钍试剂分光光度法测定固定源烟气中SO3

以80%(体积分数)异丙醇为吸收液采集SO3后,用过量的Ba(ClO4)2与吸收液中SO42-反应,剩余Ba2 与钍试剂生成钍-钡络合物,测定该络合物在530 nm处的吸光度,由此间接计算出固定源烟气中SO3的浓度.钍试剂分光光度法对溶液SO42-测定范围为2.00～60.00 μg/mL,检出限为1.17 μg/mL.不同浓度样品的重复性实验和回收率检验结果证明了该法具有很好的精确度和准确度.样品中含有少量的Ca2 、Na 、K 、CO2-3、Cl-等,对测定结果无显著影响.     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Aerostat-lofted instrument and sampling method for determination of emissions from open area sources

An aerostat-borne instrument and sampling method was developed to characterize air samples from area sources, such as emissions from open burning. The 10 kg battery-powered instrument system, termed “the Flyer”, is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by means of one or two tethers. The Flyer can be configured variously for continuous CO₂ monitoring, batch sampling of semi-volatile organic compounds (SVOCs), volatile organic compounds (VOCs), black carbon, metals, and PM by size. The samplers are controlled by a trigger circuit to avoid unnecessary dilution from background sampling when not within the source plume. The aerostat/Flyer method was demonstrated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnance. A carbon balance approach was used to derive emission factors that showed excellent agreement with published values.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

Characterization of emissions from a variable gasoline/methanol fueled car.

In response to the occurrence of the increasingly severe ambient ozone exceedances, regional environmental managers are examining the possibility of a cleaner fuel for automobiles. At this time the leading candidate appears to be methanol. In anticipation of a shift to methanol, flexible-fueled automobiles capable of operating on gasoline and/or methanol are being developed. This study examines both the exhaust and evaporative emissions from a prototype General Motors Variable Fuel Corsica. Results are reported for tests conducted at temperatures of 40 degrees, 75 degrees, and 90 degrees F, and for fuels M0 M25, M50, M85, and M100. In addition to regulated emissions and fuel economy, emission rates for methanol, aldehydes, and a large number of hydrocarbon compounds were measured. The data indicate that increasing the fuel's methanol content does not affect the exhaust organic emission rate (calculated in accordance with the regulation) from flexible-fueled cars, but formaldehyde and methanol comprise increasingly greater portions of the organic material while hydrocarbons comprise less. Increasing fuel methanol content has no significant effect on exhaust regulated emission rates (organic material, carbon monoxide, and nitrogen oxides) nor on the composition of total hydrocarbons, except for methane, which increases substantially. The effect of ambient temperature on both exhaust and evaporative emissions is similar to its effect on gasoline cars: organic and carbon monoxide exhaust emissions increase substantially at the lower temperatures, and evaporative emissions increase steadily with increases in temperature.     

Bisphenol A: emissions from point sources

Bisphenol A is widely used for the production of epoxy resins and polycarbonate plastics. Special in vitro test systems and animal experiments showed a weak estrogenic activity for Bisphenol A. Based on in vitro receptor interaction studies, the activity was estimated to be 2 x 10(-3) lower than that of estradiol. Especially aquatic wildlife could be endangered by waste water discharges. To manage possible risks arising from Bisphenol A contamination, the major fluxes need to be obtained and the contributors to the contamination of municipal treatment plants need to be determined. In this study, industrial emitters and communal waste waters were monitored simultaneously. Mixed samples were taken over periods of one week at nine sample sites. The results showed that the concentrations and fluxes were variable. The paper industry was the major Bisphenol A contributor to the influent of the waste water treatment plant. All the other fluxes measured, including two household areas, were considerably low. About 90% of the total load was removed during the waste water treatment.     

Design of a compact dilution sampler for stationary combustion sources

The dilution sampling method simulates the rapid cooling and dilution processes after hot flue gas have left the stack. This allows gases or vapors to nucleate both homogeneously and heterogeneously, and to condense on preexisting particles in processes analogous to those that occur in the ambient environment. Using this method the authors can collect filterable particulate matter (PM) and condensible PM, that is, primary PM, simultaneously. In order to make this method more suitable for field investigation, a compact dilution sampler was developed. The sampler enhances mixing of dilution air with the stack gas, and thus shortens the length of the mixing section. The design decreases the nominal flow rate through the aging section, and accordingly reduces the size of the residence chamber. The decreased size of the sampler is suitable for field test. Sampling gas is pressured into the residence chamber, and air pressure in the chamber is micro-positive. Uncollected redundant gas is automatically discharged through unused sampling ports, which keeps the unit stable. Performance evaluation tests demonstrate that the design is reasonable. The sampler has been applied to characterize PM emissions from various combustion sources in China.     

Atmospheric emissions of mercury from Australian point sources

The UN Global Mercury Assessment (GMA) estimates that atmospheric emissions of mercury from Australian stationary combustion sources were 97.0 tonnes for the year of 1995. This is more than 90% of the estimated emissions from stationary combustion for the whole of North America, and seems abnormally high for a country with a population of around 20 million, in spite of the fact that most of Australia's stationary energy supply is provided by coal. It is also significantly larger than previous estimates of mercury emissions from Australian sources. New estimates of Australian mercury emissions from stationary energy sources, based on both a top down and bottom up approach, are presented. These estimates can be reconciled for black coal fired power stations, but suggest that the bottom up approach (the Australian National Pollutant Inventory) significantly under-estimates emissions from brown coal fired plant, if mercury capture efficiencies in these plants are low, as observed for lignite-fired plant. The major uncertainties in these estimates are the coal mercury content in coals burnt in Australian power stations, and the mercury capture efficiency in particulate control devices used at these stations. Based on these estimates, Australian emissions of mercury from stationary energy are currently 2–8 tonnes/year, significantly lower than the GMA estimate.     

Direct measurement of fugitive emissions of hydrocarbons from a refinery

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C2+ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C2+ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C2+ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C2+ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C2+ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

固定源氮氧化物排放及控制技术应用

固定源是氮氧化物排放的一个主要来源。通过对主要固定源氮氧化物生成机理及现有的排放控制技术进行论述，分析我国固定源氮氧化物排放的实际情况，提出我国固定源氮氧化物排放控制还处于起步阶段，氮氧化物排放标准相对宽松，氮氧化物排放控制技术有待进一步普及，并提出固定源氮氧化物排放治理的一些建议。     

Particulate emissions from a stationary engine fueled with ultra-low-sulfur diesel and waste-cooking-oil-derived biodiesel

Stationary diesel engines, especially diesel generators, are increasingly being used in both developing countries and developed countries because of increased power demand. Emissions from such engines can have adverse effects on the environment and public health. In this study, particulate emissions from a domestic stationary diesel generator running on ultra-low-sulfur diesel (ULSD) and biodiesel derived from waste cooking oil were characterized for different load conditions. Results indicated a reduction in particulate matter (PM) mass and number emissions while switching diesel to biodiesel. With increase in engine load, it was observed that particle mass increased, although total particle counts decreased for all the fuels. The reduction in total number concentration at higher loads was, however, dependent on percentage of biodiesel in the diesel-biodiesel blend. For pure biodiesel (B100), the reduction in PM emissions for full load compared to idle mode was around 9%, whereas for ULSD the reduction was 26%. A large fraction of ultrafine particles (UFPs) was found in the emissions from biodiesel compared to ULSD. Nearly 90% of total particle concentration in biodiesel emissions comprised ultrafine particles. Particle peak diameter shifted from a smaller to a lower diameter with increase in biodiesel percentage in the fuel mixture.     

A novel field measurement method for determining fine particle and gas emissions from residential wood combustion

Emission data from residential wood combustion are usually obtained on test stands in the laboratory but these measurements do not correspond to the operational conditions in the field because of the technological boundary conditions (e.g. testing protocol, environmental and draught conditions). The field measurements take into account the habitual practice of the operators and provide the more reliable results needed for emission inventories. In this study, a workable and compact method for measuring emissions from residential wood combustion in winter conditions was developed. The emissions for fine particle, gaseous and PAH compounds as well as particle composition in real operational conditions were measured from seven different appliances. The measurement technique worked well and was evidently suitable for winter conditions. It was easy and fast to use, and no construction scaffold was needed. The dilution of the sample with the combination of a porous tube diluter and an ejector diluter was well suited to field measurement. The results indicate that the emissions of total volatile organic carbon (TVOC) (17 g kg⁻¹ (of dry wood burned)), carbon monoxide (CO) (120 g kg⁻¹) and fine particle mass (PM₁) (2.7 g kg⁻¹) from the sauna stove were higher than in the other measured appliances. In the masonry heaters, baking oven and stove, the emissions were 2.9–9 g kg⁻¹ TVOC, 28–68 g kg⁻¹ CO and 0.6–1.6 g kg⁻¹ PM₁. The emission of 12 PAHs (PAH₁₂) from the sauna stove was 164 mg kg⁻¹ and consisted mainly of PAHs with four benzene rings in their structure. PAH₁₂ emission from other appliances was, on average, 21 mg kg⁻¹ and was dominated by 2-ring PAHs. These results indicate that despite the non-optimal operational practices in the field, the emissions did not differ markedly from the laboratory measurements.     

Carbonyl emissions from commercial cooking sources in Hong Kong

Cooking fumes are an important carbonyl emission source, especially in a highly urbanized city, such as Hong Kong. Cooking exhaust from 15 commercial kitchens of a variety of cooking styles was sampled and analyzed for a suite of 13 carbonyl compounds. Carbonyl compositions were varied among the different cooking styles. Formaldehyde was generally the most abundant carbonyl, and its contribution to the total carbonyl amount on a molar basis ranged from 12 to 60%. Acrolein was also found to be an abundant carbonyl in the cooking exhaust. The highest contribution by acrolein to the total carbonyls was found to be 30% in the exhaust of a western-style steak restaurant. Long-chain saturated carbonyls, that is, heptanal, octanal, and nonanal, accounted for a significant fraction (> 40%) of the total carbonyls in kitchens that always used heated cooking oils. Two dicarbonyls, glyoxal and methylglyoxal, had a various presence in the cooking emissions, ranging from negligible to 10%. The presence of benzaldehyde and tolualdehyde was mostly negligible in the sampled kitchen exhaust. Annual emission rates of both individual carbonyls and total carbonyls were estimated for various types of commercial kitchens. Local-style fast-food shops contributed the highest total carbonyl emissions per year mainly because of the large number of this kind of restaurant in Hong Kong. The citywide annual emission rates of the three most toxic carbonyls, formaldehyde, acetaldehyde, and acrolein, were estimated assuming that the limited number of sampled restaurants were representative of the average restaurants. Such estimates of carbonyl emission rates were comparable to the estimated carbonyl emissions from vehicular sources, suggesting the importance of commercial cooking as a source for carbonyls in Hong Kong.     

Carbonyl emissions from vehicular exhausts sources in Hong Kong

Vehicular emission (VE) is one of the important anthropogenic sources for airborne carbonyls in urban area. Six types of VE-dominated samples were collected at representative locations in Hong Kong where polluted by a particular fueled type of vehicles, including (i) a gas refilling taxis station (liquefied petroleum gas [LPG] emission); (ii) a light-duty passenger car park (gasoline emission); (iii) a minibus station (diesel emission); (iv) a single-deck-bus depot (diesel emission); (v) a double-deck-bus depot (diesel emission); and (vi) a whole-food market entrance for light- and heavy-duty vehicles (diesel emission). A total of 15 carbonyls in the samples were quantified. Formaldehyde was the most abundant carbonyl among the VE-dominated samples, and its contribution to the total quantified amount on a molar basis ranged from 54.8% to 60.8%. Acetaldehyde and acetone were the next two abundant carbonyls. The carbonyls were quantified at three roadside locations in Hong Kong. The highest concentrations of formaldehyde and acetaldehyde, 22.7 +/- 8.4 and 6.0 +/- 2.8 microg/m3, respectively, were determined in the samples collected at a main transportation gate for goods between Hong Kong and Mainland China. The total quantified carbonyl concentration, 37.9 +/- 9.3 microg/m3, was the highest at an entrance of a cross-harbor tunnel in downtown area. The theoretical carbonyls compositions of the three roadside locations were estimated according to the VE-dominated sample profiles and the statistics on vehicle numbers and types during the sampling period. The measured compositions of formaldehyde were much higher than the theoretical compositions in summer, demonstrating that photochemical reactions significantly contributed to the formaldehyde production in the roadsides.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Toxic emissions from mobile sources: a total fuel-cycle analysis for conventional and alternative fuel vehicles

Mobile sources are among the largest contributors of four hazardous air pollutants--benzene, 1,3-butadiene, acetaldehyde, and formaldehyde--in urban areas. At the same time, federal and state governments are promoting the use of alternative fuel vehicles as a means to curb local air pollution. As yet, the impact of this movement toward alternative fuels with respect to toxic emissions has not been well studied. The purpose of this paper is to compare toxic emissions from vehicles operating on a variety of fuels, including reformulated gasoline (RFG), natural gas, ethanol, methanol, liquid petroleum gas (LPG), and electricity. This study uses a version of Argonne National Laboratory's Greenhouse Gas, Regulated Emissions, and Energy Use in Transportation (GREET) model, appropriately modified to estimate toxic emissions. The GREET model conducts a total fuel-cycle analysis that calculates emissions from both downstream (e.g., operation of the vehicle) and upstream (e.g., fuel production and distribution) stages of the fuel cycle. We find that almost all of the fuels studied reduce 1,3-butadiene emissions compared with conventional gasoline (CG). However, the use of ethanol in E85 (fuel made with 85% ethanol) or RFG leads to increased acetaldehyde emissions, and the use of methanol, ethanol, and compressed natural gas (CNG) may result in increased formaldehyde emissions. When the modeling results for the four air toxics are considered together with their cancer risk factors, all the fuels and vehicle technologies show air toxic emission reduction benefits.     

Correlating emissions with time and temperature to predict worst-case emissions from open liquid area sources

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry's law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H2S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H2S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85-90 degrees F), the constant emission rate underestimated odor impact significantly (by 73%).     

Application of a combined measurement and modeling method to quantify windblown dust emissions from the exposed playa at Mono Lake, California

Particulate matter < or =10 microm (PM10) emissions due to wind erosion can vary dramatically with changing surface conditions. Crust formation, mechanical disturbance, soil texture, moisture, and chemical content of the soil can affect the amount of dust emitted during a wind event. A refined method of quantifying windblown dust emissions was applied at Mono Lake, CA, to account for changing surface conditions. This method used a combination of real-time sand flux monitoring, ambient PM10 monitoring, and dispersion modeling to estimate dust emissions and their downwind impact. The method identified periods with high emissions and periods when the surface was stable (no sand flux), even though winds may have been high. A network of 25 Cox sand catchers (CSCs) was used to measure the mass of saltating particles to estimate sand flux rates across a 2-km2 area. Two electronic sensors (Sensits) were used to time-resolve the CSC sand mass to estimate hourly sand flux rates, and a perimeter tapered element oscillating microbalance (TEOM) monitor measured hourly PM10 concentrations. Hourly sand flux rates were related by dispersion modeling to hourly PM10 concentrations to back-calculate the ratio of vertical PM10 flux to horizontal sand flux (K-factors). Geometric mean K-factor values (K(f)) were found to change seasonally, ranging from 1.3 x 10(-5) to 5.1 x 10(-5) for sand flux measured at 15 cm above the surface (q15). Hourly PM10 emissions, F, were calculated by applying seasonal K-factors to sand flux measurements (F = K(f) x q15). The maximum hourly PM10 emission rate from the study area was 76 g/m2 x hr (10-m wind speed = 23.5 m/sec). Maximum daily PM10 emissions were estimated at 450 g/m2 x day, and annual emissions at 1095 g/m2 x yr. Hourly PM10 emissions were used by the U.S. Environmental Protection Agency (EPA) guideline AERMOD dispersion model to estimate downwind ambient impacts. Model predictions compared well with monitor concentrations, with hourly PM10 ranging from 16 to over 60,000 microg/m3 (slope = 0.89, R2 = 0.77).     

An inverse Gaussian plume approach for estimating atmospheric pollutant emissions from multiple point sources

A method is developed for estimating the emission rates of contaminants into the atmosphere from multiple point sources using measurements of particulate material deposited at ground level. The approach is based on a Gaussian plume type solution for the advection–diffusion equation with ground-level deposition and given emission sources. This solution to the forward problem is incorporated into an inverse algorithm for estimating the emission rates by means of a linear least squares approach. The results are validated using measured deposition and meteorological data from a large lead–zinc smelting operation in Trail, British Columbia. The algorithm is demonstrated to be robust and capable of generating reasonably accurate estimates of total contaminant emissions over the relatively short distances of interest in this study.