Release of Mercury Vapor from Coal Combustion Ash

Abstract

The long-term stability of Hg in coal combustion byproducts (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material.

Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 °C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10^-8 lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevalu-ate results reported in this article.     

Sorption of 2,4-D on Natural and Organic Amended Soils of Different Characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unamended soils. In contrast, the ST soil showed the largest adsorption for unamended soil.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

An Assessment of the Significance of Mercury Release from Coal Fly Ash

Abstract

Some mercury (Hg) naturally present in coal is retained in the fly ash remaining after combustion. Concern has been raised regarding the potential for release of this Hg to the environment. The exchange of Hg between fly ash and the atmosphere was measured in the laboratory and in situ at a fly ash landfill. All samples of fly ash used in the laboratory study, with the exception of that derived from lignite-type coal, acted as a sink for atmospheric Hg. Deposition rates were found to increase as air Hg concentrations increased and to decrease with incident light and increased temperature. Addition of water to fly ash samples resulted in re-emission of deposited atmospheric Hg. Deposition was the dominant flux measured in situ at a fly ash landfill. Atmospheric Hg was deposited to all samples collected as part of two demonstration projects using carbon injection for enhanced Hg capture. Hg concentrations of extracts derived using U.S. Environmental Protection Agency Method 1312 (Synthetic Precipitation Leaching Procedure) were ≤14.4 ng/L. Data developed demonstrate that fly ash, including that collected from Hg removal projects, will release little Hg to the air or water, and under certain conditions, absorbs Hg from the air.     

Investigation of a Mercury Speciation Technique for Flue Gas Desulfurization Materials

Abstract

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl₂), mercurous chloride (Hg₂Cl₂), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO₄) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg₂Cl₂ and HgCl₂ could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.     

A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

Heavy Metal Uptake by Two Edible Amaranthus Herbs Grown on Soils Contaminated with Lead,Mercury, Cadmium,and Nickel

The uptake of an element by a plant is primarily dependent on the plant species, its inherent controls, and the soil quality. Amaranthus hybridus (green herbs) and Amaranthus dubius (red herbs) were chosen to investigate their response and ability to accumulate and tolerate varying levels of elements in their roots and shoots. Red herbs and green herbs were grown in soil pots contaminated with three mixtures of Cd(II), Ni(II), Pb(II), and Hg(II). Plants in the control treatment were grown in the absence of the heavy metals mixture. The distribution of Cd, Ni, Pb, and Hg in the plants (in roots, stems, and leaves) was determined in two stages. Stage 1, after 5 weeks of plant growth and stage 2, full grown after 10 weeks of growth. In the red herbs the Cd concentration in the leaves at stage 2 was 150 ppm and was present in higher concentrations than Ni, Hg, and Pb. At the highest contamination level, in the green herbs plant, Hg was present in the highest concentration in the root, i.e., 336 ppm at stage 1, while the level in the leaves was 7.12 ppm. Both the green and red herbs species showed an affinity for Ni and Cd with moderate to high levels detected in the leaves, respectively.     

Conditioning of Fly Ash with Ammonia

This paper presents the results of an investigation of the conditioning of fly ash with ammonia in electrostatic pre-cipitators of power plants operated by the Tennessee Valley Authority. It focuses attention primarily on the mechanisms of conditioning encountered under the particular circumstances available for study. No effect of ammonia on the electrical resistivity of fly ash was evident. Instead, the effect of ammonia appeared to be an enhancement pf the space-charge component of the electric field used for charging and precipitating particles of fly ash. In addition, a second effect appeared to be an increase in the cohesiveness of precipitated ash and a reduction in the quantity of ash reentrained during electrode rapping. Data demonstrating the value of ammonia conditioning for lowering the emission pf fly ash during three precipitator studies are presented. Reasons for the ineffectiveness of ammonia conditioning during a fourth precipitator study are discussed. In conclusion, comments are made about the effects to be expected from ammonia conditioning under circumr stances different from those investigated experimentally, particularly with ammonia as a conditioning agent for fly ash from low sulfur western coal.     

Phytoavailability and Fractions of Iron and Manganese in Calcareous Soil Amended with Composted Urban Wastes

Little is known about the effects of applying composted urban wastes on the phytoavailability and distribution of iron (Fe) and manganese (Mn) among chemical fractions in soil. In order to study this concern several experiments in pots containing calcareous soil were carried out. The received treatments by adding separately two rates (20 and 80 Mg ha^?1) of municipal solid waste (MSW) compost and/or municipal solid waste and sewage sludge (MSW-SS) co-compost. The cropping sequence was a lettuce crop followed by a barley crop. It was observed that treatments amended with composted urban wastes tended to promote slight increases in lettuce yield compared to the control. The highest Fe levels in lettuce were found when higher rates of MSW-SS co-compost were applied; these values were significant compared to those obtained in the other treatments. In all cases, the application of organic materials increased the concentration and uptake of Mn in lettuce compared to the control; however, these increases were significant only when higher rates of MSW compost were applied. The organic amendments had beneficial delayed effects on barley yields, showing, in most cases, significant increases compared to the control. In this context, treatments with MSW compost were found to be more effective than the equivalent treatments amended with MSW-SS co-compost. Compared to the control, composted urban wastes increased Fe concentration in straw and rachis, and decreased Fe concentration in barley grain. Similarly, a decreased concentration of Mn in the dry matter of barley crop grown in soils treated with composted urban wastes was observed.     

Electrostatic Precipitation Tests with Fuel Oil Ash

The main characteristics of the electrostatic collection of fuel oil ash has been investigated at a pilot precipitator installed in a laboratory rig. The relationship between collection efficiency, dust concentration and air velocity is studied and the influence of the spacing between the collection plates on both efficiency and effective migration velocity is discussed. Emphasis is put on the high degrees of efficiency attainable under suitable operating conditions.     

Air Particulates Associated with the Ash Whitefly

Unusual air particulates are linked to recent heavy infestations of the ash whitefly in California using high-performance liquid chromatography, scanning electron microscopy, optical and infrared microscopy, ion chromatography and X-ray fluorescence spectrometry. The unusual particles apparently are microdroplets of ash whitefly honeydew. Most of the suspended honeydew is in microdroplets with diameters between about two and twenty microns. The microdroplets were found to contain substantial amounts of sugars, primarily the oligosaccharides stachyose and raffinose. They also contain about 1 percent potassium, mainly as K⁺ The unusual microdroplets have been found in samples of air particulates taken in many areas of California after 1988.

Using a receptor model, the suspended honeydew was calculated to add as much as 40 microgm/M³ to PM₁₀ mass. The highest levels of suspended honeydew occurred between late August and early November.     

Measurement of Particulate Bound Mercury,Gaseous Elemental Mercury,and Reactive Gaseous Mercury Concentrations by Using an Ambient Air Mercury Collection System

In this investigation, the concentrations of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate bound mercury (PBM) in ambient air were measured at the Hung Kuang (traffic) sampling site during September 27 to October 6, 2014. An ambient air mercury collection system (AAMCS) was utilized to measure simultaneously PBM, GEM, and RGM concentrations in ambient air. The results thus obtained demonstrate that the mean concentrations of PBM, GEM, and RGM were 38.57 ± 11.4 (pg/m³), 17.67 ± 5.56 (ng/m³) and 10.78 ± 2.8 (pg/m³), respectively, at this traffic-sampling site. The mean GEM/PBM and GEM/RGM concentration ratios were 458 and 1639, respectively. The results obtained herein demonstrate that AAMCS can be utilized to collect three phases of mercury simultaneously. The mean PBM, GEM, and RGM concentrations herein were compared with others found in Asia, America, Europe and Antarctica. The mean PBM, GEM, and RGM concentrations were found to be lowest in Asia and Antarctica. The mean PBM concentration in Europe was approximately eight times that in this investigation. The mean GEM and RGM concentrations in this study were 1.21 and 170 times those found in the United States.     

Field Detector Evaluation of Organic Clay Soils Contaminated with Diesel Fuel

Due to numerous types of uncontrolled petroleum releases into the environment such as leaking storage tanks, spills, and improper disposal of petroleum wastes, there is a need for quicker, more efficient methods to determine the levels of soil contamination for site remediation. The portable field detectors used most often in preliminary site evaluations are the flame ionization detector (FID) and the photoionization detector (PID). This research explored the relationship between these two instruments in analysis of two clay soil sites contaminated with diesel fuel. As in previous research, a log-log linear correlation was found between the PID and FID instruments for diesel fuel-contaminated soil at each site (R 2 > 0.91). Also, the correlation factors (0.64 and 0.60) between the field instruments at each site were found to be similar. It was asserted that either field instrument can be used to delineate the diesel fuel contamination at that site based upon a previously calculated correlation between the two instruments, and an overall numerical correlation between the field instruments can be used at various sites of similar soil and contamination characteristics. The implementation of the relationships between these two instruments could facilitate and accelerate site characterization in the future.     

Evaluation of an Offline Method for the Analysis of Atmospheric Reactive Gaseous Mercury and Particulate Mercury

Abstract

Reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected in Milwaukee, WI, between April 2004 and May 2005, and in Riverside, CA, between July 25 and August 7, 2005 using sorbent and filter substrates. The substrates were analyzed for mercury by thermal desorption analysis (TDA) using a purpose-built instrument. Results from this offline-TDA method were compared with measurements using a real-time atmospheric mercury analyzer. RGM measurements made with the offline-TDA agreed well with a commercial real-time method. However, the offline TDA reported PHg concentrations 2.7 times higher than the real-time method, indicating evaporative losses might be occurring from the real-time instrument during sample collection. TDA combined with reactive mercury collection on filter and absorbent substrates was cheap, relatively easy to use, did not introduce biases due to a semicontinuous sample collection strategy, and had a dynamic range appropriate for use in rural and urban locations. The results of this study demonstrate that offline-TDA is a feasible method for collecting reactive mercury concentrations in a large network of filter-based samplers.     

原子荧光法测定土壤中的汞

建立了原子荧光光度计测定土壤中汞的分析方法，对影响土壤中汞测定的各种因素，如空白值的控制、样品的消解、共存离子的干扰和标准溶液的存放等作了研究，从而提出了土壤中汞测定的最佳条件及分析方法。     

Design Variables Associated with Fiberglass/Fly Ash Fabric Filter Cleaning

This paper documents the variation in pressure drop and collection efficiency for fiberglass/fly ash fabric filter systems caused by variations in cleaning intensity (reverse air and reverse pulse), air to cloth ratio, and dust loading. Reverse air rates greater than 2 fpm were required to produce stable pressure characteristics. Pulse jet pressure greater than 50 psi reduced collection efficiency. Increased air to cloth ratios produced decreased collection efficiency.     

A Mercury Vapor Detector Based upon the Automatic Adjustment of Lamp Intensity to the Mercury Concentration

An office containing about 65 employees was found to have 8-h average CO concentrations of 18-26 ppm during a week in winter. On one Friday afternoon, 20 nonsmoking office workers had alveolar CO levels of 23 ± 3 ppm compared to levels of 8 ± 2 ppm in six nonsmoking workers in other offices in the same building. After a weekend at home, the affected office workers displayed reduced alveolar CO levels of 7 ± 2 ppm. The source of the high CO levels was attributed to a parking garage on the same level as the office. Closing fire doors and activating garage fans rectified the situation. The breath sampling method is found to require a correction factor based on the difference between the true alveolar CO and the CO level in the surrounding air. The methods and equipment employed in this study (personal air monitors, electronic data loggers, breath sampling) are recommended for screening and identifying potential CO problems in buildings with similar conditions.     

Mercury in soils of three agricultural experimental stations with long-term fertilization in China

Mercury (Hg) in the agricultural ecosystem is a global concern because of its high potential toxicity. The objectives of this study were to determine the concentration and distribution of Hg in soils from three long-term experimental stations, i.e., Taoyuan (TY) and Qiyang (QY) in Hunan Province and Fengqiu (FQ) in Henan Province of China, and thus to assess the possible food and health risk of long-term applications of fertilizers. Soil samples at each site were collected from different fertilization plots and also from soil profiles with depths 0-100 cm. There were significant differences in soil Hg concentrations in 0-20 cm (A) or 20-40 cm (B) horizon among the three experimental stations. QY station showed significantly higher Hg concentrations than TY and FQ stations. However, there were no significant differences in soil Hg concentrations between A and B horizons at each station. It was concluded that the soil Hg concentrations at the three sites were mainly controlled by the parent materials. Moreover, chemical fertilizer, especially phosphorous fertilizers, could influence the soil Hg concentrations to some extent at the station with lower soil Hg concentrations, for example, at TY station. There were minimal amounts of Hg resulting from applications of the other chemical fertilizers and organic manure, and thus the fertilization had very low risk to the food security of the agro-ecosystems in the terms of Hg inputs and contamination.     

Two-Compartment Sorption of Phenanthrene on Eight Soils with Various Organic Carbon Contents

Sorption characteristics of phenanthrene (PHE) were studied on eight soils with organic carbon contents spanning over an order of magnitude using phase distribution relationships (PDRs) at 1 h, 48 h, and 720 h contact times. A new algebraic method was employed to describe the sorption characteristics at different time intervals (between 1 h and 48 h, and 1 h and 720 h). It was found that nonlinearity increased with increasing contact time and sorption that occurred in the subsequent time interval following the initial 1 h exhibited stronger isotherm nonlinearity. Sorption coefficients were positively correlated with the organic carbon contents of the soils. Detailed sorption dynamics were also examined on these soils. A two-compartment, first-order model was used to describe the sorption dynamics. The rate constants of the two compartments differed 18–170 times, suggesting the dissimilar sorption behaviors of the mathematically separated compartments. These two compartments were labeled fast and slow sorption compartment according to the rate constants. Calculation showed that the fast compartment accounted for over 80% of the overall sorption at the initial 1 h, while the slow compartment predominated the total sorption in the following 47 h. By combining the discussion of PDRs and sorption dynamics, the contributions of the two compartments to linear and nonlinear sorption were differentiated. The slow sorption compartment made a major contribution to nonlinear sorption and possibly to sequestration of organic pollutants by these soils.     

Airborne Emissions of Mercury from Municipal Solid Waste. II: Potential Losses of Airborne Mercury before Landfill

Abstract

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg⁰) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg⁰ to the air if it is initially present or formed by chemical reduction of Hg^II to Hg⁰ within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (～100 mg/hr) and from dumpsters in the field (～30 mg/hr for 1,000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg⁰ signals, indicating that much of the Hg was already present in a metallic (Hg⁰) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg⁰ at 10 to >100 μg/hr and continued to act as near constant sources for several days.