Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Control of mercury vapor emissions from combustion flue gas

GOAL, SCOPE AND BACKGROUND: Mercury (Hg) emission from combustion flue gas is a significant environmental concern due to its toxicity and high volatility. A number of the research efforts have been carried out in the past decade exploiting mercury emission, monitoring and control from combustion flue gases. Most recently, increasing activities are focused on evaluating the behavior of mercury in coal combustion systems and developing novel Hg control technologies. This is partly due to the new regulatory requirement on mercury emissions from coal-fired combustors to be enacted under the U.S. Title III of the 1990 Clean Air Act Amendments. The aim of this review work is to better understand the state-of-the-art technologies of flue gas mercury control and identify the gaps of knowledge hence areas for further opportunities in research and development. MAIN FEATURES: This paper examines mercury behaviors in combustion systems through a comprehensive review of the available literature. About 70 published papers and reports were cited and studied. RESULTS AND DISCUSSION: This paper summarizes the mechanisms of formation of mercury containing compounds during combustion, its speciation and reaction in flue gas, as well as subsequent mobilization in the environment. It also provides a review of the current techniques designed for real-time, continuous emission monitoring (CEM) for mercury. Most importantly, current flue gas mercury control technologies are reviewed while activated carbon adsorption, a technology that offers the greatest potential for the control of gas-phase mercury emissions, is highlighted. CONCLUSIONS AND RECOMMENDATIONS: Although much progress has been achieved in the last decade, techniques developed for the monitoring and control of mercury from combustion flue gases are not yet mature and gaps in knowledge exist for further advancement. More R&D efforts are required for the effective control of Hg emissions and the main focuses are identified.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Predictions for isomer distributions of toxic dioxins and furans in selected industrial combustion processes

Three thermodynamic databases of polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) have been used to simulate the PCDD/F isomer distribution in industrial combustion processes. The three databases had been derived using the Group Additivity approach and two computational molecular modelling methods, Modified Neglect of Diatomic Overlap (MNDO) and Parametrized Model 3 (PM3), respectively. The predictions of the toxic PCDD/F isomer distributions using the three different databases have been compared with measured values from industrial processes. An excellent agreement between the predictions using the MNDO method and the measured data has been obtained. It is concluded that the PCDD/F isomer distributions within each group observed in these combustion processes may be thermodynamically controlled.     

Survey-based inventory for atmospheric emissions from residential combustion in Vietnam

Environmental Science and Pollution Research - Local questionnaire surveys were conducted to collect representative activity data for calculation of annual emissions from residential combustion in...     

煤化工企业火炬NOx排放的模拟燃烧实验

针对煤化工企业火炬气燃烧特点,设计了一套模拟燃烧装置,分别研究液化气添加量及燃烧温度对NOx的影响,并对火炬系统NOx的排放系数进行核算。结果表明,火炬系统NOx排放浓度和排放量随液化气添加量的增加而增大;同时研究发现,NOx与燃烧温度之间成正比关系,即温度升高有利于NOx的产生。根据核算结果,火炬系统NOx排放系数在0．099～0．185kg／t之间,平均为0．139kg／t。     

Evaluation of mercury emissions to the atmosphere from coal combustion,China

Mercury emissions from the coal smoke is the main source of anthropogenic discharge and mercury pollution in atmosphere. The calculated total amount of mercury emissions of China in 1995 is approximately 213.8 tonnes, which accounts for c. 5% of estimated total global discharge of 4000 tonnes in the same period. From 1978 to 1995, total coal consumption increased fourfold. Based on these data it is estimated that the mercury emissions will increase at a rate of 5% a year, and the predicted emissions will be 273 tonnes in China in 2000. Controlling and solving mercury emissions from coal combustion are among the most important environmental tasks facing China.     

Dioxins/furans emissions from fluidized bed combustion of salt-laden hog fuel

Polychlorinated dibenzodioxins/furans (PCDD/F) were formed in substantial quantities in a pilot-scale fluidized bed combustor burning salt-laden waste wood, a common fuel for Canadian coastal pulp and paper mills. Formation of PCDD/F increased with increasing chloride content in the feed, and appeared to correlate with the chlorine content in the fly ash. It took a very long time for the ash chlorine content to stabilize, suggesting that chlorine transferred slowly from the flue gas to the ash. The baghouse may contribute largely to formation of the PCDD/F, owing to its temperature range and the potentially long residence time for ash particles. Controlling the baghouse temperature to reduce the PCDD/F formation in the baghouse should be effective in reducing the total emission level. While sulphur addition was found to reduce the emission level by as much as 90%, the emission level was still above the regulated level for the mills burning salt-laden wood under the conditions of the present study. No relation between the emission level and CO concentration in the flue gas was observed.     

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.     

Updating the conceptual model for fine particle mass emissions from combustion systems

Atmospheric transformations determine the contribution of emissions from combustion systems to fine particulate matter (PM) mass. For example, combustion systems emit vapors that condense onto existing particles or form new particles as the emissions are cooled and diluted. Upon entering the atmosphere, emissions are exposed to atmospheric oxidants and sunlight, which causes them to evolve chemically and physically, generating secondary PM. This review discusses these transformations, focusing on organic PM. Organic PM emissions are semi-volatile at atmospheric conditions and thus their partitioning varies continuously with changing temperature and concentration. Because organics contribute a large portion of the PM mass emitted by most combustion sources, these emissions cannot be represented using a traditional, static emission factor. Instead, knowledge of the volatility distribution of emissions is required to explicitly account for changes in gas-particle partitioning. This requires updating how PM emissions from combustion systems are measured and simulated from combustion systems. Secondary PM production often greatly exceeds the direct or primary PM emissions; therefore, secondary PM must be included in any assessment of the contribution of combustion systems to ambient PM concentrations. Low-volatility organic vapors emitted by combustion systems appear to be very important secondary PM precursors that are poorly accounted for in inventories and models. The review concludes by discussing the implications that the dynamic nature of these PM emissions have on source testing for emission inventory development and regulatory purposes. This discussion highlights important linkages between primary and secondary PM, which could lead to simplified certification test procedures while capturing the emission components that contribute most to atmospheric PM mass.     

Mercury (Hg) emissions from domestic biomass combustion for space heating

Three mercury (Hg) species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM_2.5)) were measured in the stack of a small scale wood combustion chamber at 400 °C, in the stack of an advanced wood boiler, and in two areas influenced by wood combustion. The low temperature process (lab-scale) emitted mostly GEM (∼99% when burning wood pellets and ∼95% when burning unprocessed wood). The high temperature wood boiler emitted a greater proportion of oxidized Hg (approximately 65%) than the low temperature system. In field measurements, mean PBM_2.5 concentrations at the rural and urban sites in winter were statistically significantly higher than in warmer seasons and were well correlated with Delta-C concentrations, a wood combustion indictor measured by an aethalometer (UV-absorbable carbon minus black carbon). Overall the results suggest that wood combustion may be an important source of oxidized mercury (mostly in the particulate phase) in northern climates in winter.     

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.     

Nitrogen oxides emissions from the MILD combustion with the conditions of recirculation gas

The nitrogen oxides (NO_x) reduction technology by combustion modification which has economic benefits as a method of controlling NO_x emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NO_x reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NO_x in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N₂), carbon dioxide (CO₂) and steam (H₂O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NO_x concentration greatly. Implications: We investigated the influence of factors determining the nitrogen oxides (NO_x) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NO_x emissions the most.     

Volatile organic compound emissions from dry mill fuel ethanol production

Ethanol fuel production is growing rapidly in the rural Midwest, and this growth presents potential environmental impacts. In 2002, the U.S. Environmental Protection Agency (EPA) and the Minnesota Pollution Control Agency (MPCA) entered into enforcement actions with 12 fuel ethanol plants in Minnesota. The enforcement actions uncovered underreported emissions and resulted in consent decrees that required pollution control equipment be installed. A key component of the consent decrees was a requirement to conduct emissions tests for volatile organic compounds (VOCs) with the goal of improving the characterization and control of emissions. The conventional VOC stack test method was thought to underquantify total VOC emissions from ethanol plants. A hybrid test method was also developed that involved quantification of individual VOC species. The resulting database of total and speciated VOC emissions from 10 fuel ethanol plants is relatively small, but it is the most extensive to date and has been used to develop and gauge compliance with permit limits and to estimate health risks in Minnesota. Emissions were highly variable among facilities and emissions units. In addition to the variability, the small number of samples and the presence of many values below detection limits complicate the analysis of the data. To account for these issues, a nested bootstrap procedure on the Kaplan-Meier method was used to calculate means and upper confidence limits. In general, the fermentation scrubbers and fluid bed coolers emitted the largest mass of VOC emissions. Across most facilities and emissions units ethanol was the pollutant emitted at the highest rate. Acetaldehyde, acetic acid, and ethyl acetate were also important emissions from some units. Emissions of total VOCs, ethanol, and some other species appeared to be a function of the beer feed rate, although the relationship was not reliable enough to develop a production rate-based emissions factor.     

A study of volatile organic sulfur emissions causing urban odors

Levels of hydrogen sulfide and sulfur containing organic compounds were studied in the air at the deltas of the polluted creeks in the city of Izmir, Turkey in summer 2001. High concentrations of these malodorous compounds were measured in the air samples. Presence of these compounds in the air was connected with the dark appearance and rising gas bubbles in the studied segments of the creeks. These creeks were like open sewers carrying wastewaters from the industry and residential areas into the inner Izmir Bay until September 2001.Within the scope of this study organic sulfur compounds such as methane thiol, ethane thiol, 2-propane thiol, 2-butane thiol, dimethylsulfide, dimethyldisulfide, thiophene, diphenylsulfide and hydrogen sulfide were studied in the air at selected urban sites where odor nuisance was recognized. Flux measurements from polluted surfaces were preferred rather than direct ambient air measurements. Organic sulfur emission fluxes from the creek surfaces were found above the values reported in the literature. Their concentrations and fluxes were higher in June field program. A limited number of measurements of reduced sulfur compound emission concentrations from the wastewater treatment plant equalization tank and the sludge drying beds as well as the landfill soil surface were also included in the study.Concentrations of total organic sulfur compounds and certain individual components such as dimethylsulfide and hydrogen sulfide in emitted gases from river surfaces were correlated with ambient SO(2) concentrations.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.