A Device for Measuring Volatile Organic-Carbon Emissions from Cooling-Tower Water

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.     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

From Air Repair to EM: A&WMA’s Publications through a Century of Change

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.     

Relating Summer Ambient Particulate Sulfur,Sulfur Dioxide,and Light Scattering to Gaseous Tracer Emissions from the MOHAVE Power Project

ABSTRACT

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-northeast of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO₂, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data.

Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO₂ to par-ticulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO₂ and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO₂ and tracer emission “signals” to particulate sulfur or light scattering.     

空速和二氧化碳对沼气脱硫剂硫容确定的影响

为了弄清空速与二氧化碳含量对氧化铁脱硫剂硫容确定的影响,分别在实验气源为纯硫化氢,空速为40、80、120和160 h-1以及实验气源为二氧化碳含量分别在0%、20%、40%和80%,其余为硫化氢,空速为80 h-1条件下,对T502(粗脱硫剂)和HXT-2(精脱硫剂)2种氧化铁脱硫剂进行了不同测试条件对氧化铁硫容确定影响的研究。研究结果表明,T502和HXT-2氧化铁脱硫剂硫容测试结果随着空速和二氧化碳含量增加而减少,结果显示了在空速较低条件下(120h-1),二氧化碳含量在40%以下时对氧化铁脱硫剂硫容测试结果影响不大,但二氧化碳含量在40%以上时,对氧化铁脱硫剂硫容测试结果影响显著。     

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.     

MnO2对煤粉中CaO固硫效率影响机理

采用热力学计算和实验方法对钙硫比n（CaO）/n（S）=2.0条件下不同钙基固硫剂的固硫效果进行了比较,发现：CaO的固硫效率最高。以CaO为固硫剂,研究了添加剂MnO2对CaO固硫效果的影响。结果表明,加入MnO2可以提高CaO的固硫效率,且其含量为1%时对CaO固硫的促进效果最佳。这是因为煤粉燃烧过程中MnO2将逐级分解,分解产物依次为Mn2O3和Mn3O4,锰的氧化物一方面可以催化CaO的固硫反应,另一方面,Mn3O4本身也参与到固硫反应之中,生成MnSO4,从而促进钙基固硫剂的固硫效果。     

The relationship of sulfur emissions to sulfate in precipitation—II. Gas phase processes

A climatological box model is applied to wet deposition of sulfur in eastern North America using the extreme assumption that all wet-deposited sulfates originate in sulfate aerosol. The measured sulfate in precipitation during 1977–1979 constrains the probability that an SO₂ molecule emitted in the eastern United States is oxidized before deposition or outflow from the region to values greater than 0.5 and more likely near 1.0. This result implies that uniform SO₂ emission reductions will produce nearly proportional reductions in wet sulfates originating in those emissions and deposited on land. A similar result was obtained previously using the more likely assumption that oxidation and removal of SO₂ in precipitating clouds is the major source of wet deposition of sulfur. Therefore, it is argued that uniform regional reductions in annual average SO₂ emissions will produce nearly proportional reductions in wet sulfur deposited on land and originating in those emissions. The amount of wet sulfate deposition is demonstrated to constrain the mean scale of transport along air parcel trajectories for the precursor of wet sulfur, whether SO₂ or sulfate aerosol, to values greater than 900 km. An examination of previous microscopic photochemical models indicates that the sulfate aerosol formation rate is roughly proportional to local SO₂ concentrations, an inference which is consistent with the result of the climatological model.     

Influence of ozone, relative humidity, and flow rate on the deposition and oxidation of sulfur dioxide on yellow sand

To evaluate the influences of O₃, relative humidity (RH), and flow rate on the reaction between yellow sand and SO₂, the SO₂ deposition velocity and the oxidation state of sulfur were investigated by means of exposure experiments in a cylindrical flow reactor. Early in the reaction, the deposition velocity was not influenced by the RH or the presence of O₃; as the reaction progressed, however, the deposition velocity increased in the presence of O₃ and at high humidity. The oxidation of sulfur from S(IV) to S(VI) was also enhanced under these conditions. The amount of sulfur oxidation was positively correlated with the amount of deposited O₃. Furthermore, the SO₂ deposition velocity increased with increasing flow rate. However, changes in the flow rate had no noticeable effect on the amount of SO₂ oxidation.     

Formation of particulate sulfur species (sulfate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach

To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO₄²⁻) and methanesulfonate (MS_x 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.     

The Relationship of Carbon Dioxide Emissions with Coal Rank and Sulfur Content

Carbon dioxide emissions, on an equivalent energy basis, were calculated for 504 North American coals to explore the effects of coal rank and sulfur content on CO₂ emissions. The data set included coals ranging in rank from lignite through low-volatile bituminous from 15 U.S. states and Alberta, Canada. Carbon dioxide emissions were calculated from the carbon content and gross calorific value of each coal. The lowest CO₂ emissions are calculated for the high-volatile bituminous coals (198 to 211 lbs CO₂/MMBtu) and the highest for lignites and subbituminous coals (209 to 224 lbs CO₂/MMBtu). The lower CO₂ emissions from the high-volatile bituminous coals result in part from their generally higher sulfur content. However, even at equivalent sulfur contents the high-volatile bituminous coals give lower CO₂ emissions than the lower-rank coals. On average, the lowerrank coals produce 5 percent more CO₂ upon combustion than the highvolatile bituminous coals, on the basis of gross calorific value. This difference increases to 9 percent on the basis of estimated net calorific value. The net calorific value is better indicator of power plant energy production than the gross calorific value. The difference in CO₂ emissions resulting from the use of high-volatile bituminous coals and lower-rank coals is of the same order of magnitude as reductions expected from near-term combustion efficiency improvements. These results are useful to those interested in current and future CO₂ emissions resulting from coal combustion.     

Sulfur Toxicity and Media Capacity for H2S Removal in Biofilters Packed with a Natural or a Commercial Granular Medium

Abstract

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.     

Laboratory measurement of the dry deposition of sulfur dioxide onto northern Chinese soil samples

We investigated soil surface resistance R_c to dry deposition of sulfur dioxide (SO₂) onto different types of soils in laboratory experiments, using samples collected from the arid loess plateau and deserts of northern China. We evaluated the factors that affect R_c, which depends on the physical and chemical interaction between a trace constituent and the deposition surface. We observed that the values of R_c for SO₂ decreased with increase of soil weight and increased with SO₂ concentration, although surface coverage had little effect on R_c. The SO₂ uptake rate by all the northern Chinese soil samples seemed to be, on the whole, dependent on relative humidity (RH). In all of the northern Chinese soil samples, R_c was in the range 0.028–0.65 s mm⁻¹, and was exponentially related to the effective surface area of each soil sample, regardless of RH. Wet chemical analysis of sulfur deposited onto the soil samples showed that oxidation ratio of sulfur(IV) to sulfur(VI) was related to RH, which might be related to complex interactions among the amount of water on the soil sample, the pH, and the metallic ions in the liquid phase.     

Analysis of observations relevant to long-range transport and deposition of pollutants

Observations of annual wet deposition of sulfur made during 1980 at 62 stations in northeastern America are interpreted using a statistical long-range transport model. This work is meant to demonstrate the role of an empirical model in the analysis of observations. Our analysis points to the following conclusions:

• 1.(1) The parameters that represent the conversion of SO₂ to SO₄ and the wet and dry removal of sulfur are insensitive to concentration levels,
• 2.(2) the variation of the wet deposition field is closely related to the distribution of sulfur emissions and
• 3.(3) observations demand efficient wet scavenging of SO₂.

     

Wet and dry deposition of sulfur and nitrogen compounds in Ontario

Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO₄²⁻ andNO₃⁻ in precipitation, and of SO₂,SO₄²⁻ andNO₃⁻ in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO₄²⁻ deposition rate of 20 kg ha¹⁻ y¹⁻, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

Effect of SME biodiesel blends on PM2.5 emission from a heavy-duty engine

To explore the effect of biodiesel and sulfur content on PM_2.5 emissions, engine dynamometer tests were performed on a Euro II engine to compare the PM_2.5 emissions from four fuels: two petroleum diesel fuels with sulfur contents of 50 and 100 ppm respectively, and two B20 fuels in which soy methyl ester (SME) biodiesel was added to each of the above mentioned petroleum diesel fuels (v/v: 80%/20% for petroleum diesel and SME respectively). Gaseous pollutants and PM_2.5 emissions were sampled with an AVL AMA4000 and Model 130 High-Flow Impactor (MSP Corp). Measurements were made of the PM_2.5 mass, organic carbon (OC), elemental carbon (EC) and the water-soluble ion distribution. The results showed that PM_2.5 emissions decreased with lower sulfur content or blending with SME biodiesel, and the decrease would be more by applying both two methods together. Particles of approximately 0.13 μm contributed 48–83% of PM_2.5 emissions. The impact of sulfur content on this percentage was different for low and high engine speed. The majority of PM_2.5 was comprised of OC and EC, and the carbon emission rate had the same trend as PM_2.5. Since the EC abatement of B20 was larger than OC, the OC/EC ratio of B20 was always larger than that of petroleum diesel. For petroleum diesel, the OC/EC increased with sulfur content, which was not the case for B20. The SO₄^2? had highest emission rate in the water-soluble ions of PM.     

The Sulfur Balance of Incinerators

Municipal refuse usually contains only 0.10-0.15% sulfur. During combustion a minor fraction of the sulfur is released as SO₂, while the major fraction is fixed in the ash, which contains alkaline oxides. Contrasted with coal and heavy fuel oil, municipal refuse is a minor to negligible source of SO₂ air pollution.     

Anthropogenic emissions of SO2 and NOx in Asia: Emission inventories

The anthropogenic emissions of SO₂ and NO_x for 25 Asian countries east of Afghanistan and Pakistan have been calculated for 1975, 1980, 1985, 1986 and 1987 based on fuel consumption, sulfur content in fuels and emission factors for used fuels in each emission category. The provincial- and regional-based calculations have also been made for China and India. The total SO₂ emissions in these parts of Asia have been calculated to be 18.3 and 29.1 Tg in 1975 and 1987, respectively. The calculated total NO_x emissions were 9.4 and 15.5 Tg in 1975 and 1987, respectively. The SO₂ and NO_x emissions in East Asia (China, Japan, South Korea, North Korea and Taiwan) were 23.4 and 10.7 Tg in 1975 and 1987, respectively.Keyword: Emission inventories, sulfur dioxide emissions, nitrogen oxide emissions, Asian emissions, anthropogenic emissions.