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1.
Measurements of OH, H2SO4, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HOx sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HOx radical source in the form of snow emissions of CH2O and/or H2O2. This would lead one to think that either CH2O and/or H2O2 snow emissions represent a significant HOx radical source under summertime conditions at SP. Observations of H2SO4 and MSA revealed both species to be present at very low concentrations (e.g., 5 × 105 and 1 × 105 molec cm?3, respectively), but similar to those reported in 2000. The first measurements of SO2 at SP demonstrated a close coupling with the oxidation product H2SO4. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.  相似文献   

2.
Soils have long been recognised as sulfur dioxide (SO2) sinks, but we show that they can also be sources of atmospheric SO2. Using static chambers and micrometeorological techniques, we have measured emissions of SO2 from coastal lowland soils containing sulfides (mostly pyrite), commonly referred to as acid sulfate soils in Australia. SO2 evolution seems coupled to evaporation of soil water containing sulfite. The global emissions of S from acid sulfate soils is estimated at about 3 Tg/year, which is of the same order as emissions from terrestrial biogenic sources and biomass burning and is about 3% of known anthropogenic emissions of S.  相似文献   

3.
A manual method for measuring reduced sulfur compounds in kraft pulp mill and sulfur recovery plant emissions was evaluated. The method involves removing SO2 from the gas stream (if present) with a citric acid-potassium citrate buffer that passes reduced sulfur compounds; thermal oxidation of all reduced sulfur compounds to SO2; collection of the SO2 in H2O2; and a titrimetric analysis of the H2O2 for SO4 2?. A heated filter removes alkaline particulate matter that would produce a negative interference if absorbed by the buffer. When used at kraft pulp mills, the method agrees closely with Reference Method 16, provided that nonregulated reduced sulfur compounds, such as carbonyl sulfide, are not present in the emissions. At sulfur recovery plants, nonregulated reduced sulfur compounds, such as thiophene, are likely to be present in the emissions and will produce a positive bias in the results obtained with this method. The precision of the method ranges from 1 to 7 percent relative standard deviation.  相似文献   

4.
Abstract

In Mexico City, the use and composition of fuels determine that carbon monoxide (CO) comes mostly from mobile sources, and sulfur dioxide (SO2) from fixed and mobile sources. By simultaneously measuring hydrocarbons (HC), CO, and SO2 in the atmosphere of Mexico City, the relative amounts coming from different sources can be estimated. Assuming that some HC are emitted proportionally to CO emissions, we can establish that [HC]1= m1? [CO], where the proportionality constant ml corresponds to the ratio of emissions factor for HC and CO in mobile sources. Similarly for fuels containing sulfur, it can be assumed that [HC]2 = m2 ? [SO2]. In this way, the total HC are [HC]total=[HC]0+ ml ? [CO]+ m2 ? [SO2], where [HC]0 corresponds mainly to other sources like solvent evaporation, gas consumption, and natural emissions. In this way, it can be estimated that in Mexico City 75% of average HC comes from mobile sources, 5% from sulfur-related sources, and 19% from natural sources and solvent evaporation. Compared with the HC/CO ratio measured in the exhaust pipe of vehicles, we estimated that 70% of HC emitted from mobile sources are evaporative losses, and only 30% come through the exhaust system.  相似文献   

5.
This paper presents an examination of industrial coal-fired boiler waste products. Presently the atmospheric emissions from all new boilers larger than 250 × 106 Btu/hr are controlled by existing New Source Performance Standards, and boilers smaller than 250 × 106 Btu/hr are controlled to levels required by the regulations of the particular state in which the facility is located. The 1977 Clean Air Act Amendments, however, specify categories of sources for which EPA must develop revised New Source Performance Standards. Industrial coal-fired boilers are included as one of these categories, and a relevant issue concerns the potential amount of solid waste generated as a result of tightened emission standards that require flue gas desulfurization. This paper examines the air quality and solid waste impacts of moderate and stringent emission controls for particulate and SO2 emissions from industrial coal-fired boilers.

Comparisons are presented of physical and chemical characterizations of the emissions and solid wastes produced when boilers are equipped with particulate and SO2 control equipment. The SO2 systems examined are lime spray drying, lime/limestone, double alkali, sodium throwaway, physically cleaned coal, and fluidized-bed combustion. The solid waste disposal alternatives and the disposal costs are discussed. The most common disposal methods used are landfill for dry wastes and impoundment for sludges, with special wastewater treatment requirements for the sodium throwaway aqueous wastes.  相似文献   

6.
Abstract

Emitted pollutants from the Agios Dimitrios lignite-fired power plant in northern Greece show a very strong linear correlation with the free calcium oxide content of the lignite ash. Dust (fly ash) emissions are positively correlated to free calcium oxide content, whereas sulfur dioxide (SO2) emissions are negatively correlated. As a result, at present, the Agios Dimitrios Power Plant operates very strictly within the legislative limits on atmospheric particulate emission. In the present study, the factors to be considered in assessing the impact of lignite combustion on the environment are presented and evaluated statistically. The ash appears to have a remarkable SO2 natural dry scrubbing capability when the free calcium oxide content ranges between 4 and 7%. Precipitator operating problems attributable to high ash resistivity can be overcome by injecting sulfur trioxide to reduce the ash resistivity, with, of course, a probable increase in operating costs.  相似文献   

7.
Plant species release appreciable quantities of volatile organic substances to the atmosphere. The major compounds emitted are monoterpenes (C10) like α-pinene, β-pinene, and limonene and the hemiterpene (C5) isoprene. The rate of emission of isoprene is light dependent and ranges between 0.04 to 2.4 ppb/cm2/min/l for oak, cottonwood, and eucalyptus foliage. The rate of emission of a- and/3-pinene and limonene is dependent on the rate of transpiration, structural integrity of the oil cells and resin glands, and temperature of the foliage. Rates of emission for conifer foliage range from 0.4 to 3.5 ppb/g/min/l. An inventory of North American forest regions for the frequency of occurrence of these chemicals released by different tree species showed that 15% was the lowest value for a specific forest-type that emitted terpenes to the atmosphere. More commonly 100% of the trees of a given forest-type emitted terpenes to the atmosphere. An average of 70% is typical of the United States forested regions as a whole. The annual contribution of forest hydrocarbon emissions to the air pollution problem on a global basis is reflected in the 175 × 106 tons of reactive hydrocarbons from tree foliage sources compared to the 27 × 106 tons from man’s activities; in other words, there is a 6.2-fold greater emission level from natural sources than from man made sources. The fate of these gaseous olefins in the atmosphere is undetermined.  相似文献   

8.
Multi-year inventories of vehicular emissions at a high spatial resolution of 40 km×40 km were established in China using the GIS methodology for the period 1980–2005, based on provincial statistical data from yearbooks regarding vehicles and roads, and on the emission factors for each vehicle category in each province calculated by COPERT III program. Results showed that the emissions of CH4, CO, CO2, NMVOC, NOx, PM10, and SO2 increased from 5, 1066, 19 893, 169, 174, 26, and 16 thousand tons in 1980 to 377, 36 197, 674 629, 5911, 4539, 983, and 484 thousand tons in 2005 at an annual average rate of 19%, 15%, 15%, 15%, 14%, 16%, and 15%, respectively. Statistical analysis of vehicular emissions and GDP showed that they were well positively correlated, which revealed that increase of pollutant emissions has been accompanying the growth of GDP. Spatial distribution of pollutant emissions was rather unbalanced: over three-quarters of the total emissions concentrated in developed regions of China's southeastern, northern and central areas covering only 35.2% of China's territory, while the remaining emissions were distributed over the southwestern, northwestern and northeastern regions covering as much as 64.8% of the territory. In 2005, the Beijing–Tianjin–Hebei region, the Yangtze River Delta, and the Pearl River Delta covering only 2.3%, 2.2%, and 1.9%, respectively, of the territory, generated about 10%, 19%, and 12%, respectively, of the total emissions. Since 1990, motorcycles have been the major contributors to the CH4, CO, NMVOC, and PM10 emissions, due to the large population. Heavy-duty vans were the major contributors to the NOx and SO2 emissions because of high emission factors. Passenger cars contributed about one third of the emissions of each pollutant. Contributions of vehicle categories to emissions varied from province to province, due to the diversity of vehicle compositions among provinces.  相似文献   

9.
The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H2S, CH3SH, DMS, CS2, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO2) was produced photochemically during the summer (about 34% of total SO2 concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO2 was dominated by H2S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO2 concentrations occurred around the D-LF during summer. The total SO2 concentrations produced from source type N around the D-LF during the summer (a mean SO2 concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO2 emissions and their photochemistry along with the wind convergence.  相似文献   

10.
Due to the dynamic nature of the atmosphere, substantial amounts of gaseous and particulate pollutants are transported to the areas distant from their sources. In order to determine the regional concentration levels of atmospheric pollutants in Lithuania, concentrations of gaseous O3, SO2, NO2 and other pollutants have been measured at the Preila background station (55°20′ N and 21°00′ E, 5 m a.s.l.) since 1981. The long-term concentration data set enabled us to get temporal trends, both on a seasonal and longer time scale, to identify source areas of pollutants and to relate them to the emission data. Based on the data obtained, the different tendencies in the pollutant concentration changes were revealed. Positive trends for ozone (of 2.9% per year during 1983–2000) and a distinct negative trend for both sulphur dioxide (of 3.8% per year during 1981–2000) and nitrogen dioxide (of 3.8% per year during 1983–2000) were found. The air mass back-trajectory analysis was used to assess the source region of air pollutants transported to Lithuania. The pollutant concentration levels were compared with their emission changes in Europe and Lithuania. The general trends in SO2 as well as in NO2 concentrations observed are consistent with changes in SO2 and NO2 emissions in Europe and Lithuania.  相似文献   

11.
Abstract

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter y CO2max, which is equal to the maximum carbon dioxide (CO2) content by vol ume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.  相似文献   

12.
Electron microscopy-energy dispersive spectroscopy (EM/EDS) can be used to determine the elemental composition of individual particles. However, the accuracy with which atmospheric particle compositions can be quantitatively determined is not well understood. In this work we explore sources of sampling and analytical bias and methods of reducing bias. Sulfuric acid [H2SO4] and ammonium sulfate [(NH4)2SO4] particles were collected on beryllium, silicon, and carbon substrates with similar deposition densities. While [(NH4)2SO4] particles were observed on all substrates, [H2SO4] and ammonia-treated [H2SO4] particles could not be found on beryllium substrates. Interactions between the substrate and sulfuric acid particles are implicated. When measured with EM/EDS, [H2SO4] particles exposed to ammonia overnight were found having lower beam damage rates (0.000 ± 0.002 fraction s−1) than those without any treatment (0.023 ± 0.006 fraction s−1) For laboratory-generated [C10H6(SO3Na)2] particles, the composition determined using the experimental k-factors evaluated from independent particle standards of similar composition and size shows an error less than 20% for all constituents, while greater than 78% errors were found when k-factors were calculated from the theory. This study suggests (1) that sulfate beam damage can be reduced by exposure of atmospheric particle samples to ammonia before analysis, (2) that beryllium is not a suitable substrate for atmospheric particle analysis, and (3) calibration (k-factor determination) using particle standards of similar size and composition to particles present in the atmosphere shows promise as a way of improving the accuracy of quantitative EM analysis.  相似文献   

13.
To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO42−) and methanesulfonate (MSx used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS levels. The modelling results indicate that about 80% of the production of MS can be attributed to heterogeneous reactions.Observed submicron nss-SO42− levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO2) to sulfuric acid (H2SO4), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO42− can be explained by condensation of gas-phase H2SO4, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO2 and H2SO4) in good agreement with earlier estimates for the area.  相似文献   

14.
ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF6) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H2SO4. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF6 dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF6 concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF6 dissociation, mainly H2SO4, SO2, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF6, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF6 concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF6 concentration is kept at a low ppb level.  相似文献   

15.
Title IV of the Clean Air Act Amendments of 1990 establishes a unique “market-based“ approach to reduce national electric utility sulfur dioxide (SO2) emissions during the next century by about 10 million tons/year below the corresponding level in 1980. This program is designed to provide utility operators with the flexibility to achieve the applicable SO2 emissions limitations (total tons) using the most cost-effective approach. However, in reality, it is unlikely that many utility operators would have such operational flexibility, especially in the case of plants located in the Western United States. This is due to the fact that these sources may also be subject to other more stringent provisions of the Act, such as to protect public health and visibility, which override the Title IV provisions.

This paper examines the Phase II allowance allocations for the utility units located in the 11 western states and assesses the potential impacts of the current federal/state air quality regulatory programs on the allowance market in the West. This analysis shows that, even after accounting for the projected population growth and the accompanying growth in electric power demand during the next decade, the West should have a surplus of allowances, especially if new regulations are initiated to further reduce SO2 emissions, mainly for the purpose of improving visibility in Western Class I areas.  相似文献   

16.
Bacteriogenic production of H2S occurs in fine-grained anoxic muds, is promoted by organic and nutrient pollution of water, peaks in the warm months of the year, and is the source of most of the estimated 100 to 200 million tons of biogenic sulfur annually contributed to the global atmosphere. We tested the hypothesis that biogenic sulfur contributes to the atmospheric load of sulfate in urban and nonurban sites by statistical analyses of the 24 hour sulfate levels measured in 4 coastal and 3 Inland nonurban sites where pollutant sulfur dioxide emissions are absent or negligible, and in 8 coastal and 10 inland urban sites, all located in New England or Middle Atlantic states.

Comparisons of annual and seasonal mean sulfate levels show that in nonurban groups summertime sulfate levels significantly exceed wintertime levels, and in summer, sulfate levels in urban sites are nearly the same as in nonurban sites. Comparisons of group sulfate means in 4 New York cities near extended bodies of polluted water with those in 10 inland upstate New York cities show significantly higher levels in the cities near polluted water in spring, summer, and fall and for the year as a whole, but not in winter, when the levels were similar. When the nonurban and urban sites are grouped for proximity to coasts (where bacterial sulfate reduction is active in sediments) paired groups of coastal and inland urban and nonurban sites show no significant differences in sulfate levels in summer and fall.

Studies of the summertime sulfate means in New York state show no evidence of an elevated anthropogenic background which could explain the high summertime sulfate level observed in one nonurban site in that state, while analyses of the day to day fluctuations in urban and nonurban sites support the conclusion that nonurban sites have large local (biogenic) sulfate sources in summer and fall, and that local sulfate sources also exist in spring and may exist in winter.

We conclude that biogenic sulfate sources contribute most of the sulfate observed in the cities studied during summer and fall, and in some cities also contribute in other seasons. These biogenic contributions vary with local conditions and are estimated to contribute up to 6 µg/m3 (50%) or more to the annual geometric mean sulfate levels observed in some cities located near extensive bodies of polluted water.  相似文献   

17.
Airborne measurements of gaseous and particulate sulfur and nitrogen pollutants were made in southwestern Kentucky on the afternoon of October 21, 1979. Back-trajectory analysis indicates that the sampled air parcel moved over northern Florida, Alabama, and western Tennessee during the two days prior to sampling. Before moving over Florida, the air parcel was over the Atlantic Ocean for at least five days. Analytical long-range transport (LRT) model predictions based on anthropogenic emissions account for only about 75% of the airborne measured concentrations of 14.7 μg m?3 for SO2 and 4.8 μg m?3 for SO4 2?. The remaining 25 % is thought to be due to biogenic sulfur emissions from the extensive wetland areas along the Gulf Coast.

Forward-trajectory analysis indicates that the air parcel moved to the Adirondack Mountains of New York State 24 hours after sampling. Model predictions indicate that SO2 and SO4 2? mean layer concentrations at the Adirondacks were 24 and 16 μg?3, respectively. Almost half of this sulfur was estimated to come from emissions in the heavily industrialized region along the Ohio River Valley.

Further comparisons used a measurement data base obtained in southeastern Canada and the state of Arkansas during August 1976. An air parcel was tracked for seven days as it entered the north central United States, stagnated over the lower midwest, and then moved to eastern Canada. Model predictions were in substantial agreement with regional SO4 2? concentrations measured at a number of ground-level sites. Average SO4 2? concentrations measured in central Arkansas on August 10, 1976 were 20 μ m?3 vs. a modeled value of 19 μ m?3. Average SO4 2? concentrations measured in Nova Scotia four days later were 22 μg?3 vs. a modeled estimate of 24 μg?3.  相似文献   

18.
Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water, over the range of atmospheric concentrations of 0.81?8.73 mg SO2/M3, is a function of the concentration of SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmospheric SO2. The pH of the exposed water samples reached values of 4.0 or less, comparable to values observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in distilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.  相似文献   

19.
A study was carried out to investigate the emissions of SO2 and primary sulfate materials (H2SO4 and inorganic particulate matter) from a boiler burning fossil fuel and using a wet-limestone scrubber for SO2 removal. Experiments were designed to assess the scrubbing efficiency for SO2 and sulfate, as well as the potential for scrubber liquor reentrainment. The boiler studied was an 820 MW cyclone-fired unit equipped with a wet, limestone scrubber, consisting of eight two-stage venturi-absorber modules designed to treat a flue gas flow rate of 2,760,000 acfm. The boiler fuel was a low-grade sub-bituminous coal with ash and sulfur contents of 25 and 5%, respectively. Multiple-sampling methods were employed concurrently on the inlet and outlet of a candidate absorber module to measure SO2, total water-soluble sulfate, and free H2SO4. Samples were collected during three field experiments from September 1977 through April 1978. The average SO2 scrubbing efficiency was 76% and was observed to decrease over the 5 day operation/maintenance cycle of the module. The total water-soluble sulfate input to the scrubber amounted to approximately 1% of the total sulfur oxides and was composed of a 5:1 ratio of H2SO4 to particulate sulfate. The total sulfate scrubbing efficiency, averaging about 29%, was invariant with respect to SO2 removal. The sulfate emissions measured in the scrubber exit gas consisted of about 85 % H2SO4 as a fine aerosol. Mass emissions of acid and particulate sulfate were calculated as 1730 Ib/hr and 305 Ib/hr, respectively.  相似文献   

20.
One of the more common and useful methods of testing for SO2 in the atmosphere is to use the Huey sulfation plate.1 It has a layer of PbÕ2 particles suspended in an inert substrate which reacts with ambient SO2 gas to form PbSÛ4. The amount of PbSÛ4 can be determined by gravimetric, spec-trophotometric, or turbidimetric methods. The amount of atmospheric SO2 is estimated by assuming a linear correlation between it and measured PbS04 on the plate.  相似文献   

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