Effect of topography on sulfate redistribution in cumulonimbus cloud development

An aqueous chemical module is created and included into a complex three-dimensional atmospheric cloud-resolving mesoscale model. In the chemical module, oxidation of S(IV) by ozone and hydrogen peroxide in cloud-water and rainwater, as important process of the sulfate production is included. To examine the impact of topography on the sulfate redistribution in a clean and a polluted environment, the complex topography of Serbia is included in the model. Numerical simulations of an isolated summer Cumulonimbus cloud shows that thunderstorms generate very strong vertical sulfate redistribution from the planetary boundary layer to the upper troposphere. This redistribution is sensitive to cloud dynamics, while cloud microphysics and precipitation determine wet removal of the chemical species. In simulations with realistic topography, the chemical species are transported over larger distances close to the surface, while in the upper atmosphere, there is no difference compared to the simulations without topography. The sensitivity tests of cloud chemistry to the physical processes are made. Omission of nucleation and impact scavenging of aerosols in the model simulations shows that 75.8 and 62.5 % of total sulfur mass deposited in the base experiment for the clean and the polluted environment, respectively, is the result of other processes. Exclusion of oxidation accounted for 19.2 and 37.7 % of total sulfur deposited for clean and polluted environment. Ignoring the ice phase almost not change mass of deposited sulfur: there is an increase of 2.9 and 1.5 % for clean and polluted atmosphere, respectively. Real topography conditions affect the sulfate redistribution in the sense of greater possibilities of transport. Numerical simulations without real topography give an artificial increase of deposited sulfur mass of about 25?30 %.     

Source and Budget of Sulfate in Precipitation From Central Alberta,Canada

Rain, hail, and snow samples collected in central Alberta have been analyzed for sulfate and chloride content using a conductometric titration method. The mean values of sulfate concentration in rain and hail collected in the region of sulfur extraction gas plants were 2.7 mg/l and 2.9 mg/l respectively. The mean value of the sulfate content of a large number of hail samples collected from one severe storm well removed from a major SO₂ source was only 0.6 mg/l. Several snow samples collected in Alberta and southern British Columbia had a mean sulfate content of less than 0.5 mg/l. These results are discussed in terms of the efficiency with which SO₂ is removed from the atmosphere by the different precipitation processes. The results strongly suggest that most of the sulfate found in central Alberta precipitation is of local industrial origin.

By comparing the sulfate deposition in precipitation around one isolated gas plant with the known SO₂ emission rate, a local atmospheric sulfur budget is derived. This budget indicates that the summertime convective storms are a very efficient mechanism for removing the SO₂ from the atmosphere, with between 32 and 46% of the sulfur emitted as SO₂ arriving at the ground as sulfate sulfur within a radius of 25 miles of the source. In contrast snow is a very inefficient removal mechanism, since in winter less than 2% of the sulfur emission is deposited in the snowfall near the source.     

Sulfur deposition simulations over China, Japan, and Korea: a model intercomparison study for abating sulfur emission

In response to increasing trends in sulfur deposition in Northeast Asia, three countries in the region (China, Japan, and Korea) agreed to devise abatement strategies. The concepts of critical loads and source?Creceptor (S?CR) relationships provide guidance for formulating such strategies. Based on the Long-range Transboundary Air Pollutants in Northeast Asia (LTP) project, this study analyzes sulfur deposition data in order to optimize acidic loads over the three countries. The three groups involved in this study carried out a full year (2002) of sulfur deposition modeling over the geographic region spanning the three countries, using three air quality models: MM5-CMAQ, MM5-RAQM, and RAMS-CADM, employed by Chinese, Japanese, and Korean modeling groups, respectively. Each model employed its own meteorological numerical model and model parameters. Only the emission rates for SO₂ and NO_x obtained from the LTP project were the common parameter used in the three models. Three models revealed some bias from dry to wet deposition, particularly the latter because of the bias in annual precipitation. This finding points to the need for further sensitivity tests of the wet removal rates in association with underlying cloud?Cprecipitation physics and parameterizations. Despite this bias, the annual total (dry plus wet) sulfur deposition predicted by the models were surprisingly very similar. The ensemble average annual total deposition was 7,203.6?±?370 kt S with a minimal mean fractional error (MFE) of 8.95?±?5.24?% and a pattern correlation (PC) of 0.89?C0.93 between the models. This exercise revealed that despite rather poor error scores in comparison with observations, these consistent total deposition values across the three models, based on LTP group's input data assumptions, suggest a plausible S?CR relationship that can be applied to the next task of designing cost-effective emission abatement strategies.     

Haze trends over the United States, 1980–1995

The patterns and trends of haze over the United States for the period of 1980–1995 are presented. Haze measurements are based on human visual range observations at 298 synoptic meteorological stations operated by the United States Weather Service. There was a significant (∼10%) decline in haziness over the 15-yr period. The reductions were evident throughout the eastern United States as well as over the hazy air basins of California. During the same period, in the eastern United States sulfur emissions also declined by about 10%. However, a causality for the reductions has not been established. This report is an update of an earlier survey of haze patterns and trends from 1950 to 1980.     

Estimation of Trends in Atmospheric Concentrations of Sulfate in the Northeastern United States

Abstract

Daily atmospheric concentrations of sulfate collected at six locations in the northeastern United States are regressed against meteorological factors, ozone, seasonal cycles, and time in order to determine if a significant trend in sulfate can be detected. The data used in this analysis were collected during the Sulfate Regional Experiment (SURE, 1977-1978) and the Eulerian Model Evaluation Field Study (EMEFS, 1988-1989). Ozone, specific humidity, and seasonal terms (reflecting the potential of the atmosphere for oxidation of sulfur dioxide) emerged as important explanatory variables. After accounting for the variability explained by environmental factors, the median estimated change in sulfate concentration from the six locations over the 11-year period is -22% (or -28% if ozone is not used as an explanatory variable). Although there are wide variations among locations, these changes are commensurate with an estimated 25% decline in sulfur emissions in the northeastern U.S. during the same period. These analyses provide insight into methods for detecting reductions in sulfate that may be expected to occur as a result of the Clean Air Act Amendments of 1990. Uncertainties in the estimates, with consideration of serial correlation in the data, imply a minimum detectable reduction of 10% using this modeling procedure with similar data availability.     

Transport and transformation of sulfur compounds over East Asia during the TRACE-P and ACE-Asia campaigns

On the basis of the recently estimated emission inventory for East Asia with a resolution of 1×1°, the transport and chemical transformation of sulfur compounds over East Asia during the period of 22 February through 4 May 2001 was investigated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the regional atmospheric modeling system (RAMS). For evaluating the model performance simulated concentrations of sulfur dioxide (SO₂) and aerosol sulfate (SO₄²⁻) were compared with the observations on the ground level at four remote sites in Japan and on board aircraft and vessel during the transport and chemical evolution over the Pacific and Asian Pacific regional aerosol characterization experiment field campaigns, and it was found that the model reproduces many of the important features in the observations, including horizontal and vertical gradients. The SO₂ and SO₄²⁻ concentrations show pronounced variations in time and space, with SO₂ and SO₄²⁻ behaving differently due to the interplay of chemical conversion, removal and transport processes. Analysis of model results shows that emission was the dominant term in regulating the SO₂ spatial distribution, while conversion of SO₂ to SO₄²⁻ in the gas phase and the aqueous phase and wet removal were the primary factors that controlled SO₄²⁻ amounts. The gas phase and the aqueous phase have the same importance in oxidizing SO₂, and about 42% sulfur compounds (25% in SO₂) emitted in the model domain was transported out, while about 57% (35% by wet removal processes) was deposited in the domain during the study period.     

Spotting zones of dissimilatory sulfate reduction in a forested catchment: the 34S-35S approach

The localization of sulfate reducing sites in forested catchments is of major importance, because dissimilatory sulfate reduction can be a considerable sink for deposited sulfate. To localize dissimilatory sulfate reduction sites in a forested catchment (northeastern Bavaria, Germany), three sites within the catchment (upland site, intermittent seep, fen) were investigated for delta 34S depth profiles of soil sulfur and potential sulfate reduction rates were measured with 35S radiolabeling. Stable sulfur isotopes indicate that aerobic metabolism is the dominant process on the upland site and the intermittent seep (delta 34S of soil sulfur between +1.6 and +9.0@1000) and dissimilatory reduction is not a significant sink for sulfate. However, results of the 35S radiolabeling indicated for the upland site that the soil has potentially high sulfate reduction rates under laboratory conditions. Soil sulfur of the fen was markedly depleted in 34S (delta 34S between -6 and +2.6@1000). Both, 34S and 35S data indicated that dissimilatory sulfate reduction is an ongoing process on this site. The 34S and 35S approaches are complementary. While measurements using 35S can show momentary potential for dissimilatory bacterial sulfate reduction, delta 34S data reflect long-term predominance of either assimilatory or dissimilatory S metabolism at a particular site.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Long-range transport of acidifying substances in East Asia—Part II: Source–receptor relationships

Region-to-grid source–receptor (S/R) relationships are established for sulfur and reactive nitrogen deposition in East Asia, using the Eulerian-type Community Multiscale Air Quality (CMAQ) model with emission and meteorology data for 2001. We proposed a source region attribution methodology by analyzing the non-linear responses of the CMAQ model to emission changes. Sensitivity simulations were conducted where emissions of SO₂, NO_x, and primary particles from a source region were reduced by 25%. The difference between the base and sensitivity simulations was multiplied by a factor of four, and then defined as the contribution from that source region. The transboundary influence exhibits strong seasonal variation and generally peaks during the dry seasons. Long-range transport from eastern China contributes a significant percentage (>20%) of anthropogenic reactive nitrogen as well as sulfur deposition in East Asia. At the same time, northwestern China receives approximately 35% of its sulfur load and 45% of its nitrogen load from foreign emissions. Sulfur emissions from Miyakejima and other volcanoes contribute approximately 50% of the sulfur load in Japan in 2001. Sulfur inflows from regions outside the study domain, which is attributed by using boundary conditions derived from the MOZART global atmospheric chemistry model, are pronounced (10–40%) over most parts of Asia. Compared with previous studies using simple Lagrangian models, our results indicate higher influence from long-range transport. The estimated S/R relationships are believed to be more realistic since they include global influence as well as internal interactions among different parts of China.     

低温等离子体治理H2S污染的实验研究

低温等离子体技术是一种高效、快速的污染消除技术，国内外都在对其进行广泛而深入的研究。采用脉冲电晕放电等离子体对空气中的硫化氢进行降解研究，探索了、脉冲峰压、脉冲频率、气体流量以及气体初始浓度对净化效果的影响，气体浓度由气相色谱仪测定。结果表明，脉冲电晕放电可以有效消除硫化氢污染，净化率随脉冲峰压和脉冲频率的增加而提高，随气体初始浓度和流量的增加而下降，且在初始浓度360mg／m^2、流量1200mL／min、脉冲峰压30kV、脉冲频率80Hz的条件下，处理后的气体中已检测不到H2S，根据色谱检测限（0．29mg／m^3）计算出的净化率≥99．92％。采用离子色谱对产物进行了定性分析，发现H2S经放电处理后主要产物为SO2和SO3。     

低温等离子体治理H2S污染的实验研究

低温等离子体技术是一种高效、快速的污染消除技术,国内外都在对其进行广泛而深入的研究.采用脉冲电晕放电等离子体对空气中的硫化氢进行降解研究,探索了、脉冲峰压、脉冲频率、气体流量以及气体初始浓度对净化效果的影响,气体浓度由气相色谱仪测定.结果表明,脉冲电晕放电可以有效消除硫化氢污染,净化率随脉冲峰压和脉冲频率的增加而提高,随气体初始浓度和流量的增加而下降,且在初始浓度360 mg/m3、流量1200 mL/min、脉冲峰压30 kV、脉冲频率80 Hz的条件下,处理后的气体中已检测不到H2S,根据色谱检测限(0.29 mg/m3)计算出的净化率≥99.92%.采用离子色谱对产物进行了定性分析,发现H2S经放电处理后主要产物为SO2和SO3.     

Assessing the costs and environmental benefits of IMO regulations of ship-originated SOx and NOx emissions in the Baltic Sea

To assess the value of the environmental benefits of the Sulphur Emission regulation (SECA) that came into force in 2015, changes in depositions of SOx and NOx from ship exhaust gas emissions were modelled and monetized for the Baltic Sea region for the years 2014 and 2016. During this period, the total deposition of SOx in the study area decreased by 7.3%. The decrease in ship-originated SOx deposition from 38 kt to 3.4 kt (by over 88%) was translated into a monetary value for the ecosystem impacts of nearly 130 million USD, according to the EcoValue08 model. This is less than the modelled health benefits, but it is not insignificant. For NOx, there was no decreasing trend. The exceedance of the critical loads of SOx and NOx was also estimated. The effect of Baltic shipping on the exceedance of critical loads of acidification after SECA is very small, but Baltic shipping still has a considerable effect on the exceedance of critical loads for eutrophication.     

Sulfur dioxide and nitrogen oxides emissions from U.S. pulp and paper mills, 1980-2005

Comprehensive surveys conducted at 5-yr intervals were used to estimate sulfur dioxide (SO,) and nitrogen oxides (NO.) emissions from U.S. pulp and paper mills for 1980, 1985, 1990, 1995, 2000, and 2005. Over the 25-yr period, paper production increased by 50%, whereas total SO, emissions declined by 60% to 340,000 short tons (t) and total NO, emissions decreased approximately 15% to 230,000 t. The downward emission trends resulted from a combination of factors, including reductions in oil and coal use, steadily declining fuel sulfur content, lower pulp and paper production in recent years, increased use of flue gas desulfurization systems on boilers, growing use of combustion modifications and add-on control systems to reduce boiler and gas turbine NO, emissions, and improvements in kraft recovery furnace operations.     

Product Guide/1970

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.     

Nitrogen fixation estimates for the Baltic Sea indicate high rates for the previously overlooked Bothnian Sea

Dense blooms of diazotrophic filamentous cyanobacteria are formed every summer in the Baltic Sea. We estimated their contribution to nitrogen fixation by combining two decades of cyanobacterial biovolume monitoring data with recently measured genera-specific nitrogen fixation rates. In the Bothnian Sea, estimated nitrogen fixation rates were 80 kt N year⁻¹, which has doubled during recent decades and now exceeds external loading from rivers and atmospheric deposition of 69 kt year⁻¹. The estimated contribution to the Baltic Proper was 399 kt N year⁻¹, which agrees well with previous estimates using other approaches and is greater than the external input of 374 kt N year⁻¹. Our approach can potentially be applied to continuously estimate nitrogen loads via nitrogen fixation. Those estimates are crucial for ecosystem adaptive management since internal nitrogen loading may counteract the positive effects of decreased external nutrient loading.     

Natural desulfurization in coal-fired units using Greek lignite

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 gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume 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.     

Relation between estimated dry deposition and throughfall in a coniferous forest exposed to controlled levels of SO2 and NO2

Throughfall was collected in a Scots pine forest exposed to about 14 microg m(-3) of both SO2 and NO2, and in a control forest with 1 microg m(-3) SO2 and < 1 microg m(-3) NO2. Precipitation was collected in a nearby open field. Collection was performed on an event basis during the whole vegetation period. Exposure was made by an open-air release system during the vegetation period, except during rain and at night. Additional sulfate deposition in the exposed forest (compared to control forest) was nearly equal to dry deposition of sulfur dioxide, as estimated with a stomatal conductance model adapted for the particular forest. It is thus concluded that essentially all of the dry deposited sulfur dioxide is eventually extracted and appears in throughfall-including the fraction that has been deposited through stomata. Attempts to relate net throughfall deposition to dry deposition of sulfate in the control forest were inconclusive, since a minor (10%) uncertainty in the water balance had a major influence on calculated deposition velocity for particulate sulfate. Nitrate throughfall deposition is about half of the open field wet deposition, both for the exposed and control forest. Thus, a long-term exposure with about 14 microg m(-3) NO2 decreased nitrate throughfall deposition.     

Biogenic Sulfur Gas Emissions from Soils in Eastern and Southeastern United States

Data are presented for the first systematic measurements of biogenic sulfur gas flux from the major soil orders within the eastern and southeastern United States. Sulfur flux samples were collected and analyzed on-site during the fall of 1977, spring and summer of 1978 and summer of 1979. A total of 27 sampling locales in 17 states were examined. Eight additional sites were visited in 1980.

At some locales, two to four soils were examined, providing an even broader sampling of the soil orders. Three of the locales were revisited two or three times during the course of the study to establish the influence of seasonal climatology upon the measured emission rates and chemical composition of the sulfur flux mixtures.

The sulfur gas enhancement of sulfur-free sweep air passing through dynamic emission flux chambers placed over selected sampling areas was determined by combined cryogenic enrichment sampling and wall-coated, open tubular, capillary column, cryogenic gas chromatography (WCOT/GC) using a sulfur selective, flame photometric detector (FPD).

Sulfur gas mixtures varied with soil order, ambient temperature, insolation, soil moisture, cultivation, and vegetative cover. Statistical analyses indicated strong temperature and soil order relationships for sulfur emissions from soils.

Fluxes ranged from 0.001 g to 1940 g of total sulfur as S/m²/yr. The calculated mean annual sulfur flux, weighted by soil order, was 0.03 g S/m²/yr for the study land area, or 110,872 metric tons (mT). The estimated annual average sulfur flux increased from 65 mT per 6400 km² for the land grids in the northernmost east-west grid tier to an average 1800 mT for the land grids in the southern Florida grid tiers.

This systematic sampling of major soils provides a much broader data base for estimating biogenic sulfur flux than previously reported for isolated intertidal sites, and presents the first sulfur flux estimates for inland soils which make up approximately 93% of the land of the eastern United States.     

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada)

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.     

Sulfur toxicity and media capacity for H2S removal in biofilters packed with a natural or a commercial granular medium

Two types of media, a natural medium (wood chips) and a commercially engineered medium, were evaluated for sulfur inhibition and capacity for removal of hydrogen sulfide (H2S). Sulfate was added artificially (40, 65, and 100 mg of S/g of medium) to test its effect on removal efficiency and the media. A humidified gas stream of 50 ppm by volume H2S was passed through the media-packed columns, and effluent readings for H2S at the outlet were measured continuously. The overall H2S baseline removal efficiencies of the column packed with natural medium remained >95% over a 2-day period even with the accumulated sulfur species. Added sulfate at a concentration high enough to saturate the biofilter moisture phase did not appear to affect the H2S removal process efficiency. The results of additional experiments with a commercial granular medium also demonstrated that the accumulation of amounts of sulfate sufficient enough to saturate the moisture phase of the medium did not have a significant effect on H2S removal. When the pH of the biofilter medium was lowered to 4, H2S removal efficiency did drop to 36%. This work suggests that sulfate mass transfer through the moisture phase to the biofilm phase does not appear to inhibit H2S removal rates in biofilters. Thus, performance degradation for odor-removing biofilters or H2S breakthrough in field applications is probably caused by other consequences of high H2S loading, such as sulfur precipitation.