Diel variations in photoinduced oxidation of Hg0 in freshwater

Experiments have been conducted to determine diel variations in photoinduced Hg0 oxidation in lake water under natural Hg0(aq) concentrations. Pseudo-first-order rates of photooxidation (k') were calculated for water freshly collected in a Canadian Shield lake, Lake Croche (45 degrees 56' N, 74 degrees 00' W), at different periods of the day and subsequently incubated in the dark. Hg0 oxidation rates ranged from 0.02 to 0.07 h(-1), increasing from sunrise to noon and then decreasing throughout the remainder of the day. These changes paralleled those in sunlight intensity integrated over 1 h preceding water collection, and suggested that the water freshly collected in daylight was rich in photochemically produced Hg0 oxidants. It was also estimated that under intense solar radiation, even if oxidation rates reached a peak, reduction of Hg(II) was the prevalent redox process. Inversely, Hg0 oxidation overcame DGM production during the night or at periods of weaker light intensity. Overall, these findings explain the decreases in the DGM pool generally observed overnight. They also support previous reports that, during summer days, volatilization of Hg0 from water represent an important step in the Hg cycle in freshwater systems.     

A predictive mechanism for mercury oxidation on selective catalytic reduction catalysts under coal-derived flue gas

This paper introduces a predictive mechanism for elemental mercury (Hg(o)) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH3)/nitric oxide (NO) ratio and concentrations of Hg(o) and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg(o) oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH3 and that Hg(o) contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg(o) oxidation by NH3, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH3 adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg(o) oxidation. But once NH3 has been consumed, the Hg(o) oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH3/NO ratios, promote Hg(o) oxidation. This mechanism accurately interprets the reported tendencies for greater extents of Hg(o) oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg(o) oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg(o) oxidation by NH3 for NH3/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg(o) oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.     

Comparison of mercury chemistry models

Five mercury (Hg) chemistry models are compared using the same data set for model initialisation. All five models include gas-phase oxidation of Hg(0) to Hg(II) (except for one model), fast reduction–oxidation aqueous reactions between Hg(0) and Hg(II), and adsorption of Hg(II) species to soot particles within droplets. However, the models differ in their detailed treatments of these processes. Consequently, the 48-h simulations reveal similarities but also significant discrepancies among the models. For the simulation that included all Hg species (i.e., Hg(0), Hg(II) and Hg(p)) as well as soot in the initial conditions, the maximum simulated Hg(II) aqueous concentrations ranged from 55 to 148 ng l⁻¹ whereas the minimum concentrations ranged from 20 to 110 ng l⁻¹. These results suggest that further experimental work is critically needed to reduce the current uncertainties in the formulation of Hg chemistry models.     

Chromium transport, oxidation, and adsorption in manganese-coated sand

We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (beta-MnO2)-coated sand. We find that beta-MnO2 effectively oxidizes Cr(III) to Cr(VI) and that the extent of oxidation is sensitive to changes in pH, pore water velocity, and influent concentrations of Cr(III). Cr(III) oxidation rates, although initially high, decline well before the supply of beta-MnO2 is depleted, suggesting that a reaction product inhibits the conversion of Cr(III) to Cr(VI). Rate-limited reactions govern the weak adsorption of each chromium species, with Cr(III) adsorption varying directly with pH and Cr(VI) adsorption varying inversely with pH. The breakthrough data on chromium transport can be matched closely by calculations of a simple model that accounts for (1) advective-dispersive transport of Cr(III), Cr(VI), and dissolved oxygen, (2) first-order kinetics adsorption of the reduced and oxidized chromium species, and (3) nonlinear rate-limited oxidation of Cr(III) to Cr(VI). Our work supplements the limited database on the transport of redox-sensitive metals in porous media and provides a means for quantifying the coupled processes that contribute to this transport.     

Influence of resorcinol chemical oxidation on the removal of resulting organic carbon by activated carbon adsorption

Activated carbon adsorption and chemical oxidation followed by activated carbon adsorption of resorcinol in water has been studied. Three chemical oxidants have been used: hypochlorite, permanganate and Fenton's reagent. The influence of concentrations of resorcinol and activated carbon on adsorption removal rates has been investigated. Both isotherm and adsorption kinetics have been studied. Results are fit well by Freundlich isotherms and adsorption rates of resorcinol were found to follow a pseudo-second-order kinetic model. However, pyrogallol, an intermediate of resorcinol oxidation with permanganate and Fenton's reagent, showed an unfavourable isotherm type. At the conditions investigated, chemical oxidation allows slight reductions of TOC and intermediates formed were found to inhibit the adsorption rate of TOC in the case of permanganate and Fenton's reagent oxidation, likely due to formation of some polymer pyrogallol product. The adsorption process was found to be controlled by pore internal diffusion, which justifies the poor affinity of oxidation intermediates toward activated carbon since molecules of larger size should diffuse rapidly for the adsorption to be effective.     

Uptake of atmospheric mercury by deionized water and aqueous solutions of inorganic salts at acidic,neutral and alkaline pH

Mercury (Hg) is well known as a toxic environmental pollutant that is among the most highly bioconcentrated trace metals in the human food chain. The atmosphere is one of the most important media for the environmental cycling of mercury, since it not only receives mercury emitted from natural sources such as volcanoes and soil and water surfaces but also from anthropogenic sources such as fossil fuel combustion, mining and metal smelting. Although atmospheric mercury exists in different physical and chemical forms, as much as 90% can occur as elemental vapour Hg0, depending on the geographic location and time of year. Atmospheric mercury can be deposited to aquatic ecosystems through both wet (rain or snow) and dry (vapour adsorption and particulate deposition) processes. The purpose of the present study was to measure, under laboratory conditions, the rate of deposition of gaseous, elemental mercury (Hg0) to deionized water and to solutions of inorganic salt species of varying ionic strengths with a pH range of 2-12. In deionized water the highest deposition rates occurred at both low (pH 2) and high (pH 12). The addition of different species of salt of various concentrations for the most part had only slight effects on the absorption and retention of atmospheric Hg0. The low pH solutions of various salt concentrations and the high pH solutions of high salt concentrations tested in this study generally showed a greater tendency to absorb and retain atmospheric Hg0 than those at a pH closer to neutral.     

Structural effect of the in situ generated titania on its ability to oxidize and capture the gas-phase elemental mercury

Structural effect of the in situ generated TiO(2) sorbent particle was examined for its ability to capture elemental mercury under UV irradiation in a simulated combustion flue gas. Titania particles were prepared by thermal gas-phase oxidation of Titanium (IV) isopropoxide (TTIP) using a high temperature electric furnace reactor. The structural characteristics of the in situ generated TiO(2) at various synthesis temperatures were investigated; size distribution and the geometric mean diameter were measured using a scanning mobility particle sizer, while fractal dimension and radius of gyration were evaluated from the transmission electron microscopy images. Results from the Hg(0) capture experiment show that with increasing titania synthesis temperature, the overall aggregate size increases and the morphology becomes more open-structured to gas-phase Hg(0) and UV light, resulting in the improved mercury removal capability.     

An assessment of the significance of mercury release from coal fly ash

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 < or = 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.     

Polar organic marker compounds in PM2.5 aerosol from a mixed forest site in western Germany

The molecular composition of PM2.5 (particulate matter with an aerodynamic diameter <2.5 microm) aerosol samples collected during a very warm and dry 2003 summer period at a mixed forest site in Jülich, Germany, was determined by gas chromatography/mass spectrometry in an effort to evaluate photooxidation products of biogenic volatile organic compounds (BVOCs) and other markers for aerosol source characterization. Six major classes of compounds represented by twenty-four individual organic species were identified and measured, comprising tracers for biomass combustion, short-chain acids, fatty acids, sugars/sugar alcohols, and tracers for the photooxidation of isoprene and alpha-/beta-pinene. The tracers for the photooxidation of alpha-/beta-pinene include two compounds, 3-hydroxyglutaric acid and 3-methyl-1,2,3-butanetricarboxylic acid, which have only recently been elucidated. The characteristic molecular distribution of the fatty acids with a strong even/odd number carbon preference indicates a biological origin, while the presence of isoprene and terpene secondary organic aerosol products suggests that the photooxidation of BVOCs contributes to aerosol formation at this site. The sum of the median concentrations of the isoprene oxidation products was 21.2 ng m(-3), while that of the terpene oxidation products was 19.8 ng m(-3). On the other hand, the high median concentration of malic acid (37 ng m(-3)) implies that photooxidation of unsaturated fatty acids should also be considered as an important aerosol source process. In addition, the occurrence of levoglucosan and pyrogallol indicates that the site is affected by biomass combustion. Their median concentrations were 30 and 8.9 ng m(-3), respectively.     

Mass transfer within electrostatic precipitators: trace gas adsorption by sorbent-covered plate electrodes

Varying degrees of mercury (Hg) capture have been reported within the electrostatic precipitators (ESPs) of coal-fired electric utility boilers. There has been some speculation that the adsorption takes place on the particulate-covered plate electrodes. This convective mass transfer analysis of laminar and turbulent channel flows provides the maximum potential for Hg adsorption by the plate electrodes within an ESP under those conditions. Mass transfer calculations, neglecting electrohydrodynamic (EHD) effects, reveal 65% removal of elemental Hg for a laminar flow within a 15-m-long channel of 0.2-m spacing and 42% removal for turbulent flow within a similar configuration. Both configurations represent specific collection areas (SCAs) that are significantly larger than conventional ESPs in use. Results reflecting more representative SCA values generally returned removal efficiencies of <20%. EHD effects, although potentially substantial at low Reynolds numbers, diminish rapidly with increasing Reynolds number and become negligible at typical ESP operating conditions. The present results indicate maximum Hg removal efficiencies for ESPs that are much less than those observed in practice for comparable ESP operating conditions. Considering Hg adsorption kinetics and finite sorbent capacity in addition to the present mass transfer analyses would yield even lower adsorption efficiencies than the present results. In a subsequent paper, the author addresses the mass transfer potential presented by the charged, suspended particulates during their collection within an ESP and the role they potentially play in Hg capture within ESPs.     

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.     

Removal of mercury (II) from aqueous solution by activated carbon obtained from furfural

The adsorption of Hg(II) from aqueous solution at 293 K by activated carbon obtained from furfural is studied. The carbon is prepared by polymerization of furfural following carbonization and activation of the obtained polymer material with water vapor at 800 degrees C. Adsorption studies of Hg(II) are carried out varying some conditions: treatment time, metal ion concentration, adsorbent amount and pH. It is determined that Hg(II) adsorption follows both Langmuir and Freundlich isotherms. The adsorption capacity of the carbon is 174 mg/g. It is determined that Hg(II) uptake increases with increasing pH. Desorption studies are performed with hot water. The percent recovery of Hg(II) is 6%.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

Mercury in the Mediterranean,part I: spatial and temporal trends

The present paper provides an overview of mercury studies performed in the Mediterranean Sea region in the framework of several research projects funded by the European Commission and on-going national programmes carried out during the last 15 years. These studies investigated the temporal and spatial distribution of mercury species in air, in the water column and sediments, and the transport mechanisms connecting them. It was found that atmospheric concentrations of Hg compounds, particularly oxidised Hg species observed at five coastal sites in the Mediterranean Sea Basin, are significantly higher compared with those recorded at five coastal sites distributed across N Europe, most probably due to natural emissions. Hg levels in water are comparable to other oceans. Anthropogenic and natural point sources show locally limited enrichments, while natural diffusive sources influence Hg speciation over larger areas. Results and statistic comparison of mercury species concentrations within Mediterranean compartments will be presented and discussed.     

Hg reactions in the presence of chlorine species: homogeneous gas phase and heterogeneous gas-solid phase

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (alpha), overall rate constant (k'), and activation energy (Ea), were estimated based on the simple overall reaction pathway. The reaction order with respect to C(Hg), k', and Ea were found to be 1.55, 5.07 x 10(-2) exp(-1939.68/T) [(microg/m3)(-055)(s)(-1)]. and 16.13 [kJ/ mol], respectively. The effect of chlorine species (HCl, CH2Cl2) on the in situ Hg capture method previously developed (28) was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Modeling the effects of concentration history on the slow desorption of trichloroethene from a soil at 100% relative humidity

To determine the effects of concentration history on slow sorption processes, desorption kinetic profiles for trichloroethene (TCE) were measured for a soil at 100% relative humidity subject to different exposure concentrations and exposure times. Exposure concentrations ranged from 1% to 80% of the saturation vapor pressure (Ps) for TCE, and exposure times (i.e., time allowed for sorption before desorption begins) ranged from 1 to 96 days. A spherical diffusion model based on a gamma distribution of sorption rates and a gamma distribution of desorption rates was developed and applied to the data. At 80% P/Ps, the entire gamma distributions of sorption and desorption rates were available for TCE. In accordance with a micropore filling mechanism, the fraction of these distributions available for TCE sorption decreased with decreasing P/Ps. Experimental results are consistent with a micropore-filling mechanism, where the amount of slow desorbing mass decreased with decreasing exposure time, and the fraction of slow desorbing sites filled decreased with decreasing exposure concentration. Simulation results suggest that diffusion limits the rates that micropores fill, and that rates of sorption and desorption for soil contaminated at smaller values of P/Ps are, on average, less than those at larger values of P/Ps (i.e., slow desorption rates are a function of exposure concentration). Simulation results also suggest that the model adequately describes the effects of exposure concentration and exposure time on the rates of sorption and desorption, but not on the capacity of the slow sites for TCE. This work is important because contaminant concentrations in the subsurface vary in space and time, and the proposed model represents a new and mechanistically based approach to capture the effects of this heterogeneity on slow desorption.     

Heterogeneous mercury reaction chemistry on activated carbon

Experimental and theory-based investigations have been carried out on the oxidation and adsorption mechanism of mercury (Hg) on brominated activated carbon (AC). Air containing parts per billion concentrations of Hg was passed over a packed-bed reactor with varying sorbent materials at 140 and 30 degrees C. Through X-ray photoelectron spectroscopy surface characterization studies it was found that Hg adsorption is primarily associated with bromine (Br) on the surface, but that it may be possible for surface-bound oxygen (O) to play a role in determining the stability of adsorbed Hg. In addition to surface characterization experiments, the interaction of Hg with brominated AC was studied using plane-wave density functional theory. Various configurations of hydrogen, O, Br, and Hg on the zigzag edge sites of graphene were investigated, and although Hg-Br complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The Hg-carbon (C) bond length ranged from 2.26 to 2.34 A and is approximately 0.1 A shorter when O is a nearest-neighbor atom rather than a next-nearest neighbor, resulting in increased stability of the given configuration and overall tighter Hg-C binding. Through a density of states analysis, Hg was found to gain electron density in the six p-states after adsorption and was found to donate electron density from the five s-states, thereby leading to an oxidized surface-bound Hg complex.     

The effect of water on gas–particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems

An investigation of the effect of relative humidity on aerosol formation from m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. Experiments were performed in the presence and absence of ammonium sulfate seed particles (both aqueous and dry) to ascertain the effect of partitioning of oxidation products into a strong electrolytic solution or onto dry crystalline seed particles. In marked contrast to the α-pinene/ozone system, the final measured secondary organic aerosol yield was unaffected by the presence of gas-phase or liquid-phase water at relative humidities (RH) up to 50%. The hygroscopic nature of the aerosol generated upon photooxidation of m-xylene and 1,3,5-trimethylbenzene was examined; the hygroscopicity of the aerosol at 85% RH for both parent organics increased with the extent of the reaction, indicating that the first-generation oxidation products undergo further oxidation. Limited identification of the gas- and aerosol-phase products of m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. It is evident that a more complete molecular identification of aromatic photooxidation aerosol awaits analytical techniques not yet brought to bear on this problem.     

Surface compositions of carbon sorbents exposed to simulated low-rank coal flue gases

Bench-scale testing of elemental mercury (Hg0) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg0. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to approximately 4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg0 vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg2+), the competition of Hg2+ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.     

Nucleation of sulfuric acid-water and methanesulfonic acid-water solution particles: Implications for the atmospheric chemistry of organosulfur species

Binary nucleation theory is applied to the formation of aqueous sulfuric acid and aqueous methanesulfonic acid particles and the relative rates of aerosol formation in humid atmospheres are compared. An integral model is presented which describes nucleation of solution particles, aerosol growth, and condensable vapor source and depletion rates. To extend this model, the water activities of the ternary solution, sulfuric acid-methanesulfonic acid-water, are estimated, and growth of the nucleated aerosol by incorporation of both types of acid is considered. Predictions of both forms of the model are compared with the experimental results of Hatakeyama et al. [Atmospheric Environment19, 135–141 (1985)] for the photooxidation of dimethylsulfide in humid air.