Activated Carbons Impregnated with Na2S and H2SO4: Texture, Surface Chemistry and Application to Mercury Removal from Aqueous Solutions

The effects of treatment of an activated carbon with Sulphur precursors on its textural properties and on the ability of the complex synthesized for mercury removal in aqueous solutions are studied. To this end, a commercial activated carbon has been modified by treatments with aqueous solutions of Na2S and H2SO4 at two temperatures (25 and 140 °C) to introduce sulphur species on its surface. The prepared adsorbents have been characterized by N2 (-196 °C) and CO2 (0 °C) adsorption, thermogravimetric analysis, temperature-programmed decomposition and X-ray photoelectron spectroscopy, and their adsorption capacities to remove Hg(II) ions in aqueous solutions have been determined. It has been shown that the impregnation treatments slightly modified the textural properties of the samples, with a small increase in the textural parameters (BET surface area and mesopore volumes). By contrast, surface oxygen content was increased when impregnation was carried out with Na2S, but it decreased when H2SO4 was used. However, the main effect of the impregnation treatments was the formation of surface sulphur complexes of thiol type, which was only achieved when the impregnation treatments were carried out at low temperature (25 °C). The presence of surface sulphur enhances the adsorption behaviour of these samples in the removal of Hg(II) cations in aqueous solutions at pH 2. In fact, complete Hg(II) removal is only obtained with the sulphur-containing activated carbons.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Mercury in Gas Operations - Occupational Health Risk Assessment

The project goal was to determine plant operations and maintenance worker’s level of exposure to mercury during routine and non-routine (i.e. turnarounds and inspections) maintenance events in eight gas processing plants. The project team prepared sampling and analysis plans designed to each plant’s process design and scheduled maintenance events. Occupational exposure sampling and monitoring efforts were focused on the measurement of mercury vapor concentration in worker breathing zone air during specific maintenance events including: pipe scrapping, process filter replacement, and process vessel inspection. Similar exposure groups were identified and worker breathing zone and ambient air samples were collected and analyzed for total mercury. Occupational exposure measurement techniques included portable field monitoring instruments, standard passive and active monitoring methods and an emerging passive absorption technology. Process sampling campaigns were focused on inlet gas streams, mercury removal unit outlets, treated gas, acid gas and sales gas. The results were used to identify process areas with increased potential for mercury exposure during maintenance events. Sampling methods used for the determination of total mercury in gas phase streams were based on the USEPA Methods 30B and EPA 1631 and EPA 1669. The results of four six-week long sampling campaigns have been evaluated and some conclusions and recommendations have been made. The author’s role in this project included the direction of all field phases of the project and the development and implementation of the sampling strategy. Additionally, the author participated in the development and implementation of the Quality Assurance Project Plan, Data Quality Objectives, and Similar Exposure Groups identification. All field generated data was reviewed by the author along with laboratory reports in order to generate conclusions and recommendations.

Selective Mercury Sequestration from a Silver/Mercury Cyanide Solution

Silver and mercury are both dissolved in cyanide leaching and the mercury co-precipitates with silver during metal recovery. Mercury must then be removed from the silver/mercury amalgam by vaporizing the mercury in a retort, leading to environmental and health hazards. The need for retorting silver can be greatly reduced if mercury is selectively removed from leaching solutions. Theoretical calculations were carried out based on the thermodynamics of the Ag/Hg/CN- system in order to determine possible approaches to either preventing mercury dissolution, or selectively precipitating it without silver loss. Preliminary experiments were then carried out based on these calculations to determine if the reaction would be spontaneous with reasonably fast kinetics. In an attempt to stop mercury from dissolving and leaching the heap leach, the first set of experiments were to determine if selenium and mercury would form a mercury selenide under leaching conditions, lowering the amount of mercury in solution while forming a stable compound. From the results of the synthetic ore experiments with selenium, it was determined that another effect was already suppressing mercury dissolution and the effect of the selenium could not be well analyzed on the small amount of change. The effect dominating the reactions led to the second set of experiments in using silver sulfide as a selective precipitant of mercury. The next experiments were to determine if adding solutions containing mercury cyanide to un-leached silver sulfide would facilitate a precipitation reaction, putting silver in solution and precipitating mercury as mercury sulfide. Counter current flow experiments using the high selenium ore showed a 99.8% removal of mercury from solution. As compared to leaching with only cyanide, about 60% of the silver was removed per pass for the high selenium ore, and around 90% for the high mercury ore. Since silver sulfide is rather expensive to use solely as a mercury precipitant, another compound was sought which could selectively precipitate mercury and leave silver in solution. In looking for a more inexpensive selective precipitant, zinc sulfide was tested. The third set of experiments did show that zinc sulfide (as sphalerite) could be used to selectively precipitate mercury while leaving silver cyanide in solution. Parameters such as particle size, reduction potential, and amount of oxidation of the sphalerite were tested. Batch experiments worked well, showing 99.8% mercury removal with only ≈1% silver loss (starting with 930 ppb mercury, 300 ppb silver) at one hour. A continual flow process would work better for industrial applications, which was demonstrated with the filter funnel set up. Funnels with filter paper and sphalerite tested showed good mercury removal (from 31 ppb mercury and 333 ppb silver with a 87% mercury removal and 7% silver loss through one funnel). A counter current flow set up showed 100% mercury removal and under 0.1% silver loss starting with 704 ppb silver and 922 ppb mercury. The resulting sphalerite coated with mercury sulfide was also shown to be stable (not releasing mercury) under leaching tests. Use of sphalerite could be easily implemented through such means as sphalerite impregnated filter paper placed in currently existing processes. In summary, this work focuses on preventing mercury from following silver through the leaching circuit. Currently the only possible means of removing mercury is by retort, creating possible health hazards in the distillation process and in transportation and storage of the final mercury waste product. Preventing mercury from following silver in the earlier stages of the leaching process will greatly reduce the risk of mercury spills, human exposure to mercury, and possible environmental disasters. This will save mining companies millions of dollars from mercury handling and storage, projects to clean up spilled mercury, and will result in better health for those living near and working in the mines.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Separation of mercury (II), lead (II), and silver (I) from aqueous solution using an aminopolycarboxylate silica

A quartz crystal microbalance modified by the attachment of silica particles derivatized with the aminopolycarboxylate ligand N-[(3-trimethoxysilyl)propyl]ethylenediamine-N,N',N'-triacetic acid has been employed to assess conditions under which mercury (II), lead (II), and silver (I) nitrates may be separated in aqueous solution. The separation protocol, which involved removal of Hg(II), as [HgI4](2-), and Pb(II) with H+ was successfully applied to a batchwise separation of the 3 metal ions.

Adsorption kinetics of removal of yellow lanasol dyestuff using gallinaceous feathers

Gallinaceous feathers are an abundant solid waste from the poultry processing industries, which poses disposal problems. A kinetic study dealing with the adsorption process of wool reactive dye, Yellow Lanasol 4G (CI Reactive Yellow 39), on gallinaceous (Gallus gallus, Cobb 500) feathers was carried out. The main research goals of this work were to evaluate the viability of using this waste as adsorbent and to study the kinetics of the adsorption process, using a synthetic effluent. The characterization of feathers was performed by scanning electron microscopy, mercury porosimetry and B.E.T. method. The study of several factors (stirring, particles size, initial dye concentration and temperature) showed their influence over the adsorption process. An adapted version of the Schumckler and Goldstein´s unreacted core model fitted the experimental data. The best fit was obtained when the rate-limiting step was the diffusion through the reacted layer, which was expected considering the size of the dyestuff molecules. The comparison with the granular activated carbon (GAC) Sutcliffe GAC 10-30 indicate that in spite of the high adsorption capacities shown by feathers the GAC presented higher values, the values obtained were respectively 150 and 219 mg g-1, for an initial concentration of 500 mg L-1. The results obtained might open future perspectives both to the valorization of feathers and to the economical treatment of textile wastewaters.

Calixarene and Resorcarene Based Receptors: From Structural and Thermodynamic Studies to the Synthesis of a New Mercury(II) Selective Material

Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from water relative to Cu(II) and Ag (I) shows that the cation selectivity pattern of the inmobilized receptor is the same as that observed for the free receptor in methanol. These findings demonstrate that fundamental studies play a critical role in the selection of the receptor to be attached to silicates as well as in the reaction medium used for the synthesis of the new decontaminating agent.

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 +/- 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, Si-29- and C-13-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 I K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 +/- 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The Delta H and Delta G values for the interaction were determined to be -56.34 +/- 1.07 and -2.14 +/- 0.11 kJ mol(-1). This interaction process was accompanied by a decrease of entropy value (- 182 J mol(-1) K-1). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect. (c) 2007 Elsevier B.V. All rights reserved.

Thermal and electrochemical study of solid-state reaction of mercury with Pt-20% Rh alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Contribution to the study of the reaction of mercury with platinum and a platinum-iridium alloy

Thermogravimetry (TG) and other analysis techniques have been used to study the reaction of mercury with Pt and a PtIr alloy. The results suggested that, when heated, the electrodeposited Hg film reacts with Pt or with PtIr to form products of different stabilities, indicated by at least three weight loss steps. In the first step, between room temperature and 170°C, only the bulk Hg is removed. From this temperature to about 280°C the mass loss can be attributed to the desorption of a monolayer of mecury. The last step, from 280 to ≈600°C, can be ascribed to the removal of Hg from a solid solution with Pt and PtIr alloy. © 1995.

Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

Mercury species concentrations near Casey station, Antarctica and along the SR3 CASO-GEOTRACES transect

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the 'snow-sea ice-seawater' continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (Hg(T)) concentrations varied from 0.63 to 2.76 pmol/L with 'transient-type' vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean Hg(T) concentrations (1.35 ± 0.39 pmol/L) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol/L). Labile Hg (Hg(R)) concentrations varied from 0.01 to 2.28 pmol/L, with a distribution showing that the Hg(T) enrichment south of the SPF consisted mainly of Hg(R) (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg(T)) concentrations ranged from 0.02 to 0.86 pmol/L. All vertical MeHg(T) profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for Hg(T), low mean MeHg(T) concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg(T) concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg(T) vs Apparent Oxygen Utilization (AOU) relationship (p <0.001). The proportion of Hg(T) as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station Hg(T) and Hg(R) concentrations found in the 'snow-sea ice-seawater' continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of Hg(T) there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHg(T) concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol/L. The MeHg(T) vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg(T) concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010; doi:10.1021/es903839n), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.