Inter-Laboratory Comparison of No2 and SO2 Generated by Dynamic Dilution System Under Laboratory Conditions: A Technical Discussion

A workshop on analytical quality control (AQC) of ambient air quality measurement methods for nitrogen dioxide (NO₂) and sulphur dioxide (SO₂) was conducted by Central Pollution Control Board (CPCB) for officials involved in National Ambient Air Quality Monitoring (NAAQM) in India. Concentrations of NO₂ and SO₂ were generated by dynamic dilution system under laboratory conditions at low and high levels and measured using static dilution system and wet chemical methods laid down by CPCB under section 16(2)(h) of the air act 1981. CPCB provided the measured values as reference values for comparing the means obtained by the officials participated from thirteen organizations. A tolerance limit of ±15% of the reference values was specified to accept the results. Generated concentrations, which were unknown to the participants, were measured using gaseous sampling assembly (Envirotech APM 411, New Delhi, India), and wet chemical methods laid down by CPCB i.e. the same methodology which is used by the organizations to generate the data of NO₂ and SO₂ in ambient air. Simultaneously, concentrations were checked by CPCB using automatic analyzers as a check on reference concentration. It is observed that results of automatic analyzers for NO₂ and SO₂ were within a tolerance of ±5% with %RSD below 3. On the other hand, results of most of the participants showed variability in the measurements with %RSD ranging between ±0.8 and ±88.6 and exceedences of means from the tolerance limit with bias ranging between 1.4 and −59%. To check the cause of high variability in the measurements obtained under identical conditions, duplicate sampling was performed by one of the participants for SO₂ at low concentration level. In this study, results of wet chemical methods, automatic analyzers and results of duplicate sampling are analysed statistically to assess the cause of high variability in the measurements. Analysis of t-test and analysis of variance (ANOVA) showed highly significant results for NO₂ and SO₂ at high concentration levels (α 0.05) and for SO₂ at both the levels (α 0.01) respectively indicating some bias is existing either in the sampling or in analytical technique. Duplicate sampling performed to check precision in parallel measurements showed high %RSD indicating the presence of systematic error in sampling technique as the same calibration factor (CF) was used to measure the concentration of duplicate samples. Statistical analysis of flow rates of duplicate sampling showed that the sampling assembly could not maintain the constant flow rate within the ±10% with that measured at the start of the sampling. This resulted in high %RSD and deviation from the reference values for the results of most of the participants, even after accepting ±15% tolerance limit. There is a need to improve and evaluate this gaseous sample collection device under laboratory conditions to generate reliable database of NO₂ and SO₂ in ambient air.     

川南6市空气中SO2和NO2空间分布特征

利用简单、方便、不用电源的被动采样技术分别对川南地区6市区域范围内空气中SO2和NO2在雨季和旱季的空间分布特征进行研究。按16 km×16 km的均匀网格布设点位162个,并在雨季于6市各选1个空气自动站布设城区点位采集空气中SO2和NO2。获得的样品经0.3%的双氧水浸提后采用离子色谱法进行分析,经换算后获得空气中SO2和NO2的浓度,了解了其含量水平,绘制了SO2和NO2的空间分布图,掌握了其空间分布特征,并对可能的来源进行了浅析。将被动采样监测结果与自动站监测结果进行相关分析,两者高度线性相关,NO2和SO2线性相关系数分别为0.901 3和0.874 5,均大于r0.05(4)=0.811 4。     

离子色谱法测废印刷电路板真空热解气相污染物中HBr、NO2和SO2

在淋洗液中加入H2O2和三乙醇胺配制成吸收液,通过离子色谱法同时测定废印刷电路板真空热解气相产物中HBr、NO_2和SO_2的含量,方法简单、快速、准确。当用50 m L吸收液、采样体积为30 L时,3种污染物的检出限分别为0.000 005 7、0.000 003 4、0.000 002 9 mg/L。该方法加标回收率为95.7%~104.8%,完全能满足废印刷电路板真空热解气相污染物中HBr、NO_2和SO_2的同时测定要求。利用该方法和行标方法同时测定环境空气中的HBr、NO_2和SO_2,再利用Excel分析工具对测定数据进行F检验和t检验,检验结果表明2种测定方法无显著差异。     

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air

The performances and applicability of a diffusion tubesampler for the simultaneous measurements of NO₂ andSO₂ in ambient air were evaluated. SO₂ andNO₂are collected by the passive sampler using triethanolamine astrapping agent and are determined as sulphate and nitrite withion chromatography. The detection limit (2.3 g m^-3 ofNO₂ and 4.2 g m^-3 of SO₂ for two weekssampling) is adequate for the determination of concentrationsin urban and industrial areas. Precision of the method as RSDis in mean 5% for NO₂ and 12% for SO₂ at theconcentration levels in urban areas. Calibration of the methodwas performed in the field conditions by comparison between theresponses of sampler and the concentrations measured by thecontinuous monitors. High degree of linearity (correlationcoefficients > 0.8) is found between the passive sampler tubeand the continuous monitor data for both NO₂ and SO₂.To reduce the wind velocity influence on passive sampling ofdiffusion tubes, a protective shelter was tested in this study.The overall uncertainty of one measure for the optimised methodis estimated at 5 g m^-3 for NO₂ and 6g m^-3 for SO₂. Suitability of this passivesampling method for air pollution monitoring in urban areas wasdemonstrated by the results shown in this paper on a campaigncarried out in the French agglomeration.     

A necessary distinction between spatial representativeness of an air quality monitoring station and the delimitation of exceedance areas

The European legislation on ambient air quality introduces the concepts of spatial representativeness of a monitoring station and spatial extent of an exceedance zone. Spatial representativeness is an essential macro-scale siting criterion which should be evaluated before the setting-up and during the life of a monitoring point. As for the exceedance area, it has to be defined each time an environmental objective is exceeded in an assessment zone. No specific approach is prescribed to delimit such areas. A probabilistic methodology is presented, based on a preliminary kriging estimation of atmospheric concentrations at each point of the domain. It is applied to NO₂ pollution on the urban scale. In the proposed approach, a point belongs to the area of representativeness of a station if its concentration differs from the station measurement by less than a given threshold. To take the estimation uncertainty into account, the standard deviation of the kriging error is used in a probabilistic framework. The choice of the criteria used to deal with overlapping areas is first tested on NO₂ annual mean concentration maps of France, built by combining surface monitoring observations and outputs from the CHIMERE chemistry transport model. At the local scale, data from passive sampling surveys and high -resolution auxiliary variables are used to provide a more precise estimation of the background pollution in different French cities. The traffic-related pollution can also be accounted for in the map by additional predictors such as distance to the road, and traffic-related NO_x emissions. Similarly, the proposed approach is implemented to identify the points, at a given statistical risk, where the NO₂ concentration is above the annual limit value.     

Seasonal trends of atmospheric nitrogen dioxide and sulfur dioxide over North Santa Clara, Cuba

Atmospheric nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) levels were monitored simultaneously by means of Radiello passive samplers at six sites of Santa Clara city, Cuba, in the cold and the warm seasons in 2010. The dissolved ionic forms of NO₂ and SO₂ as nitrate and sulfite plus sulfate, respectively, were determined by means of ion chromatography. Analysis of NO₂ as nitrite was also performed by UV–Vis spectrophotometry. For NO₂, significant t tests show good agreement between the results of IC and UV–Vis methods. The NO₂ and SO₂ concentrations peaked in the cold season, while their minimum levels were experienced in the warm season. The pollutant levels do not exceed the maximum allowable limit of the Cuban Standard 39:1999, i.e., 40 μg/m³ and 50 μg/m³ for NO₂ and SO₂, respectively. The lowest pollutant concentrations obtained in the warm season can be attributed to an increase in their removal via precipitation (scavenging) while to the decreased traffic density and industrial emission during the summer holidays (e.g., July and August).     

Inspection of non-CO2 greenhouse gases from emission sources and in ambient air by Fourier-transform-infrared-spectrometry: Measurements with FTIS-MAPS

Infrared spectrometry is a versatile basis to analyse greenhouse gases in the atmosphere. A multicomponent air pollution software (MAPS) was developed for retrieval of gas concentrations from radiation emission as well as absorption measurements. Concentrations of CO, CH₄, N₂O, and H₂O as well as CO₂, NO, NO₂, NH₃, SO₂, HCl, HCHO, and the temperature of warm gases are determined on-line. The analyses of greenhouse gases in gaseous emission sources and in ambient air are performed by a mobile remote sensing system using the double-pendulum interferometer K300 of the Munich company Kayser-Threde. Passive radiation measurements are performed to retrieve CO, N₂O, and H₂O as well as CO₂, NO, SO₂, and HCl concentrations in smoke stack effluents of thermal power plants and municipal incinerators and CO and H₂O as well as CO₂ and NO in exhausts of aircraft engines. Open-path radiation measurements are used to determine greenhouse gas concentrations at different ambient air conditions and greenhouse gas emission rates of diffusive sources as garbage deposits, open coal mining, stock farming together with additional compounds (e.g. NH₃), and from road traffic together with HCHO. Some results of measurements are shown. A future task is the verification of emission cadastres by these inspection measurements.     

Effect of Temperature on Absorption Efficiency of NO2 in Arsenite Method

The sodium arsenite method developed by Jacobs andHochheiser is one of the most widely used manualmethods for nitrogen dioxide (NO₂) monitoring inambient air, particularly in developing countries. Asreported, the method gives 82% NO₂ absorptionefficiency (NAE) in the concentration range from 40 to750 g/m³, when only one impinger tube isemployed in the sampling train at a flow rate of 0.2lpm and for 24 h sampling duration. Accordingly,a uniform correction factor (0.82) is used indenominator to calculate the ultimate concentration ofNO₂ in ambient air.In the present investigation, the effect oftemperature on absorption efficiency of NO₂ isstudied employing four impinger tubes in series tocollect the maximum NO₂ generated in the gasstream. The study conducted at 16, 26 and 36 °Ctemperatures shows maximum absorption efficiency(average) of 87.8% at 26°C in 1st impingertube. At lower and higher temperatures, it is foundconsiderably less. A suitable correction factor,therefore, must be applied to estimate actual NO₂concentration in ambient air using arsenite method, intropical countries like India, where atmospherictemperature variations are large (less than 5°Cin winter and more than 45°C in summer).     

Study on concentration of ambient NH 3 and interactions with some other ambient trace gases

We present diurnal variation of ambient ammonia (NH₃) in relation with other trace gases (O₃, CO, NO, NO₂, and SO₂) and meteorological parameters at an urban site of Delhi during winter period. For the first time, ambient ammonia (NH₃) was monitored very precisely and continuously using ammonia analyzer, which operates on chemiluminescence method. NH₃ estimation efficiency of the chemiluminescence method (>90%) is much higher than the conventional chemical trapping method (reproducibility 4.5%). Ambient NH₃ concentration reaches its maxima (46.17 ppb) at night and minimum during midday. Result reveals that the ambient ammonia (NH₃) concentration is positively correlated with ambient NO (r ²?=?0.79) and NO₂ (r ²?=?0.91) mixing ratio and negatively correlated with ambient temperature (r ²?=???0.32). Wind direction and wind speed indicates that the nearby (~500 m NW) agricultural fields may be major source of ambient NH₃ at the observational site.     

Comparison of Two Manual Methods of Nitrogen Dioxide Determination in Ambient Air

Sodium arsenite (modified Jacobs and Hochheiser method; hereafter referred as SA), the most widely used manual monitoring method for determination of nitrogen dioxide (NO₂) in ambient air, particularly in developing countries has been evaluated and compared with US EPA recommended equivalent method of TGS-ANSA (hereafter referred as ANSA). NO₂ concentrations generated from laboratory test atmosphere were analyzed by these two methods and were compared statistically. Laboratory evaluations showed that SA method has high sensitivity to different sampling conditions, which normally vary during actual field monitoring. Hence, correction factors for absorption efficiency were estimated for SA and ANSA methods. Absorption efficiency of NO₂ in SA method was found to be much lower (64%) as against the reported value of 82% at the method recommended sampling conditions, whereas for ANSA method, it was found 1.0 as against the reported value of 0.93. After applying derived correction factors, both the methods produced almost similar concentration values of NO₂.     

Assessment of Urban Air Quality in South Estonia by Simple Measures

In countries having limited resources, it is difficult to assess urban air quality on contemporaneously, due to the absence of on-line information about air pollution levels and emission rates. An alternative approach is recommended for smaller cities with lower demands of resources. The applied scheme consists of a database of air pollution sources (NO _x and CO from industry, traffic, and domestic heating), the simple Gaussian-plume model AEROPOL and a series of measurements by passive monitors. This method was used in Tartu, a small city situated in the valley of the river Emajõgi, within a landscape with noteworthy topographical variations. Simulations of annual average and maximal concentrations were performed, and a fair agreement obtained with NO₂ monitoring results from passive Palmes monitors. Inventories of pollution sources in 1998 revealed that official statistics of stationary sources covered 64% of SO₂,36% of CO, 37% of NO _x and 32% of total particulate matter emissions. Recommendations for measures for reducing air pollution levels and for further investigations towards improving air quality assessment and management, are given.     

Development of a personal monitoring method for nitrogen dioxide and sulfur dioxide with Sep-Pak C18 cartridge sampling and ion chromatographic determination

Personal monitoring methods for the determination of hourly integrated concentrations of NO2 and SO2 in ambient air have been developed. Triethanolamine (TEA)-impregnated C18 Sep-Pak cartridges were used to collect NO2 and SO2 simultaneously. After sampling, NO2 and SO2 as their nitrite, nitrate, sulfite and sulfate analogues were stripped from the cartridges with a solution of 5% methanol in distilled, deionized water (DDW) and then determined by ion chromatography. Laboratory tests were conducted to evaluate the sampling rate, collection and recovery efficiencies, breakthrough volumes, absorption capacity, interference and sample stability on the cartridge during storage. NO2 and SO2 detection limits of 0.3 and 0.4 ppb respectively for 1 h samples were obtained. Recoveries for both NO2 and SO2 exceeded 85%.     

A New All Season Passive Sampling System for Monitoring Ozone in Air

A new all season passive sampling system for monitoring O₃ in the atmosphere has been developed in the laboratory and validated in the field. The unique features for this system include a newly designed passive sampler and a rain shelter, which allow the passive sampler to be installed in the field facing downwards. An equation associated with meteorological parameters is used to calculate the passive sampling rates. This system has been extensively tested in the lab (temperature from –18 to 20°C, relative humidity from 13 to 81%, and wind speed from 0.5 to 150 cm/s) and validated in the field in climates of all seasons. The accuracy of the ozone concentrations in the atmosphere obtained with the use of the new passive sampling system was higher than 85% compared to those obtained with continuous ozone analyzers. The new ozone passive sampling system can be used to measure ambient O₃ concentrations ranging from 3 ppb to 1000 ppb based on one-day exposure and 0.1 ppb to 140 ppb for a monthly exposure period. It is also reasonable to conclude that the new passive sampling system can be used for eight-hour exposure study because of the low field blanks and high sampling rates.     

Spatial and temporal analysis of ground level ozone and nitrogen dioxide concentration across the twin cities of Pakistan

The analyses presented in this paper include the concentration levels of NO₂ and O₃ measured during 2 successive years in twin cities (Rawalpindi and Islamabad) of Pakistan from November 2009 to March 2011. NO₂ was determined using the passive sampling method, while ozone was determined by Model 400E ozone analyzer. The average NO₂ and O₃ concentration in twin cities of Pakistan was found to be 44?±?6 and 18.2?±?1.24 ppb, respectively. Results indicate that the concentration of NO₂ and O₃ show seasonal variations. Results also depict that NO₂ and O₃ concentration levels are high in areas of intense traffic flow and congestion. Rawalpindi has more elevated levels of NO₂ and O₃ as compared to the Islamabad due to the narrow roads, enclosing architecture of road network and congestion. Climatic variables also influenced the NO₂ and O₃ concentration, i.e., temperature is positively related with O₃, while negatively related with NO₂, relative humidity is directly related with NO₂ and inversely related with O₃, whereas rainfall show negative association with both NO₂ and O₃ concentration. Comparing the results with WHO standards reveals that NO₂ concentration levels at all the sampling points are above the permissible limit, while ozone concentration is still lower than the WHO standards. Thus, there is a need to take appropriate steps to control these continuously increasing levels of NO₂ and O₃ before they become a serious hazard for the environment and people living in those areas.     

Systematic Biases in Measurement of Urban Nitrogen Dioxide using Passive Diffusion Samplers

Measurement of nitrogen dioxide using passivediffusion tube over 22 months in Cambridge, U.K. areanalysed as a function of sampler exposure time, andcompared with NO₂ concentrations obtained from aco-located chemiluminescence analyser. The averageratios of passive sampler to analyser NO₂ at acity centre site (mean NO₂ concentration 22 ppb)are 1.27 (n = 22), 1.16 (n = 34) and 1.11 (n = 7) forexposures of 1, 2 and 4-weeks, respectively. Modellingthe generation of extra NO₂ arising from chemicalreaction between co-diffusing NO and O₃ in thetube gave a ratio (modelled/measured) of 1.31 for1-week exposures. Such overestimation is greatest whenNO₂ constitutes, on average, about half of totalNO_x (= NO + NO₂) at the monitoring locality.Although 4-week exposures gave concentrations whichwere not significantly different from analyserNO₂, there was no correlation between thedatasets. At both the city-centre site and anothersemi-rural site (mean NO₂ concentration 11 ppb)the average of the aggregate of four consecutive1-week sampler exposures or of two consecutive 2-weeksampler exposures was systematically greater than fora single 4-week exposure.The results indicate two independent and opposingsystematic biases in measurement of NO₂ bypassive diffusion sampler: an exposure-timeindependent chemical overestimation with magnitudedetermined by local relative concentrations of NO andO₃ to NO₂, and an exposure-time dependentreduction in sampling efficiency. The impact of theseand other potential sources of systematic bias on theapplication of passive diffusion tubes for assessingambient concentrations of NO₂ in short (1-week)or long (4-week) exposures are discussed in detail.     

Seasonal characteristics of SO2, NO2, and CO emissions in and around the Indo-Gangetic Plain

Anthropogenic emissions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and carbon monoxide (CO) exert significant influence on local and regional atmospheric chemistry. Temporal and spatial variability of these gases are investigated using surface measurements by the Central Pollution Control Board (India) during 2005–2009 over six urban locations in and around the Indo-Gangetic Plain (IGP) and supported using the satellite measurements of these gases. The stations chosen are Jodhpur (west of IGP), Delhi (central IGP), Kolkata and Durgapur (eastern IGP), Guwahati (east of IGP), and Nagpur (south of IGP). Among the stations studied, SO₂ concentrations are found to be the highest over Kolkata megacity. Elevated levels of NO₂ occur over the IGP stations of Durgapur, Kolkata, and Delhi. Columnar NO₂ values are also found to be elevated over these regions during winter due to high surface concentrations while columnar SO₂ values show a monsoon maximum. Elevated columnar CO over Guwahati during pre-monsoon are attributed to biomass burning. Statistically significant correlations between columnar NO₂ and surface NO₂ obtained for Delhi, Kolkata, and Durgapur along with very low SO₂ to NO₂ ratios (≤0.2) indicate fossil fuel combustion from mobile sources as major contributors to the ambient air over these regions.     

Impact of Diwali celebrations on urban air and noise quality in Delhi City,India

A study was conducted in the residential areas of Delhi, India, to assess the variation in ambient air quality and ambient noise levels during pre-Diwali month (DM), Diwali day (DD) and post-Diwali month during the period 2006 to 2008. The use of fireworks during DD showed 1.3 to 4.0 times increase in concentration of respirable particulate matter (PM₁₀) and 1.6 to 2.5 times increase in concentration of total suspended particulate matter (TSP) than the concentration during DM. There was a significant increase in sulfur dioxide (SO₂) concentration but the concentration of nitrogen dioxide (NO₂) did not show any considerable variation. Ambient noise level were 1.2 to 1.3 times higher than normal day. The study also showed a strong correlation between PM₁₀ and TSP (R ² ≥ 0.9) and SO₂ and NO₂ (R ² ≥ 0.9) on DD. The correlation between noise level and gaseous pollutant were moderate (R ² ≥ 0.5). The average concentration of the pollutants during DD was found higher in 2007 which could be due to adverse meteorological conditions. The statistical interpretation of data indicated that the celebration of Diwali festival affects the ambient air and noise quality. The study would provide public awareness about the health risks associated with the celebrations of Diwali festival so as to take proper precautions.     

Monitoring of Fogwater Chemistry in the Gulf Coast Urban Industrial Corridor: Baton Rouge (Louisiana)

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002–2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻. The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO₃⁻ but partly offset by high NH₄⁺. The measured gaseous SO₂ accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO₂ to sulfate in fogwater. The gaseous NO_x accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 μM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 μM. Small concentrations of Mn (7.8 μM), Cu (2 μM), Pb (0.07 μM) and As (0.32 μM) were also observed in the fogwaters, and these were shown to result from particulates (PM_2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1–2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.     

An Analysis of Secondary Pollutants in Buenos Aires City

Air pollutant concentrations from a monitoring campaign in Buenos Aires City, Argentina, are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO _x (=NO + NO₂). This campaign undertaken by the electricity sector was aimed at elucidating the apportionment of thermal power plants to air quality deterioration. Concentrations of carbon monoxide (CO) and sulphur dioxide (SO₂) were also registered. Photo stationary state (PSS) of the NO, NO₂, O₃ and peroxy radicals species has been analysed. The ‘oxidant’ level concept has been introduced, OX (=O₃ + NO₂), which varies with the level of NO _x . It is shown that this level is made up of NO _x -independent and NO _x -dependent contributions. The former is a regional contribution that equates the background O₃ level, whereas the latter is a local contribution that correlates with the level of primary pollution. Furthermore, the anticorrelation between NO₂ and O₃ levels, which is a characteristic of the atmospheric photo stationary cycle has been verified.The analysis of the concentration of the primary pollutants CO and NO strongly suggests that the vehicle traffic is the principal source of them. Levels of continuous measurements of SO₂ for Buenos Aires City are reported in this work as a complement of previously published results.     

Measurements and Modelling of Air Pollution in a Street Canyon in Helsinki

A measuring campaign was conducted in the street canyon 'Runeberg street' in Helsinki in 1997. Hourly concentrations of carbon monoxide (CO), nitrogen oxides (NO_X), nitrogen dioxide (NO₂) and ozone (O₃) were measured at the street and roof levels, and the relevant hourly meteorological parameters were measured at the roof level. The hourly street level measurements and on-site electronic traffic counts were conducted during the whole year 1997, and roof level measurements were conducted during approximately two months, from 3 March to 30 April in 1997. The Operational Street Pollution Model (OSPM) was used to calculate the street concentrations and the results were compared with the measurements. The overall agreement between measured and predicted concentrations was good for CO and NO_x, but the model slightly overestimated the measured concentrations of NO₂. The database, which contains all measured and predicted data, is available for a further testing of other street canyon dispersion models.