Quantifying Asian and biomass burning sources of mercury using the Hg/CO ratio in pollution plumes observed at the Mount Bachelor observatory

Total airborne mercury (TAM) and carbon monoxide (CO) were measured in 22 pollution transport “events” at Mt. Bachelor Observatory (MBO), USA (2.8 km asl) between March 2004 and September 2005. Submicron particulate scattering (${\sigma }_{\mathrm{sp}})$, ozone (${\mathrm{O}}_3)$, and nitrogen oxides (${\mathrm{NO}}_y)$ were also measured and enhancement ratios for each chemical and aerosol species with CO were calculated. Events were categorized based on their source regions, which were determined by a combination of back trajectories, satellite fire detections, chemical and aerosol enhancement ratios, and meteorology. The mean $\mathrm{\Delta }\mathrm{TAM}/\mathrm{\Delta }\mathrm{CO}$ values for each source region are: East Asian industrial ($0.0046\pm 0.0013\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=10$ events, 236 h), Pacific Northwest U.S. (PNW) biomass burning ($0.0013\pm 0.008\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=7$ events, 173 h), and Alaska biomass burning ($0.0014\pm 0.0006\mathrm{ng}{\mathrm{m}}^{-3}{\mathrm{ppbv}}^{-1}$, $n=3$ events, 96 h). The $\mathrm{\Delta }\mathrm{TAM}/\mathrm{\Delta }\mathrm{CO}$ means from Asian long-range transport (ALRT) and biomass burning events are combined with previous estimates of CO emissions from Chinese anthropogenic, global biomass burning, and global boreal biomass sources in order to estimate the emissions of gaseous elemental mercury (GEM) from these sources. The GEM emissions that we calculate here are: Chinese anthropogenic ($620\pm 180\mathrm{t}{\mathrm{y}}^{-1}$), global biomass burning $(670\pm 330\mathrm{t}{\mathrm{y}}^{-1})$, and global boreal biomass burning $(168\pm 75\mathrm{t}{\mathrm{y}}^{-1})$, with errors estimated from propagating the uncertainty in the mean enhancement ratios and CO emissions. A comparison of our results with published mercury (Hg) emissions inventories reveals that the Chinese GEM emissions from this study are higher by about a factor of two, while our estimate for global biomass burning is consistent with previous studies.     

Anthropogenic mercury emissions in China

An inventory of mercury emissions from anthropogenic activities in China is compiled for the year 1999 from official statistical data. We estimate that China's emissions were 536 (±236) t of total mercury. This value includes open biomass burning, but does not include natural sources or re-emission of previously deposited mercury. Approximately 45% of the Hg comes from non-ferrous metals smelting, 38% from coal combustion, and 17% from miscellaneous activities, of which battery and fluorescent lamp production and cement production are the largest. Emissions are heaviest in Liaoning and Guangdong Provinces, where extensive smelting occurs, and in Guizhou Province, where there is much small-scale combustion of high-Hg coal without emission control devices. Emissions are gridded at 30×30 min spatial resolution. We estimate that 56% of the Hg in China is released as Hg⁰, 32% as Hg²⁺, and 12% as Hg^p. Particulate mercury emissions are high in China due to heavy burning of coal in residential and small industrial settings without PM controls. Emissions of Hg²⁺ from coal-fired power plants are high due to the absence of flue-gas desulfurization units, which tend to dissolve the soluble divalent mercury. Metals smelting operations favor the production of elemental mercury. Much of the Hg is released from small-scale activities in rather remote areas, and therefore the activity levels are quite uncertain. Also, emissions test data for Chinese sources are lacking, causing uncertainties in Hg emission factors and removal efficiencies. Overall, we calculate an uncertainty level of ±44% (95% confidence interval) in the estimate of total emissions. We recommend field testing of coal combustors and smelters in China to improve the accuracy of these estimates.     

Particulate PAHs observed in the surrounding of a municipal incinerator

An intensive sampling campaign was undertaken in the surroundings of a municipal waste incinerator located in a French great urban centre in order to evaluate the impact of particles emissions on the ambient air and to estimate the exposure levels to toxic or carcinogenic compounds for a population living in the neighbourhood of this incinerator. To minimise the effect of industrial and road activities, sampling was performed during the 2 days of a weekend and on Monday morning. Different operating modes of the incinerator were investigated: (i) normal incinerator functioning and (ii) maintenance activity of the combustion chamber corresponding to the stop and cooling furnace periods. Particulate polycyclic aromatic hydrocarbons (PAHs) and total particulate carbon concentrations were determined in three sites situated, respectively, close to the incinerator, 2 km downwind and 1 km upwind of the plant. In normal operating mode similar concentrations were observed in the three sites. During the furnace stop an increase of total PAH concentrations was observed in the sampling site close to the incinerator. The concentration was 3 times higher than those measured in the other two sampling sites. But this increase was limited in time and in space since this phenomenon is only observed in the vicinity of the incinerator. The study of PAH profiles indicated that Pyrene and Retene showed the highest enhancement of their relative concentrations. The influence of incinerator functioning parameters on the PAHs concentrations is discussed. The furnace temperature and the mode of exhaust fumes seem to be deciding parameters to explain the increase of PAH level in the incinerator site. However, the incinerator emissions remained a minor part of the atmospheric pollution in the urban area.     

Particulate sulfur analysis: Application to high time resolution aircraft sampling in plumes

Application of vaporization flame-photometric detector (FPD) method for analysis of submicrogram amounts (> 0.3 μg) of atmospheric particulate sulfur for samples collected in plumes is described. Aerosol is deposited on a portion (0.3 cm²) of a light weight, low pressure drop glass-fiber filter with a consistent, low sulfur blank of 0.36–0.5μg cm⁻². Water extracts are analyzed for sulfur with a precision of 2.5%, while the precision of the entire analytical procedure is estimated to be 5%. The aerosol sampling is performed with a sequential two-stage tape sampler which separates the ambient aerosol in coarse (>3 μm) and fine (<3 μm) size ranges. The sampling time required by the method is 7 min for plume sulfur concentrations of 3 μg m⁻³. It was found feasible to measure the average sulfur concentration obtained during a single traverse across a large plume. The method has been used for aerosol sampling and sulfur analysis of samples collected in power plant and urban-industrial plumes in the St. Louis area.     

Real-world vehicle emissions as measured by in situ analysis of exhaust plumes

Environmental Science and Pollution Research - We conducted a 60-day roadside measurement campaign on a busy street in Münster, Germany, during summer 2016. We used gas and particle...     

Inhalable Particulate Levels in Northern Idaho from the Initial Eruptions of Mount St. Helens

ABSTRACT

This paper describes some characteristics of speciated nonmethane organic compound (NMOC) data collected in 1994 at five Photochemical Assessment Monitoring Stations (PAMS) and archived in the U.S. Environmental Protection Agency’s Aerometric Information Retrieval System (AIRS). Topics include data completeness, distribution of individual NMOCs in concentration categories relative to minimum detectable levels, percentage of total NMOC associated with the sum of the 55 PAMS target compounds, and use of scatterplots to diagnose chromatographic misidentification of compounds. This is an early examination of a database that is expanding rapidly, and the insights presented here may be useful to both the producers and future users of the data for establishing consistency and quality control.     

Particulate matter emissions from on-road vehicles in a freeway tunnel study

Particulate matter, including coarse particles (PM_2.5–10, aerodynamic diameter of particle between 2.5 and 10 μm) and fine particles (PM_2.5, aerodynamic diameter of particle lower than 2.5 μm) and their compositions, including elemental carbon, organic carbon, and 11 water-soluble ionic species, and elements, were measured in a tunnel study. A comparison of the six-hour average of light-duty vehicle (LDV) flow of the two sampling periods showed that the peak hours over the weekend were higher than those on weekdays. However, the flow of heavy-duty vehicles (HDVs) on the weekdays was significant higher than that during the weekend in this study. EC and OC content were 49% for PM_2.5–10 and 47% for PM_2.5 in the tunnel center. EC content was higher than OC content in PM_2.5–10, but EC was about 2.3 times OC for PM_2.5. Sulfate, nitrate, ammonium were the main species for PM_2.5–10 and PM_2.5. The element contents of Na, Al, Ca, Fe and K were over 0.8 μg m^?3 in PM_2.5–10 and PM_2.5. In addition, the concentrations of S, Ba, Pb, and Zn were higher than 0.1 μg m^?3 for PM_2.5–10 and PM_2.5. The emission factors of PM_2.5–10 and PM_2.5 were 18 ± 6.5 and 39 ± 11 mg km^?1-vehicle, respectively. The emission factors of EC/OC were 3.6/2.7 mg km^?1-vehicle for PM_2.5–10 and 15/4.7 mg km^?1-vehicle for PM_2.5 Furthermore, the emission factors of water-soluble ions were 0.028(Mg²⁺)–0.81(SO₄^2?) and 0.027(NO₂^?)–0.97(SO₄^2?) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively. Elemental emission factors were 0.003(V)–1.6(Fe) and 0.001(Cd)–1.05(Na) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively.     

Estimating mercury emissions from a zinc smelter in relation to China’s mercury control policies

Mercury concentrations of flue gas at inlet/outlet of the flue gas cleaning, electrostatic demister, reclaiming tower, acid plant, and mercury contents in zinc concentrate and by-products were measured in a hydrometallurgical zinc smelter. The removal efficiency of flue gas cleaning, electrostatic demister, mercury reclaiming and acid plant was about 17.4%, 30.3%, 87.9% and 97.4% respectively. Flue gas cleaning and electrostatic demister captured 11.7% and 25.3% of the mercury in the zinc concentrate, respectively. The mercury reclaiming tower captured 58.3% of the mercury in the zinc concentrate. About 4.2% of the mercury in the zinc concentrate was captured by the acid plant. Consequently, only 0.8% of the mercury in the zinc concentrate was emitted to the atmosphere. The atmospheric mercury emission factor was 0.5 g t⁻¹ of zinc produced for the tested smelter, indicating that this process offers the potential to effectively reduce mercury emissions from zinc smelting.     

The history of mercury emissions from fuel combustion in Maritime Canada

In this study, we present an inventory of historical emissions of mercury resulting from combustion of wood, coal and refined petroleum products in Maritime Canada. The pattern of emissions illustrates the strong influences of population growth, industrial development and prevailing fuel preferences in the region. According to our calculations, anthropogenic mercury releases from fuel combustion in Maritime Canada have cumulatively totaled more than 50 tonnes since 1800. We have compiled both high and low estimates of annual mercury releases in this region. Mercury emissions from fuel combustion in Maritime Canada reached a maximum level in the 1940s. At this time, emissions were between 778 (low) and 1494 (high) kg per year, coinciding with the period of most intensive coal use in Maritime Canada. In 1995, emissions were approximately 54% of the level reached in 1940, at 427 (low)-800 (high) kg per year. In presenting this emissions inventory, we hope to refine past estimates with current information on the mercury content of different fuel types, and create a comprehensive database on how mercury emissions from various sources have changed over time.     

Predictive modelling of dispersion controlled reactive plumes at the laboratory-scale

A model-based interpretation of laboratory-scale experimental data is presented. Hydrolysis experiments carried out using thin glass tanks filled with glass beads to construct a hypothetical and inert, homogeneous porous medium were analysed using a 2D numerical model. A new empirical formula, based upon results for non-reactive (tracer) experiments is used to calculate transversal dispersivity values for a range of grain sizes and any flow velocities. Combined with effective diffusion coefficients calculated from Stokes-Einstein type equations, plume lengths arising from mixing between two solutes can be predicted accurately using numerical modelling techniques. Moreover, pH and ion concentration profiles lateral to the direction of flow of the mixing species can be determined at any given point downstream, without the need for result fitting. In our case, this approach does not lead to overpredictions of lateral mixing, as previously reported when using parameters derived from non-reactive tracer experiments to describe reactive solute transport. The theory is based on the assumption of medium homogeneity.     

Vehicle emissions of radical precursors and related species observed in the 2009 SHARP campaign

The 2009 Study of Houston Atmospheric Radical Precursors (SHARP) field campaign had several components that yielded information on the primary vehicular emissions of formaldehyde (HCHO) and nitrous acid (HONO), in addition to many other species. Analysis of HONO measurements at the Moody Tower site in Houston, TX, yielded emission ratios of HONO to the vehicle exhaust tracer species NO_x and CO of 14 pptv/ppbv and 2.3 pptv/ppbv, somewhat smaller than recently published results from the Galleria site, although evidence is presented that the Moody Tower values should be upper limits to the true ratios of directly emitted HONO, and are consistent with ratios used in current standard emissions models. Several other Moody Tower emission ratios are presented, in particular a value for HCHO/CO of 2.4 pptv/ppbv. Considering only estimates of random errors, this would be significantly lower than a previous value, though the small sample size and possible systematic differences should be taken into account. Emission factors for CO, NO_x, and HCHO, as well as various volatile organic compounds (VOCs), were derived from mobile laboratory measurements both in the Washburn Tunnel and in on-road exhaust plume observations. These two sets of results and others reported in the literature all agree well, and are substantially larger than the CO, NO_x, and HCHO emission factors derived from the emission ratios reported from the Galleria site.

Implications: Emission factors for the species measured in the various components of the 2009 SHARP campaign in Houston, TX, including HCHO, HONO, CO, CO₂, nitrogen oxides, and VOCs, are needed to support regional air quality monitoring. Components of the SHARP campaign measured these species in several different ways, each with their own potential for systematic errors and differences in vehicle fleets sampled. Comparisons between data sets suggest that differences in sampling place and time may result in quite different emission factors, while also showing that different vehicle mixes can yield surprisingly similar emission factors.     

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.     

Control strategies of atmospheric mercury emissions from coal-fired power plants in China

Atmospheric mercury (Hg) emission from coal is one of the primary sources of anthropogenic discharge and pollution. China is one of the few countries in the world whose coal consumption constitutes about 70% of total primary energy, and over half of coals are burned directly for electricity generation. Atmospheric emissions of Hg and its speciation from coal-fired power plants are of great concern owing to their negative impacts on regional human health and ecosystem risks, as well as long-distance transport. In this paper, recent trends of atmospheric Hg emissions and its species split from coal-fired power plants in China during the period of 2000-2007 are evaluated, by integrating each plant's coal consumption and emission factors, which are classified by different subcategories of boilers, particulate matter (PM) and sulfur dioxide (SO2) control devices. Our results show that the total Hg emissions from coal-fired power plants have begun to decrease from the peak value of 139.19 t in 2005 to 134.55 t in 2007, though coal consumption growing steadily from 1213.8 to 1532.4 Mt, which can be mainly attributed to the co-benefit Hg reduction by electrostatic precipitators/fabric filters (ESPs/FFs) and wet flue gas desulfurization (WFGD), especially the sharp growth in installation of WFGD both in the new and existing power plants since 2005. In the coming 12th five-year-plan, more and more plants will be mandated to install De-NO(x) (nitrogen oxides) systems (mainly selective catalytic reduction [SCR] and selective noncatalytic reduction [SNCR]) for minimizing NO(x) emission, thus the specific Hg emission rate per ton of coal will decline further owing to the much higher co-benefit removal efficiency by the combination of SCR + ESPs/FFs + WFGD systems. Consequently, SCR + ESPs/FFs + WFGD configuration will be the main path to abate Hg discharge from coal-fired power plants in China in the near future. However advanced specific Hg removal technologies are necessary for further reduction of elemental Hg discharge in the long-term.     

Control of mercury emissions from a municipal solid waste incinerator in Japan

The control of Hg emissions from a municipal solid waste incinerator (MSWI) is very important, because more than 78% of municipal solid waste (MSW) is incinerated. The Hg content of coal used in utility boilers is relatively low in Japan. In this study, recent trends in the Hg content of MSW in Japan and activated carbon (AC) injection as a control technology of Hg emission from an MSWI are discussed. The effect of AC injection on Hg removal from flue gas in an MSWI was investigated by pilot-scale experiments using a bag filter (BF). The injection of AC increases the Hg reduction ratio by 20-30% compared with cases without AC injection. The Hg reduction ratio increases as the flue gas temperature decreases. The Hg reduction ratio is closely related to the inlet Hg concentration and was expressed with a Langmuir-type adsorption isotherm.     

Top-down estimate of mercury emissions in China using four-dimensional variational data assimilation

An inverse modeling method using the four-dimensional variational data assimilation approach is developed to provide a top-down estimate of mercury emission inventory in China. The mercury observations on board the C130 aircraft during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign in April 2001 are assimilated into a regional chemical transport model, STEM. Using a 340 Mg of elemental mercury emitted in 1999, the assimilation results in an increase in Hg⁰ emissions for China to 1140 Mg in 2001. This is an upper limit amount of the elemental mercury required in China. The average emission-scaling factor is ∼3.4 in China. The spatial changes in the mercury emissions after the assimilation are also evaluated. The largest changes are estimated on the China north-east coastal areas and the areas of north-center China. The influences of the observation and inventory uncertainties and the initial and boundary conditions on the emission estimates are discussed. Increasing the boundary conditions of Hg from 1.2 to 1.5 ng m⁻³, results in a top-down estimate of Hg⁰ emissions for China of 718 Mg, and leads the average scaling factor from 3.4 to 2.1.     

Atmospheric mercury in the Great Smoky Mountains compared to regional and global levels

Improvements in measurement technology are permitting development of a more detailed scientific understanding of the cycling of mercury in the global atmospheric environment. Critical to advancing the state of knowledge is the acquisition of accurate measurement of speciated mercury (gaseous and particulate) at ground research stations in a variety of settings located around the globe. This paper describes one such research effort conducted at TVA's Look Rock air quality monitoring site in Tennessee—a mountain top site (813 m elevation) just west of the Great Smoky Mountains National Park. The Great Smoky Mountains National Park is the largest National Park in the eastern US and it receives environmental protection under a variety of US statutes. Gaseous and particle mercury species along with some additional trace gases were measured at Look Rock during two field studies totaling 84 days in the spring and summer of 2004. Average results for the entire sampling period are: gaseous elemental mercury Hg(0): 1.65 ng m⁻³, reactive gaseous mercury RGM: 0.005 ng m⁻³, particulate mercury Hg(p): 0.007 ng m⁻³. Literature review indicates that these levels are within the range found for other rural/remote sites in North America and worldwide. Reactive and particulate mercury comprised together less than 1%, on average, of total airborne mercury at Look Rock. When compared to the global background mercury literature, the Look Rock measurements demonstrate that the atmospheric mercury levels in the vicinity of the Great Smoky Mountains National Park are clearly dominated by the global atmospheric pool, not by local or regional sources.     

Wind-tunnel study of entrainment in two-dimensional dense-gas plumes at the EPA's fluid modeling facility

This wind-tunnel study has been conducted as part of a collaborative effort to investigate the effect of large surface roughness on the entrainment of air from a neutrally stable simulated atmospheric boundary layer into a continuous dense-gas plume. The present study examined the entrainment rates of dense-gas plumes as they were transported over two surfaces with similar geometry but significantly different roughness lengths (factor of 6). Extensive measurements of the flow and plume structures over a wide range of source Richardson numbers (Ri*) are reported. Carbon dioxide was released from a two-dimensional source in order to obtain a plume with virtually constant Ri*. Over the small roughness, the plume depths were generally large compared with the element heights, whereas over the large roughness, plume depths were comparable with the element heights. Retardation of mean velocities in the lower levels of the dense plumes (with compensating increases in the upper levels) was observed, as well as strong suppression of turbulence over quite large fractions of the boundary-layer depth. These effects increased as Ri* increased. Propagation of dense gas was observed upstream of the source due to gravity spreading. The flow within the plumes was observed to become laminar at the larger Ri*. The primary measurements comprised longitudinal surface concentration profiles. Where the plumes were fully turbulent, the plots of inverse concentration versus downwind distance formed reasonably straight lines. The sought-after entrainment velocities are proportional to the slopes of these lines and were found to diminish quite rapidly with Ri*. More in-depth analyses and intercomparisons with the results of the other laboratories are contained in a companion paper in this same volume (Briggs et al., 2001, Atmospheric Environment 35, 2265–2284).