation skewness - x Downwind distance from source - y Crosswind distance from mean-plume centerline - z Vertical distance above ground - Instantaneous (random) concentration - Crosswind dispersion ofnth concentration moment about zero - _ny Mean-plume crosswind (absolute) dispersion - _y Plume centroid (meandering) dispersion in crosswind direction - _y,c Instantaneous plume crosswind (relative) dispersion - Normalized mean concentration in absolute coordinates:C/C ₀ - Particular value taken on by instantaneous concentration,      

In Situ Trace Gas and Particle Measurements in the Summer Lower Stratosphere during STREAM II: Implications for O3 Production

In situ aircraft measurements of O₃, CO,HNO₃, and aerosol particles are presented,performed over the North Sea region in the summerlower stratosphere during the STREAM II campaign(Stratosphere Troposphere Experiments by AircraftMeasurements) in July 1994. Occasionally, high COconcentrations of 200-300 pbbv were measured in thelowermost stratosphere, together with relatively highHNO₃ concentrations up to 1.6 ppbv. The particlenumber concentration (at standard pressure andtemperature) between 0.018-1 m decreased acrossthe tropopause, from >1000 cm^-3 in the uppertroposphere to <500 cm^-3 in the lowermoststratosphere. Since the CO sources are found in thetroposphere, the elevated CO mixing ratios areattributed to mixing of polluted tropospheric air intothe lowermost extratropical stratosphere. Further wehave used a chemical model to illustrate that nitrogenoxide reservoir species (mainly HNO₃) determinethe availability of NO_x (=NO + NO₂) andtherefore largely control the total net O₃production in the lower kilometers of thestratosphere. Model simulations, applying additionalNO_x perturbations from aircraft, show that theO₃ production efficiency of NO_x is smallerthan previously assumed, under conditions withrelatively high HNO₃ mixing ratios, as observedduring STREAM II. The model simulations furthersuggest a relatively high O₃ productionefficiency from CO oxidation, as a result of therelatively high ambient HNO₃ and NO_xconcentrations, implying that upward transport of COrich air enhances O₃ production in the lowermoststratosphere. Analysis of the measurements and themodel calculations suggest that the lowermoststratosphere is a transition region in which thechemistry deviates from both the upper troposphere andlower stratosphere.     

Determining past atmospheric HCl mixing ratios from ice core analyses

Laboratory and field measurements have been performed in order to improve our understanding of the HCl air-snow transfer function. The solubility and diffusion of HCl in laboratory grown single crystals of ice have been measured as a function of HCl partial pressure,P _HCl, between –8 and –25 °C. Measurements ofP _HCl and of the mole fraction of HCl in snow,X'_HCl, have been measured at Summit, Greenland. Comparison of the field and laboratory measurements show that theX'_HCl values are well below equilibrium values. The major processes involved in the formation of snow crystals and in their evolution after deposition are discussed in order to attempt to understand theX'_HCl values and their variations. The discussion is focussed on a few well identified snow layers. It is concluded that sublimation and recrystallization of snow probably play a major role in the evolution ofX'_HCl, but that our understanding of the HCl transfer function is very incomplete. Laboratory and field measurements are suggested to improve this situation.