Urban Air Pollution Monitoring with DOAS Considering the Local Meteorological Situation

The concentrations of ozone, NO₂ and SO₂, measured with a DOAS system 70 m above ground level in the city of Graz were compared with data from conventional ground stations. The dependence of vertical trace-gas distributions on stability categories and time of the day or year was investigated. Concerning the maximum ozone concentrations in summer, the DOAS data are representative for the ground-level situation. In average, the concentrations 70 m above ground are more than twice the ground-level concentrations. It has been shown that beside the reaction with NO, dry deposition is an important sink for ozone near the surface. The DOAS NO₂-concentrations are representative for ground-level conditions in summer, except for the morning maximum of NO₂. In winter the DOAS NO₂-concentrations amount for 73% of the ground level values in average. Concerning the slow reacting trace gas SO₂, the DOAS data are always representative for the ground-level conditions.     

Inter-seasonal and spatial distribution of ground-level greenhouse gases (CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, N<Subscript>2</Subscript>O) over Nagpur in India and their management roadmap

Ground-level concentrations of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) were monitored over three seasons, i.e., post-monsoon (September–October), winter (January–February), and summer (May–June) for 1 year during 2013–2014 in Nagpur City in India. The selected gases had moderate to high variation both spatially (residential, commercial, traffic intersections, residential cum commercial sites) and temporally (at 7:00, 13:00, 18:00, and 23:00 hours in all three seasons). Concentrations of gases were randomly distributed diurnally over city in all seasons, and there was no specific increasing or decreasing trend with time in a day. Average CO₂ and N₂O concentrations in winter were higher over post-monsoon and summer while CH₄ had highest average concentration in summer. Observed concentrations of CO₂ were predominantly above global average of 400 ppmv while N₂O and CH₄ concentrations frequently dropped down below global average of 327 ppbv and 1.8 ppmv, respectively. Two-tailed Student’s t test indicated that post-monsoon CO₂ concentrations were statistically different from summer but not so from winter, while difference between summer and winter concentrations was statistically significant (P < 0.05). CH₄ concentrations in all seasons were statistically at par to each other. In case of N₂O, concentrations in post-monsoon were statistically different from summer but not so from winter, while difference between summer and winter concentrations was statistically significant (P < 0.05). Average ground-level concentrations of the gases calculated for three seasons together were higher in commercial areas. Environmental management priorities vis a vis greenhouse gas emissions in the city are also discussed.     

Gas–particle concentration,distribution, and health risk assessment of polycyclic aromatic hydrocarbons at a traffic area of Giza,Egypt

Atmospheric particulate and gaseous polycyclic aromatic hydrocarbons (PAHs) samples were collected from an urban area in Dokki (Giza) during the summer of 2007 and the winter of 2007–2008. The average concentrations of PAHs were 1,429.74 ng/m³ in the particulate phase, 2,912.56 ng/m³ in the gaseous phase, and 4,342.30 ng/m³ in the particulate + gaseous phases during the period of study. Dokki has high level concentrations of PAH compounds compared with many polluted cities in the world. The concentrations of PAH compounds in the particulate and gaseous phases were higher in the winter and lower in the summer. Total concentrations of PAHs in the particulate phase and gaseous phase were 22.58% and 77.42% in summer and 36.97% and 63.03% in winter of the total (particulate + gaseous) concentrations of PAHs, respectively. The gaseous/particulate ratios of PAHs concentration were 3.43 in summer and 1.71 in winter. Significant negative correlation coefficients were found between the ambient temperature and concentrations of the total PAHs in the particulate and gaseous phases. The distribution of individual PAHs and different categories of PAHs based on aromatic ring number in the particulate and gaseous phases during the summer and winter were nearly similar, indicating similar emission sources of PAHs in both two seasons. Benzo(b)fluoranthene in the particulate phase and naphthalene in the gaseous phase were the most abundant compounds. Diagnostic concentration ratios of PAH compounds indicate that these compounds are emitted mainly from pyrogenic sources, mainly local vehicular exhaust emissions. Health risks associated with the inhalation of individual PAHs in particulate and gaseous phases were assessed on the basis of its benzo(a)pyrene equivalent concentration. Dibenzo(a,h)anthracene and benzo(a)pyrene in the particulate phase and benzo(a)pyrene and benzo(a)anthracene in the gaseous phase were the greatest contributors to the total health risks. The relative mean contributions of the total carcinogenic activity (concentrations) of all PAHs to the total concentrations of PAHs were 29.37% and 25.15% in the particulate phase and 0.76% and 0.92% in the gaseous phase during the summer and winter, respectively. These results suggest that PAHs in the particulate phase in the ambient air of Dokki may pose a potential health risk.     

Spatio-temporal prediction of atmospheric benzene (Part I)

Benzene is a carcinogenic and genotoxic pollutant which mainly affects the people health through the inhalation. Nevertheless, this pollutant is not frequently measured by air-quality networks. To solve this problem, some models have been published to estimate benzene concentrations in the atmosphere. However, the lack of measures makes difficult the application of complex models in order to get a detailed spatio-temporal analysis, namely in urban areas. In this work was developed a simple semi-empirical model to predict benzene concentrations based on the ratio of benzene and carbon monoxide concentrations in order to predict the concentrations of this pollutant in large areas and periods with lack of benzene measurements but with higher impact in the human health. The model was applied to an urban area, the Metropolitan Area of Oporto, for a period of 12 years (1995–2006). Monthly correlations between benzene and carbon monoxide concentrations at Custóias air-quality station are significant (p = 0.01) and higher in winter (r _s > 0.7) than in summer (0.3 > r _s > 0.7). Estimate of the monthly ratio of the concentration of these two pollutants range between 199 and 305. The methodology validation shows good results (r _s = 0.81) which allow, assuming the availability of carbon monoxide data, the use of this tool for areas with low benzene recorded data. The application of this methodology in the study area shows an annual average trend decrease of benzene concentrations during the study period, which may be linked to a general trend decrease of benzene emissions in European urban areas, including the study domain.     

Multisource emission retrieval within a biogas plant based on inverse dispersion calculations—a real-life example

Open digestate storage tanks were identified as one of the main methane (CH₄) emitters of a biogas plant. The main purpose of this paper is to determine these emission rates using an inverse dispersion technique in conjunction with open-path tunable diode laser spectroscopy (OP-TDLS) concentration measurements for multisource reconstruction. Since the condition number, a measure of “ill-conditioned” matrices, strongly influences the accuracy of source reconstruction, it is used as a diagnostic of error sensitivity. The investigations demonstrate that the condition number for a given source-sensor configuration in the highly disturbed flow field within the plant significantly depends on the meteorological conditions (e.g., wind speed, stratification, wind direction, etc.). The CH₄ emissions are retrieved by removing unrepresentative periods with high condition numbers, which indicate uncertainty in recovering the individual sources. In a final step, the CH₄ emissions are compared with the maximum biological methane potential (BMP) in the digestate analyzed under laboratory conditions. The retrieved methane emission rates represent an average of 50 % of the maximum BMP of the stored digestate in the winter months, while they comprised an average of 85 % during the measurement campaigns in the summer months. The results indicate that the open tanks have the potential to represent a substantial emission source even during colder periods.     

基于Matlab小波分析的南京北郊大气O3浓度变化特征研究

以2008年南京北郊大气中O₃ 质量浓度观测资料和常规观测资料为基础，利用Matlab小波分析工具，对O₃浓度的年时间序列进行分析，得出该地区的O₃ 日均浓度的变化特征：春、夏季节O3浓度大于秋、冬季节，最高浓度出现在春末夏初，最低浓度出现在冬季；并且全年共有5个突变点；弱高压的天气系统、较高的温度、较低的湿度和晴朗少云的天气是造成南京北郊O₃浓度突变的主要气象因素。结合HYSPLIT气流后向轨迹模拟，对污染源来源进行追踪，结果表明：南京北郊O₃高浓度污染来源主要分为本地局地污染和外来污染物输送两类；垂直方向上，O₃的区域尺度或中尺度的输送主要稳定在混合层的底层。     

Methane emissions of differently fed dairy cows and corresponding methane and nitrogen emissions from their manure during storage

This study investigated the effects of supplementing 40 g lauric acid (C₁₂) kg^-1 dry matter (DM) in feed on methane emissions from early-lactating dairy cows and the associated effects on methane, nitrous oxide and ammonia release from the manure during storage. Stearic acid (C₁₈), a fatty acid without assumed methane-suppressing potential in the digestive tract of ruminants, was added at 40 g kg^-1 DM to a control diet. The complete feed consisted of forage and concentrate in a ratio of 1.5:1 (DM basis). The manure was stored for 14 weeks either as complete slurry or, separately, as urine-rich slurry and farmyard manure representing two common storage systems. Methane release of the cows, as measured in respiratory chambers, was lower with C₁₂ by about 20%, but this was mostly resulting from a reduced feed intake and, partly, from a lower rate of fibre digestion. As milk yield declined less than feed intake, methane emission per kg of milk was significantly lower with C₁₂ (11.4 g) than with C₁₈ (14.0 g). Faeces of C₁₂-fed cows had a higher proportion of undigested fibre and accordingly methane release from their manure was higher compared with the manure obtained from the C₁₈-fed cows. Overall, manure-derived methane accounted for8.2% and 15.4% of total methane after 7 and 14 weeks of storage, respectively. The evolution of methane widely differed between manure types and dietary treatments, with a retarded onset of release in complete slurry particularly in the C₁₂ treatment. Emissions of nitrous oxide were lower in the manures from the C₁₂ treatment. This partially compensated for the higher methane release from the C₁₂ manure with respect to the greenhouse gas potential. The total greenhouse gas potential (cow and manure together) accounted for 8.7 and 10.5 kg equivalents of CO₂ cow^-1 d^-1with C₁₂ and C₁₈, respectively. At unaffected urine-N proportion ammonia and total nitrogen losses from stored manure were lower with C₁₂ than with C₁₈ corresponding to the differences in feed and nitrogen intake. The present results suggest that manure storage significantly contributes to total methane emission from dairy husbandry, and that the identification of effective dietary mitigation strategies has to consider both the digestive tract of the animals and the corresponding manure.     

Assessing environmental impacts of treated wastewater through monitoring of fecal indicator bacteria and salinity in irrigated soils

To assess the potential for treated wastewater irrigation to impact levels of fecal indicator bacteria (FIB) and salinity in irrigated soils, levels of Escherichia coli, Enterococcus, and environmental covariates were measured in a treated wastewater holding pond (irrigation source water), water leaving the irrigation system, and in irrigated soils over 2 years in a municipal parkland in Arizona. Higher E. coli levels were measured in the pond in winter (56 CFU 100 mL⁻¹) than in summer (17 CFU 100 mL⁻¹); however, in the irrigation system, levels of FIB decreased from summer (26 CFU 100 mL⁻¹) to winter (4 CFU 100 mL⁻¹), possibly related to low winter water use and corresponding death of residual bacteria within the system. For over 2 years, no increase in FIB was found in irrigated soils, though highest E. coli levels (700 CFU g⁻¹ soil) were measured in deeper (20–25 cm) soils during summer. Measurements of water inputs vs. potential evapotranspiration indicate that irrigation levels may have been sufficient to generate bacterial percolation to deeper soil layers during summer. No overall increase in soil salinity resulting from treated wastewater irrigation was detected, but distinct seasonal peaks as high as 4 ds m⁻¹ occurred during both summers. The peaks significantly declined in winter when surface ET abated and more favorable water balances could be maintained. Monitoring of seasonal shifts in irrigation water quality and/or factors correlated with increases and decreases in FIB will aid in identification of any public health or environmental risks that could arise from the use of treated wastewater for irrigation.     

城市绿地温室气体通量监测与减排研究

采用LGR-密闭式动态通量箱法对城市绿地生态系统温室气体(CO₂、CH₄)通量的日变化、季节变化特征及其影响因子等进行了较为系统的研究。城市绿地花草CO₂通量有明显的日变化和季节变化特征,白天通量值为负,是CO₂的净吸收汇;夜晚为正值,是CO₂的净释放源;7:00左右由源转为汇,17:00左右由汇转为源,不同花卉24 h总通量有正负2种结果。冬季草坪作为源的时间延长,而作为汇的时间缩短。光强和温度是影响CO₂通量日变化和季节变化的主要因素。城市绿地CH₄通量较小,不足以对温室气体总量产生显著影响。从减少温室气体排放的角度对城市绿地花草的选择提出了建议。     

Influence of coal-based thermal power plants on the spatial–temporal variability of tropospheric NO<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript> column over India

The oxides of nitrogen—NO _x (NO and NO₂)—are an important constituent of the troposphere. The availability of relatively higher spatial (0.25° grid) and temporal (daily) resolution data from ozone monitoring instrument (OMI) onboard Aura helps us to better differentiate between the point sources such as thermal power plants from large cities and rural areas compared to previous sensors. The annual and seasonal (summer and winter) distributions shows very high mean tropospheric NO₂ in specific pockets over India especially over the Indo-Gangetic plains (up to 14.2 × 10¹⁵ molecules/cm²). These pockets correspond with the known locations of major thermal power plants. The tropospheric NO₂ over India show a large seasonal variability that is also observed in the ground NO₂ data. The multiple regression analysis show that the influence of a unit of power plant (in gigawatts) over tropospheric NO₂ (×10¹⁵ molecules/cm²) is around ten times compared to a unit of population (in millions) over India. The OMI data show that the NO₂ increases by 0.794 ± 0.12 (×10¹⁵ molecules/cm²; annual) per GW compared to a previous estimate of 0.014 (×10¹⁵ molecules/cm²) over India. The increase of tropospheric NO₂ per gigawatt is found to be 1.088 ± 0.18, 0.898 ± 0.14, and 0.395 ± 0.13 (×10¹⁵ molecules/cm²) during winter, summer, and monsoon seasons, respectively. The strong seasonal variation is attributed to the enhancement or suppression of NO₂ due to various controlling factors which is discussed here. The recent increasing trend (2005–2007) over rural thermal power plants pockets like Agori and Korba is due to recent large capacity additions in these regions.     

Air quality at a snowmobile staging area and snow chemistry on and off trail in a Rocky Mountain subalpine forest, Snowy Range, Wyoming

A study was begun in the winter of 2000–2001 and continued through the winter of 2001–2002 to examine air quality at the Green Rock snowmobile staging area at 2,985 m elevation in the Snowy Range of Wyoming. The study was designed to evaluate the effects of winter recreation snowmobile activity on air quality at this high elevation site by measuring levels of nitrogen oxides (NO _x , NO), carbon monoxide (CO), ozone (O₃) and particulate matter (PM₁₀ mass). Snowmobile numbers were higher weekends than weekdays, but numbers were difficult to quantify with an infrared sensor. Nitrogen oxides and carbon monoxide were significantly higher weekends than weekdays. Ozone and particulate matter were not significantly different during the weekend compared to weekdays. Air quality data during the summer was also compared to the winter data. Carbon monoxide levels at the site were significantly higher during the winter than during the summer. Nitrogen oxides and particulates were significantly higher during the summer compared to winter. Nevertheless, air pollutants were well dispersed and diluted by strong winds common at the site, and it appears that snowmobile emissions did not have a significant impact on air quality at this high elevation ecosystem. Pollutant concentrations were generally low both winter and summer. In a separate study, water chemistry and snow density were measured from snow samples collected on and adjacent to a snowmobile trail. Snow on the trail was significantly denser and significantly more acidic with significantly higher concentrations of sodium, ammonium, calcium, magnesium, fluoride, and sulfate than in snow off the trail. Snowmobile activity had no effect on nitrate levels in snow.     

上海臭氧及前体物变化特征与相关性研究

于2010年1~12月期间,在上海城区内采用在线连续观测,分析该地区近地臭氧与其前体物的季节变化规律及相关性,探讨了臭氧浓度与OX和NO₂光解速率之间的关系。结果表明,观测期间,上海地区O₃总超标天数为13天,超标率为3.56%。O₃浓度变化呈现明显的秋冬低、春夏高的季节变化。O₃浓度日变化规律呈典型单峰变化,O₃各前体物呈双峰形分布,冬季O₃与NO_X的相关性最强。对OX的贡献中,秋冬以NO₂为主,春夏以O₃为主;夜间以NO₂为主,白天以O₃为主。臭氧浓度与OX和NO₂光解速率变化规律基本一致。     

Determination of road dust loadings and chemical characteristics using resuspension

The contribution of fugitive dust from traffic to air pollution can no longer be ignored in China. In order to obtain the road dust loadings and to understand the chemical characteristics of PM₁₀ and PM_2.5 from typical road dust, different paved roads in eight districts of Beijing were selected for dust collection during the four seasons of 2005. Ninety-eight samples from 28 roads were obtained. The samples were resuspended using equipment assembled to simulate the rising process of road dust caused by the wind or wheels in order to obtain the PM₁₀ and PM_2.5 filter samples. The average road dust loading was 3.82 g m^− 2, with the highest of 24.22 g m^− 2 being in Hutongs in the rural–urban continuum during winter. The road dust loadings on higher-grade roads were lower than those on lower-grade roads. Attention should be paid to the pollution in the rural–urban continuum areas. The sums of element abundances measured were 16.17% and 18.50% for PM₁₀ and PM_2.5 in road dust. The average abundances of OC and EC in PM₁₀ and PM_2.5 in road dust were 11.52%, 2.01% and 12.50%, 2.06%, respectively. The abundance of elements, water-soluble ions, and OC, EC in PM₁₀ and PM_2.5 resuspended from road dust did not change greatly with seasons and road types. The soil dust, construction dust, dust emitted from burning coal, vehicle exhaust, and deposition of particles in the air were the main sources of road dust in Beijing. Affected by the application of snow-melting agents in Beijing during winter, the amount of Cl⁻ and Na⁺ was much higher during that time than in the other seasons. This will have a certain influence on roads, bridges, vegetations, and groundwater.     

Diurnal trends in coarse particulate matter composition in the Los Angeles Basin

To investigate the diurnal profile of the concentration and composition of ambient coarse particles, three sampling sites were set up in the Los Angeles Basin to collect coarse particulate matter (CPM) in four different time periods of the day (morning, midday, afternoon and overnight) in summer and winter. The samples were analyzed for total and water-soluble elements, inorganic ions and water-soluble organic carbon (WSOC). In summer, highest concentrations of CPM gravimetric mass, mineral and road dust, and WSOC were observed in midday and afternoon, when the prevailing onshore wind was stronger. In general, atmospheric dilution was lower in winter, contributing to the accumulation of air pollutants during stagnation conditions. Turbulences induced by traffic become a significant particle re-suspension mechanism, particularly during winter night time, when mixing height was lowest. This is evident by the high levels of CPM mass, mineral and road dust in winter overnight at the near-freeway sites located in urban Los Angeles, and to a lesser extent in Riverside. WSOC levels were higher in summer, with a similar diurnal profile with mineral and road dust, indicating that they either share common sources, or that WSOC may be adsorbed or absorbed onto the surfaces of these dust particles. In general, the contribution of inorganic ions to CPM mass was greater in the overnight sampling period at all sampling sites, suggesting that the prevailing meteorological conditions (lower temperature and higher relative humidity) favor the formation of these ions in the coarse mode. Nitrate, the most abundant CPM-bound inorganic species in this basin, is found to be predominantly formed by reactions with sea salt particles in summer. When the sea salt concentrations were low, the reaction with mineral dust particles and the condensation of ammonium nitrate on CPM surfaces also contributes to the formation of nitrate in the coarse mode.     

Characteristics and sources of non-methane hydrocarbons and halocarbons in wintertime urban atmosphere of Shanghai, China

The characteristics and sources of major hydrocarbons and halocarbons in the wintertime ambient air of urban center of Shanghai, a mega city of China, were investigated. Propane, toluene, ethyl acetate, and benzene were the most abundant hydrocarbons. The majority of species showed significant variability in mixing ratios with occasional episodic increases. The more common use of liquefied petroleum gas fuel for taxis and light motorcycles was believed to lead to high levels of ambient propane over the urban center of Shanghai. Correlating with toluene, dichloromethane, and 1,2-dichloroethane (1,2-DCE), abundant chloromethane (up to a daily mean of 1.61?±?0.99 ppbv and a maximum of 5.34 ppbv) was mainly associated with industrial emissions, although biomass burnings exist widely in east China. The Chinese New Year (CNY) holiday period with no industrial activity over China provides a platform for the study of industrial emissions over the urban atmosphere of Shanghai. The normal weekly cycles were characterized by higher and more variable mixing ratios during weekdays which dropped during weekends. Enhanced mixing ratios were observed in the fortnight before the CNY holidays due to increased industrial emissions as a result of overtime production to make up for the holiday losses. During the CNY holidays, lower level and less variable mixing ratios were observed. A benzene/toluene (B/T) ratio of 0.6?±?0.4 (mean?±?std.) for the morning rush hour samples was identified to be the characteristic ratio of vehicular emissions. However, a B/T ratio of 0.4?±?0.2 from vehicles and other sources was derived for the ambient air.     

Carbon monoxide concentrations in Santiago City at street levels and their vertical gradient

Carbon monoxide concentrations were measured at ground level (1 m) near heavy traffic streets in downtown Santiago de Chile in periods of low (November and December), intermediate (April) and high (May) ambient concentrations. Also, measurements were carried out at several heights (from 1 to 127 m) in Santiago’s main street during winter time. Measurements carried out at ground level show maximum values during the morning rush hour, with values considerably higher than those reported by the urban air quality network, particularly in summer time. However, the measured values are below air quality standards. Vertical CO profiles were measured in a tower located in the center of downtown. Below 40 m (average altitude of neighboring buildings), the profiles do not show a consistent vertical gradient, with CO concentrations increasing or decreasing with height, regardless of atmospheric stability. In this low altitude range, the observed vertical profiles are poorly predicted by a street canyon model, and the measured concentrations can not be described by a simple exponential decay. At higher altitudes (40 and 127 m) a negative gradient in CO concentrations is observed, both for stable and unstable atmospheric conditions. The values of CO measured at 127 m are relatively well described by an Eulerian dispersion model running with current CO emission inventories for Santiago, although this model tends to predict stepper CO gradients than the observed ones.     

Vertical ozone variation in the lower troposphere of Delhi

Measurements of ozone in the urban environment of Delhi were carried out at ground level and heights of 23m, 51m, 117m and 153m at four different sites synoptically during 1989–90. A considerable ozone build up was observed all over Delhi and a significant vertical variation in its concentration was observed at all sites. At any given time O₃ levels were lowest at ground level and invariably increased with increasing distance from the ground.     

Greenhouse gas emissions from forestry,land-use changes,and agriculture in Tanzania

The purpose of the study was to identify and quantify anthropogenic sources and sinks of greenhouse gases from forestry, land-use changes and agriculture in Tanzania. The 1990 inventory revealed that, in the land-use sector, methane (CH₄) and carbon dioxide (CO₂) are the primary gases emitted. Enteric fermentation in livestock production systems is the largest source of CH₄. Although deforestation results in greenhouse gas emissions, the managed forests of Tanzania are a major CO₂ sink.     

Effectiveness of non-CO2 greenhouse gas emission reduction technologies

Non-CO₂ greenhouse gases, such as methane and nitrous oxide, can make a relevant contribution to the enhanced greenhouse effect, and hence emission reduction is desirable. In emission reduction inventories, both the magnitude of the emission reduction as well as the specific emission reduction costs should be determined. The current knowledge of the potential for and costs of reducing these emissions is still limited. Taking this into account, the following results can be obtained. Methane emissions can be considerably reduced from underground coal mining, oil production, natural gas operations, landfilling of waste, and wastewater treatment. Also emissions from enteric fermentation and animal manure can be reduced substantially. The total technical potential for methane emission reduction (given the present activity level) is estimated to be about one third. The economic potential, having net negative emission reduction costs, is estimated to be about half of this value. These reductions can be attained over a period of 10 – 20 years. The technical potential for the reduction of nitrous oxide emissions is currently estimated to be less than 10% Apart from the possibility of implementing existing techniques, there seems to be considerable room for developing techniques for more far-reaching emission reductions both for methane and nitrous oxide.     

The characteristics of size distribution of suspended particulates in the air for sulphates and selected metals in different areas and seasons

The characteristics of the distribution of particles by size were investigated for sulphates and selected metals (Pb, Fe, Mn, and Cu) in the air in two urban and an industrial area during the winter and summer periods using an Andersen cascade impactor.In the case of metals, but not sulphates, the character of the area affected the value of mass median diameter. Lowest values were obtained in a sparsely populated urban area, whereas in a densely populated urban area and in the industrial area the values were higher.In the industrial area a high correlation coefficient was found between sulphate and manganese, and between sulphate and lead, as well as a high value of the equivalent Mn²⁺/SO _inf4 ^sup2- ratio for the total sample. It may therefore be assumed that in the industrial area manganese produces a catalytic effect on SO₂ conversion to sulphate. Among the investigated metals lead stands out as a dominant cation which binds to the sulphate ion in the industrial and densely populated areas.