Particulate-bound Hg Research Articles

Dry Deposition of Atmospheric Particle-Bound Mercury in the Middle Taiwan

Atmospheric particle-bound mercury Hg(p) concentrations and dry deposition were investigated at Westing Park and Taichung airport sampling sites in the middle of Taiwan during the years 2011 and 2012.The calculated/measured dry deposition flux ratios of ambient air particles and Hg(p) with Petroff and Zhang’s model were also studied. At the Westing Park sampling site, the particle-bound Hg(p) concentration and Hg (p) dry deposition velocity were 0.022 ng/m3 and 1.74 cm/sec, respectively, while at the Taichung airport sampling site these were 0.027 ng/m3 and 1.03 cm/sec, respectively. The average calculated/measured dry deposition flux ratios for ambient air particles and Hg(p) at average particle sizes of 10, 20 and 23 μm in were 0.79, 1.22, and 1.43, and 0.93, 1.43 and 1.69 at the Westing Park sampling site, respectively. The average calculated/measured dry deposition flux ratios for ambient air particles and Hg(p) at average particle sizes of 10, 20 and 23 μm were 0.92, 1.42, and 1.67, and 1.05, 1.61 and 1.90 at the Taichung airport sampling site, respectively. This study also found that Petroff and Zhang’s model produced the best for the prediction of ambient air particulates and Hg(p) dry deposition for a particle size of 10 μm at both the Westing Park and Taichung airport sampling sites, and that the results became worse as the particle size increased.

The Effect of Wildfire on Soil Mercury Concentrations in Southern California Watersheds

Mercury (Hg) stored in vegetation and soils is known to be released to the atmosphere during wildfires, increasing atmospheric stores and altering terrestrial budgets. Increased erosion and transport of sediments is well-documented in burned watersheds, both immediately post-fire and as the watershed recovers; however, understanding post-fire mobilization of soil Hg within burned watersheds remains elusive. The goal of the current study is to better understand the impact of wildfire on soil-bound Hg during the immediate post-fire period as well as during recovery, in order to assess the potential for sediment-driven transport to and within surface waters in burned watersheds. Soils were collected from three southern California watersheds of similar vegetation and soil characteristics that experienced wildfire. Sampling in one of these watersheds was extended for several seasons (1.5 years) in order to investigate temporal changes in soil Hg concentrations. Laboratory analysis included bulk soil total Hg concentrations and total organic carbon of burned and unburned samples. Soils were also fractionated into a subset of grain sizes with analysis of Hg on each fraction. Low Hg concentrations were observed in surface soils immediately post-fire. Accumulation of Hg coincident with moderate vegetative recovery was observed in the burned surface soils 1 year following the fire, and mobilization was also noted during the second winter (rainy) season. Hg concentrations were highest in the fine-grained fraction of unburned soils; however, in the burned soils, the distribution of soil-bound Hg was less influenced by grain size. The accelerated accumulation of Hg observed in the burned soils, along with the elevated risk of erosion, could result in increased delivery of organic- or particulate-bound Hg to surface waters in post-fire systems.

Mercury Emissions Control in Coal Combustion Systems Using Potassium Iodide: Bench-Scale and Pilot-Scale Studies

Addition of halogens or halides has been reported to promote mercury removal in coal-fired power plants. In this study, bench- and pilot-scale experiments were conducted using potassium iodide (KI) for capture and removal of Hg in air and coal combustion exhaust. Two bench-scale reactor systems were used: (1) a packedbed reactor (PBR) packed with granular or powder KI and (2) an aerosol flow reactor (AFR) with injection of KI particles. It was found that a higher temperature, a higher concentration of KI, and a longer gas residence time resulted in a higher Hg removal efficiency. A 100% Hg removal was achieved in the PBR above 300 °C using 0.5 g of powder KI and in the AFR above 500 °C with a KI/Hg molar ratio of 600 at a 5.8 s residence time. The low KI injection ratio relative to Hg indicated that KI is highly effective for Hg removal in air. Formation of I2 vapor by the oxidation of KI by O2 at high temperatures, which then reacts with Hg to produce HgI2, was identified as the pathway for removal. The pilot-scale experiments were conducted in a 160 kW pulverized coal combustor. KI was introduced in two ways: as a powder mixed with coal and by spraying KI solution droplets into the flue gas. In both cases the Hg removal efficiency increased with an increase in the feed rate of KI. Mixing KI powder with coal was found to be more effective than spraying KI into the flue gas, very likely due to the higher temperature, longer residence time of KI, and the formation of a secondary reactive sorbent. The Hg removal by KI was less efficient in the pilot-scale tests than in the bench-scale tests probably due to certain flue gas components reacting with KI or I2. Hg speciation measurements in both benchand pilot-scale experiments indicated no oxidized mercury in the gas phase upon introduction of KI, indicating that the oxidation product HgI2 was captured in the particulate phase. This is very beneficial in coal-fired power plants equipped with electrostatic precipitators where particulate-bound Hg can be efficiently removed.

Mercury concentration, speciation and budget in volcanic aquifers: Italy and Guadeloupe (Lesser Antilles)

Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth's geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization [WHO (1993): WHO Guidelines for Drinking Water Quality- http://www.who.int/water_sanitation_health/GDWQ/index.htlm]. Positive co-variations of (THg) with sulphate indicate that Hg-SO 4-rich acid groundwaters receive a direct input of magmatic/hydrothermal gases carrying mercury as Hg 0 (gas). Increasing THg in a volcanic aquifer could thus be a sensitive tracer of magmatic gas input prior to an eruption. Since the complex behaviour and toxicity of mercury in waters depend on its chemical speciation, we carefully determined the different aqueous forms of this element in our samples. We find that dissolved elemental Hg 0 (aq) and particulate-bound Hg (Hg P) widely prevail in volcanic aquifers, in proportions that highlight the efficiency of Hg adsorption onto colloidal particles. Moreover, we observe that dissolved Hg 0 aq and Hg(II) forms coexist in comparable amount in most of the waters, in stark contrast to the results of thermodynamic equilibrium modelling. Therefore, chemical equilibrium between dissolved mercury species in volcanic waters is either prevented by natural kinetic effects or not preserved in collected waters due to sampling/storage artefacts. Finally, we provide a first quantitative comparison of the relative intensity of aqueous transport and atmospheric emissions of mercury at Mount Etna, a very active basaltic volcano.

Sources, fate and transport of atmospheric mercury from Asia

Environmental context. Mercury is a global problem and more than half of all anthropogenic emissions are from Asia. In this paper we review the sources of mercury coming from Asia, the environmental fate of these emissions and their global transport. Asian emissions of mercury are responsible for a small, but significant share of the mercury that deposits throughout the world, especially in the northern hemisphere. Abstract. Asian anthropogenic emissions of mercury to the atmosphere contribute 54% of all anthropogenic emissions. For this reason, it is important to understand how these emissions impact both the regional and global mercury cycle. The largest share of mercury emissions in Asia is due to coal combustion and smelting. Approximately half of the Asian anthropogenic emissions are emitted as Hg0. The remainder are emitted as gaseous Hg2+ compounds and particle-bound Hg (PHg). These latter forms of Hg are susceptible to relatively rapid removal from the atmosphere. The Asian emissions lead to very high concentrations of airborne Hg in urban and rural areas of Asia. Modelling the fate and transport of the Asian emissions using the Goddard Earth Observing System (GEOS)-Chem model of global tropospheric chemistry shows that these emissions are associated with high deposition of Hg within Asia, but there is little data with which to evaluate this model result. Observations downwind of Asia show that Hg0 is the dominant form in Asian plumes, with generally small, but variable amounts of other forms. Thus we conclude that most of the Asian Hg2+ and PHg have been removed in the source region. In addition, downwind observations show that total emissions are significantly larger than indicated by the anthropogenic emission inventory. This likely reflects either an underestimate of the anthropogenic emissions or emissions of Hg from land. Plumes containing enhancements in Asian Hg0, but not other species, have been detected as far away as North America. Because only Asian Hg0 is transported long distances, the deposition is distributed relatively uniformly in the northern hemisphere. In North America, Asian anthropogenic emissions account for 7–20% of all deposition, with an average of 16%.

Mercury distribution and transport in a contaminated river system in Kazakhstan and associated impacts on aquatic biota

Abstract The River Nura in Central Kazakhstan has been heavily polluted by Hg originating from an acetaldehyde plant. A number of studies were undertaken to investigate the transport, fate and bioavailability of Hg in this river system. The sediments within a 20 km section of the river downstream of the effluent outfall canal are highly polluted and are acting as a strong source of surface water contamination. Mercury transport in the river is dominated by the remobilization of contaminated bed sediments and river bank erosion during the annual spring flood. Peak Hg concentrations in unfiltered surface water samples during a larger than usual flood event in 2004 were in the order of 1600–4300 ng L−1. The majority of the particulate-bound Hg appears to be sedimented in the shallow Intumak reservoir ∼75 km downstream of the source of the pollution, leading to a drop in aqueous Hg concentrations by an order of magnitude. Nevertheless, background concentrations of Hg in surface water are not reached until at least 200 km downstream, and during the flood period Hg is also detected in the terminal wetlands of the river. Mercury concentrations in sediment cores taken from the river bed in the most contaminated section of the Nura ranged from 9.95 to 306 mg kg−1. Methylmercury (MeHg) levels in shallow sediment cores were highest in surface sediments and ranged between 4.9 and 39 μg kg−1, but were generally less than 0.1% of total Hg (THg). A significant inverse relationship was found between THg concentrations and the percentage of MeHg formed in the sediments, irrespective of the sampling depth. The observed relationship was confirmed by comparison with results from a different river system, indicating that it may be true also for other highly contaminated aquatic systems. It is hypothesized that at high THg levels in severely contaminated sediments, the accumulation of MeHg may be limited by increasingly efficient demethylation processes, and that this underlying trend in sediments is the reason why MeHg levels in surface water are often found to be higher at less contaminated sites compared to upstream sites. Mercury concentrations in biota in the most contaminated section of the river were 15–20 times higher than background levels. Fish were found to be impacted for more than 125 km downstream from the source, indicating significant transport of dissolved MeHg to downstream areas and/or in-situ MeHg production in less contaminated downstream reaches. There were also indications that impoundments may increase the bioavailability of Hg.

MACROINVERTEBRATE PRODUCTION AND FOOD WEB ENERGETICS IN AN INDUSTRIALLY CONTAMINATED STREAM

This study examines secondary production and periphyton-invertebrate food web energetics at two sites in an industrially contaminated, nutrient-enriched stream. Secondary production data and data from the literature were used to calculate potential amounts of mercury transferred from periphyton to chironomid larvae and into terrestrial food webs with emerging adults. The nutritional quality of periphyton was characterized using energy content, chlorophyll a, protein, ash-free dry mass (AFDM), and percentage of organic matter. Chironomid larvae (Orthocladiinae: Cricotopus spp.) comprised 96% of all macroinvertebrates collected from stones at the two sites. Cricotopus production was extremely high: production was 59.5 g AFDM x m(-2) x yr(-1) at the site upstream of a 1-ha settling basin and 32.4 g AFDM x m(-2) x yr(-1) at the site below the basin. Apparent differences in annual secondary production were associated with reduced organic content (i.e., nutritional quality) of the periphyton matrix under different loading of total suspended solids. The periphyton matrix at both sites was contaminated with inorganic (Hg(II)) and methyl (MeHg) mercury. The amount of Hg(II) potentially ingested by Cricotopus was calculated to be 49 mg Hg(II) x m(-1) x yr(-1) at the upstream site and 19 mg Hg(II)x m(-2) x yr(-1) at the downstream site. Mercury ingestion by Cricotopus at the downstream site was calculated to be 2% of the estimated annual deposition of particulate-bound Hg(II) to the stream bed. Emergence of adult Cricotopus was calculated to remove 563 microg Hg(II)x m(-2) x yr(-1) from the stream at the upstream site and 117 microg Hg(II) x m(-2) x yr(-1) at the downstream site, which amounted to 4.1 g Hg(II)/yr for the 2.1-km reach of stream included in this study. The ratio of metal export in emergence production to surface area for the study stream was 10 to 10(3) times higher than ratios calculated for lakes using data from the literature. This study is the first well-documented example of extremely high aquatic insect production in an industrially contaminated, nutrient-enriched stream, and it highlights the application of production measurements to examine the role of aquatic insect production in the trophic transfer of energy and persistent contaminants in aquatic food webs and into terrestrial food webs.

A pilot study to determine mercury exposure through vapor and bound to PM10 in a dental school environment

Mercury (Hg) is widely used in the dental working environment, exposing dental practitioners and assistants to potentially toxic Hg vapors. Concentrations of Hg in vapor and in particulate matter (PM10) were measured in the Dental Simulation Laboratory (DSL) and in the Dental Clinic (DC) at the School of Dentistry, University of Puerto Rico. PM10 samples were collected over a 36-h period and Hg vapor was collected for eight-hour periods. PM10 mass was determined gravimetically and Hg (bound to PM10 and vapor) was extracted and analyzed by atomic absorption. Indoor levels of PM10 in the DSL ranged from 9.2 to 41.6 microg/m3 and 35.0 to 68.2 microg/m3 in the DC. Levels of particle-bound Hg ranged from 0.1 to 1.2 microg/m3 and in vapor 1.1 to 3.3mg/m3 at the DSL; the DC levels ranged from <0.01 to 0.2 microg/m3 for particle bound Hg and 13.6 to 102.7 microg/m3 in vapor. PM10 concentrations were below Indoor Air Quality suggested limits for total dust (100 microg/m3). Levels of mercury bound to PM10 were low; however, mercury vapor was several times higher than the suggested OSHA (permissible exposure limit--100 microg/m3) in the DSL.

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems

The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.

Macroscopic and Microscopic Observations of Particle-Facilitated Mercury Transport from New Idria and Sulphur Bank Mercury Mine Tailings

Mercury (Hg) release from inoperative Hg mines in the California Coast Range has been documented, but little is known about the release and transport mechanisms. In this study, tailings from Hg mines located in different geologic settings--New Idria (NI), a Si-carbonate Hg deposit, and Sulphur Bank (SB), a hot-spring Hg deposit--were characterized, and particle release from these wastes was studied in column experiments to (1) investigate the mechanisms of Hg release from NI and SB mine wastes, (2) determine the speciation of particle-bound Hg released from the mine wastes, and (3) determine the effect of calcinations on Hg release processes. The physical and chemical properties of tailings and the colloids released from them were determined using chemical analyses, selective chemical extractions, XRD, SEM, TEM, and X-ray absorption spectroscopy techniques. The total Hg concentration in tailings increased with decreasing particle size in NI and SB calcines (roasted ore), but reached a maximum at an intermediate particle size in the SB waste rock (unroasted ore). Hg in the tailings exists predominantly as low-solubility HgS (cinnabar and metacinnabar), with NI calcines having >50% HgS, SB calcines having >89% HgS, and SB waste rock having approximately 100% HgS. Leaching experiments with a high-ionic-strength solution (0.1 M NaCl) resulted in a rapid but brief release of soluble and particulate Hg. Lowering the ionic strength of the leach solution (0.005 M NaCI) resulted in the release of colloidal Hg from two of the three mine wastes studied (NI calcines and SB waste rock). Colloid-associated Hg accounts for as much as 95% of the Hg released during episodic particle release. Colloids generated from the NI calcines are produced by a breakup and release mechanism and consist of hematite, jarosite/alunite, and Al-Si gel with particle sizes of 10-200 nm. ATEM and XAFS analyses indicate that the majority (approximately 78%) of the mercury is present in the form of HgS. SB calcines also produced HgS colloids. The colloids generated from the SB waste rockwere heterogeneous and varied in composition according to the column influent composition. ATEM and XAFS results indicate that Hg is entirely in the HgS form. Data from this study identify colloidal HgS as the dominant transported form of Hg from these mine waste materials.

Comment on “Mercury concentrations in coastal California precipitation: Evidence of local and trans‐Pacific fluxes of mercury to North America” by D. J. Steding and A. R. Flegal

[1] In the paper by Steding and Flegal [2002] the authors claim to identify Hg in rain from trans-Pacific sources. Specifically, Steding and Flegal (paragraph [1]) state that ‘‘the Asian fluxes appear to enhance Hg concentrations both directly, through the emission of particle-bound Hg and reactive Hg, and indirectly, by increasing the rate of oxidation of Hg in the atmosphere.’’ They arrive at this conclusion by analysis of 46 event-based precipitation measurements of total Hg from two sites in California, combined with isentropic back-trajectories to identify the source region for the sampled air masses. [2] While this paper provides some potentially useful new data on Hg in rain, we found the arguments less then convincing. It is important to note that while the authors’ conclusion is plausible, the evidence presented by Steding and Flegal [2002] is insufficient to support this conclusion. Our concern with their analysis is based on three key points.

Mercury control research: effects of fly ash and flue gas parameters on mercury speciation

Mercury Control Research: Effects of Fly Ash and Flue Gas Parameters on Mercury Speciation Chun Wai Lee and James D. Kilgroe U.S. Environmental Protection Agency National Risk Management Research Laboratory Research Triangle Park. NC S. Behrooz Ghorishi ARCADIS Geraghty & Miller, Inc. Research Triangle Park, NC In flue gas from combustion systems, mercury (Hg) is typically in the vapor phase at flue gas cleaning temperatures, and the control of Hg emissions is dependent on the specific Hg compounds that are present (speciation) and the type of air pollution devices employed. In dry and semi-dry scrubbing systems, the control of Hg emissions is dependent on the sorption of Hg by particulate matter (PM) which can be subsequently collected in a PM control device. In wet scrubbing systems, the principal mechanisms of control are the removal of soluble forms of Hg and the collection of particle-bound Hg. At combustion temperatures, Hg is believed to be predominantly in the form of elemental mercury (Hgo). As the flue gas is cooled, thermochemical equilibrium calculations indicate that Hgo is converted primarily to ionic mercury (Hg++) in the form of mercuric oxide (HgO) or mercuric chloride (HgCl2). Hgo is insoluble in water, but HgO has a low solubility while HgCl2 is highly soluble. The oxidation of Hgo to an ionic form depends on the temperature, the time-temperature proflle, the flue gas composition, the reaction kinetics, and the presence of solids that may catalyze reactions. Bench-scale experiments were conducted to study the effects of flue gas and fly ash parameters on the oxidation of HgOin simulated flue gases containing hydrogen chloride (Hel). Gas-phase studies indicated that the in-flight post-combustion oxidation of Hgo in the presence of HCI is very slow and proceeds at measurable rates only at high temperatures (>700 °C) and high HCI concentrations (>200 ppm). The presence of sulfur dioxide (S02) and water vapor in the simulated flue gas significantly inhibited the gas-phase oxidation of Hgo. On the other hand, a preliminary investigation indicated that the gas-phase reaction of Hgo with chlorine (Cl:z) is fast At 40°C and in the presence of 50 ppm C12, 100% of the input Hgo was oxidized to HgCl2 in less than 2 seconds, indicating that Cl2 is a much more active chlorinating agent than HCl. The effects of fly ash composition were investigated using a fixed-bed reactor containing different model fly ashes (simulated fly ash) consisting of mixtures of some major components found in coal and municipal waste combustor (MWC) fly ashes. Work to date has focused on the

Mercury Mass Balances: A Case Study of Two North Dakota Power Plants

ABSTRACT The Energy & Environmental Research Center (EERC) conducted a mercury-sampling program to provide data on the quantity and forms of Hg emitted and on the Hg removal efficiency of the existing air pollution control devices at two North Dakota power plants—Milton R. Young Station and Coal Creek Station. Minnkota Power Cooperative, Great River Energy, the North Dakota Industrial Commission, and EPRI funded the project. The primary objective was to obtain accurate measurements of Hg released from each plant, as verified by a material balance. A secondary objective was to evaluate the ability of a mercury continuous emission monitor (CEM) to measure total Hg at the stack. At both plants, speciated Hg measurements were made at the inlets and outlets of both the electrostatic precipi-tators (ESPs) and the flue gas desulfurization (FGD) systems. A Semtech Hg 2000 (Semtech Metallurgy AB) mercury CEM was used to measure the total Hg emissions at the stack in real time. Using these measurements and plant data, the measured Hg concentrations in the coal, FGD slurries, and ESP ash, a Hg mass flow rate was calculated at each sampling location. Excellent Hg mass balances were obtained (±15%). It was also found that the Hg was mostly in the elemental phase (~90%), and the small amount of oxidized Hg that was generated was removed by the FGD systems. Insignificant amounts of particulate-bound Hg were measured at both plants. However, 10-20% of the elemental Hg measured prior to the ESP was converted to oxidized Hg across the ESP. The data show that, at these facilities, almost all of the Hg generated is being emitted into the atmosphere as elemental Hg. Local or regional deposition of the Hg emitted from these plants is not a concern. However, the Hg does become part of the global Hg burden in the atmosphere. Also, the evidence appears to indicate that elemental Hg is more difficult to remove from flue gas than oxidized Hg is.