Arsenate adsorption on an Fe-Ce bimetal oxide adsorbent: role of surface properties

An Fe-Ce bimetal adsorbent was investigated with X-ray powder diffraction (XRD), transmission electron micrograph (TEM), Fourier transform infrared spectra (FTIR), and X-ray photoelectron spectroscopy (XPS) methods for a better understanding of the effect of surface properties on arsenate (As(V)) adsorption. In the adsorption test, the bimetal oxide adsorbent showed a significantly higher As(V) adsorption capacity than the referenced Ce and Fe oxides (CeO2 and Fe3O4) prepared by the same procedure and some other arsenate adsorbents reported recently. XRD measurement of the adsorbent demonstrated that the phase of magnetite (Fe3O4) disappears gradually with the increasing dosage of Ce4+ ions until reaching a molar ratio of Ce4+ to Fe3+ and Fe2+ of 0.08:0.2:0.1 (Fe-CeO8 refers to the adsorbent prepared at this ratio), and the phase of CeO2 begins to appear following a further increase of the Ce dose. Combined with the results of TEM observation, it was assumed that a solid solution of Fe-Ce is formed following the disappearance of the magnetite phase. Occurrence of a characteristic surface hydroxyl group (MOH, metal surface hydroxyl, 1126 cm(-1)), which showed the highest band intensity in the solid solution state, was confirmed on the bimetal oxide adsorbent by FTIR. Quantificational calculation from the XPS narrow scan results of O(1s) spectra also indicated that the formation of the bimetal Fe-CeO8 was composed of more hydroxyl (30.8%) than was the formation of CeO2 and Fe3O4 (12.6% and 19.6%). The results of adsorption tests on Fe-CeO8 at differentAs(V) concentrations indicated that both the integral area of the As-O band at 836 cm(-1) and the As(V) adsorption capacity increased almost linearly with the decrease of the integral area of M-OH bands at 1126 cm(-1), proving that the adsorption of As(V) by Fe-CeO8 is mainly realized through the mechanism of quantitative ligand exchange. The atomic ratio of Fe on Fe-CeOB decreased from 20.1% to 7.7% with the increase of the As atom ratio from 0 to 16% after As(V) adsorption, suggesting that As(V) adsorption might be realized through the replacement of the M-OH group of Fe (Fe-OH) with arsenate. The well splitting of three v3 bands at As-O band (836 cm(-1)) of FTIR and the hydroxyl ratio (1.7) of Fe-CeO8 calculated from the XPS results suggested that the diprotonated monodentate complex (SOAsO(OH)2) is possibly dominant on the surface of Fe-CeO8.     

Efficient heterogeneous catalytic reduction of perchlorate in water

A new heterogeneous catalyst that promotes the reduction by hydrogen of perchlorate ion in water under mild conditions has been developed. The catalyst is prepared by adsorption of a rhenium(VII) precursor (either ammonium perrhenate or methylrhenium trioxide) onto carbon powder containing 5% palladium by weight. Under standard batch conditions of room temperature, 1 bar of hydrogen, and 200 ppm perchlorate (as HClO4), reduction proceeded to less than 1 ppm in as little as 5 h. Extended reaction times led to residual perchlorate at low parts per billion levels. Chloride was the only observed product, with good material balance. Catalytic materials ranging from 3% to 13% Re showed (pseudo) first-order rates linearly dependent on the Re content. Representative normalized rate constants for catalysts with 5-9% Re were in the range 0.1-0.3 L h(-1) (g of cat.)(-1). Inhibition by chloride was not significant, with little change in perchlorate reduction rate in the presence of excess chloride to 1000 ppm. However, optimal activity occurred in acidic solutions (pH ca. 3), and both the rate and extent of reaction decreased at higher values of pH. In its current form the catalyst might be best applied to destroy perchlorate in the acidic regeneration stream from selective ion exchange columns.     

Fate of selenium in coal combustion: volatilization and speciation in the flue gas

In light of Title I of the Clean Air Act Amendments of 1990, selenium will most probably be considered for regulation in the electric power industry. This has generated interest for removing this element from fossil-fired flue gas. This study deals with coal combustion: selenium volatilization and its speciation in the cooled flue gas were investigated to better understand its chemical behavior to validate the thermodynamic approach to such complex systems and to begin developing emission control strategies. Se volatility is influenced by several factors such as temperature, residence time, fuel type, particle size, and Se speciation of the fuels, as well as the forms of the Se inthe spiked coal/coke. Spiked coke and coal samples were burned in a thermobalance, and atomic Se and its dioxide were identified in the cooled combustion flue gas by X-ray photoelectron spectroscopy (XPS). A thermodynamic calculation was applied to a complex system including 54 elements and 3,200 species that describes the coal combustion. Several theoretical predictions concerning Se behavior, such as its speciation in flue gas, agreed well with experiments, which supports using thermodynamics for predicting trace element chemistry in combustion systems.     

Development of a mercury transformation model in coal combustion flue gas

A bench-scale entrained-flow reactor was used to extract flue gas produced by burning a subbituminous Belle Ayr coal in a 580-MJ/h combustion system. The reactor was operated at 400 degrees, 275 degrees, and 150 degrees C with a flow rate corresponding to residence times of 0-7 s. Transformations of elemental mercury (Hg0) and total gas mercury (Hg(gas)) in the reactor were evaluated as functions of temperature and residence time. The most significant mercury transformations (Hg0 to Hg(p) and Hg0 to Hg2+) occurred at 150 degrees C, while virtually no obvious mercury transformations were observed at 275 degrees and 400 degrees C. Approximately 30% of total mercury has been oxidized at temperatures higher than 400 degrees C. A mass transfer-capacity limit model was developed to quantify in-flight mercury sorption on fly ash in flue gas at different temperatures. A more sophisticated model was developed to demonstrate not only the temperature and residence time effects but also to consider the effective surface area of fly ash and dependence of mercury vapor concentration on mercury transformations in flue gas. The reaction orders were 0.02 and 0.55 for Hg0 and Hg(gas), respectively. Only a few percent of the total surface area of the fly ash, in the range of 1%-3%, can effectively adsorb mercury vapor.     

SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species

A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.     

Impact of natural organic matter on monochloramine reduction by granular activated carbon: the role of porosity and electrostatic surface properties

Steady-state monochloramine reduction in fixed-bed reactors (FBRs) was quantified on five types of granular activated carbon (GAC) using two background waters-one natural source water (LAW) containing 2.5-3.5 mg/L organic carbon and one synthetic organic-free water (NW). While more monochloramine was reduced at steady-state using NW compared to LAW for each GAC and empty-bed contact time studied, the differences in removal varied considerably among the GACs tested. Physical characterization of the GACs suggested that the degree of interference caused by natural organic matter (NOM) increased with increasing GAC surface area contained within pores greater than 2 nm in width. Acid/base and electrostatic properties of the GACs were not found to be significant in terms of NOM uptake, which indicated that size exclusion effects of the GAC pores overwhelmed the impact of the GAC surface chemistry. Therefore, selection of GAC to limit the impact of NOM on monochloramine reduction in FBRs should be based on pore size distribution alone, with the impact of NOM decreasing with decreasing mesoporosity and macroporosity.     

Adsorption of glyphosate on goethite: molecular characterization of surface complexes

As a component of herbicides, the fate of glyphosate (PMG) in the environment is of significant interest. The nature of PMG adsorption on mineral surfaces plays a significant role in the degradation of PMG. The adsorption of PMG on goethite (alpha-FeOOH) has been studied as a function of pH and PMG concentration. Adsorption was investigated with batch experiments, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The N 1s line in XPS spectra showed deprotonation of the amine group of PMG (NH2+) with increasing pH. IR analyses showed no evidence for the interaction of PMG's carboxylate group with the goethite surface, while the phosphonate group formed inner-sphere complexes. There is evidence for intramolecular hydrogen bonding between NH2+ and both the carboxylate and the phosphonate groups at low pH. Intramolecular hydrogen bonding is lost when the amine group is deprotonated, and the trend in intramolecular hydrogen bonding between NH2+ and phosphonate shows that PMG adsorbs via predominantly monodentate complexation. A minor quantity of bidentate complexes is thought to form both at near-neutral pH and when the surface concentration of PMG is low. While the phosphonate group of PMG binds directly, the carboxylate group remains relatively "free" from complexation with goethite, leaving it subject to degradation and/or complexation with metal ions present in the environment.     

Fate of hazardous air pollutants in oxygen-fired coal combustion with different flue gas recycling

Experiments were performed to characterize transformation and speciation of hazardous air pollutants (HAPs), including SO(2)/SO(3), NO(x), HCl, particulate matter, mercury, and other trace elements in oxygen-firing bituminous coal with recirculation flue gas (RFG) from 1) an electrostatic precipitator outlet or 2) a wet scrubber outlet. The experimental results showed that oxycombustion with RFG generated a flue gas with less volume and containing HAPs at higher levels, while the actual emissions of HAPs per unit of energy produced were much less than that of air-blown combustion. NO(x) reduction was achieved in oxycombustion because of the elimination of nitrogen and the destruction of NO in the RFG. The elevated SO(2)/SO(3) in flue gas improved sulfur self-retention. SO(3) vapor could reach its dew point in the flue gas with high moisture, which limits the amount of SO(3) vapor in flue gas and possibly induces material corrosion. Most nonvolatile trace elements were less enriched in fly ash in oxycombustion than air-firing because of lower oxycombustion temperatures occurring in the present study. Meanwhile, Hg and Se were found to be enriched on submicrometer fly ash at higher levels in oxy-firing than in air-blown combustion.     

Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: a quantum mechanical study

Experimental studies have provided convincing evidence that aerosol-phase heterogeneous chemical reactions (possibly acid-catalyzed) are involved to some extent in the formation of secondary organic aerosol (SOA). We present a stepwise procedure to determine physical properties such as heats of formation, standard entropies, Gibbs free energies of formation, and solvation energies from quantum mechanics (QM), for various short-chain aldehydes and ketones. We show that quantum mechanical gas-phase Gibbs free energies of formation compare reasonably well with the literature values with a root-mean-square (RMS) value of 1.83 kcal/mol for the selected compounds. These QM results are then used to determine the equilibrium constants (reported as log K) of aerosol-phase chemical reactions, including hydration reactions and aldol condensation for formaldehyde, acetaldehyde, acetone, butanal, hexanal, and glyoxal. Results are in qualitatively agreement with previous studies. In addition, the QM results for glyoxal reactions are consistent with experimental observations. To our knowledge, this is the first QM study that supports observations of atmospheric particle-phase reactions. Despite the significant uncertainties in the absolute values from the QM calculations, the results are potentially useful in determining the relative thermodynamic tendency for atmospheric aerosol-phase reactions.     

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.     

Abiotic reduction reactions of dichloroacetamide safeners: transformations of "inert" agrochemical constituents

Safeners are so-called "inert" constituents of herbicide formulations added to protect crops from the toxic effects of herbicides. We examined the reactivity of three dichloroacetamide safeners and 12 structural analogues [all neutral compounds of the form Cl(2)CXC(═O)NRR'; X = H, Cl; R-groups include alkyl, branched alkyl, n-allyl, and cyclic moieties] in one homogeneous and two heterogeneous reductant systems: solutions of Cr(H(2)O)(6)(2+), suspensions of Fe(II)-amended goethite, and suspensions of Fe(II)-amended hematite. Analyses of reaction products indicate each safener can undergo stepwise hydrogenolysis (replacement of chlorine by hydrogen) in each system at near-neutral pH. The first hydrogenolysis step generates compounds similar (in one case, identical) to herbicide active ingredients. Rates of product formation and (when reactions were sufficiently fast) parent loss were quantified; reaction rates in heterogeneous systems spanned 2 orders of magnitude and were strongly influenced by R-group structure. The length of n-alkyl R-groups exerted opposite effects on hydrogenolysis rates in homogeneous versus heterogeneous systems: as R-group size increased, reduction rates in heterogeneous systems increased, whereas reduction rates in the homogeneous system decreased. Branched alkyl R-groups decreased hydrogenolysis rates relative to their straight-chain homologues in both homogeneous and heterogeneous systems. Reaction rates in heterogeneous systems can be described via polyparameter linear free energy relationships employing molecular parameters likely to influence dichloroacetamide adsorption. The propensity of dichloroacetamide safeners to undergo reductive transformations into herbicide-like products challenges their classification as "inert" agrochemical ingredients.     

Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon (char): attenuation of surface activity by humic and fulvic acids

Black carbon (BC) plays a potentially important role in the availability of pollutants in soils and sediments. Recent evidence points to the possible attenuation of the high surface activity of raw BC by natural substances. We studied the effects of soil humic (HA) and fulvic (FA) acids on the surface properties and affinity for organic compounds of synthesized wood charcoal. Char powder suspended in a solution of HA or FA was loaded with organic matter via adsorption, evaporation of the water, or coflocculation with Al3+. These treatments were chosen to simulate initial and more advanced stages of environmental exposure. Coevaporation dramatically reduced the N2 Brunauer-Emmett-Teller total surface area of the char, but only moderately the CO2 cumulative surface area up to 1.4 nm. Organic compound adsorption was suppressed in proportion to molecular size, benzene < naphthalene < phenanthrene and 1,2,4-trichlorobenzene < phenanthrene, for humics in the adsorbed and coflocculated states, respectively. Humic substances also increased the linearity of the isotherms. The model we propose assumes that humic substances are restricted to the external surface where they act as pore blocking agents or competitive adsorbates, depending on the temperature and adsorbate size. Nitrogen is blocked from the internal pore space due to stiffness at 77 K of humic strands extending into pore throats, giving an artificially low surface area. Together with previous results, this finding indicates that N2 may not detect BC microporosity in geosorbents. At higher temperatures (CO2, 273 K; organics, 293 K), humic strands are more flexible, allowing access to interior pores. The counterintuitive molecular size dependence of adsorption suppression by humics is due to a molecular sieving effect in pores in which the adsorption space available to the organic compound is more and more restricted to external sites.     

TEM study of PM2.5 emitted from coal and tire combustion in a thermal power station

The research presented here was conducted within the scope of an experiment investigating technical feasibility and environmental impacts of tire combustion in a coal-fired power station. Previous work has shown that combustion of a coal+tire blend rather than pure coal increased bulk emissions of various elements (e.g., Zn, As, Sb, Pb). The aim of this study is to characterize the chemical and structural properties of emitted single particles with dimensions <2.5 microm (PM2.5). This transmission electron microscope (TEM)-based study revealed that, in addition to phases typical of coal fly ash (e.g., aluminum-silicate glass, mullite), the emitted PM2.5 contains amorphous selenium particles and three types of crystalline metal sulfates never reported before from stack emissions. Anglesite, PbSO4, is ubiquitous in the PM2.5 derived from both fuels and contains nearly all Pb present in the PM. Gunningite, ZnSO4-H2O, is the main host for Zn and only occurs in the PM derived from the coal+tire blend, whereas yavapaiite, KFe3+(SO4)2, is present only when pure coal was combusted. We conclude that these metal sulfates precipitated from the flue gas, may be globally abundant aerosols, and have, through hydration or dissolution, a major environmental and health impact.     

U(VI) adsorption to heterogeneous subsurface media: application of a surface complexation model

The pH-dependent adsorption of U(VI) onto three heterogeneous, subsurface media from the Department of Energy (DOE) Oak Ridge Reservation, Savannah River Site, and Hanford Reservation was investigated. The three materials contained significant quantities of iron and manganese oxides with nearly identical extractable iron oxide contents (25.3-25.8 g/kg). A model independently developed for the adsorption of U(VI) to synthetic ferrihydrite (Waite, T. D.; Davis, J. A.; Payne, T. E.; Waychunas, G. A.; Xu, N. Geochim. Cosmochim. Acta 1994, 58, 5465-5478) was able to predict the major features of the pH-dependent U(VI) adsorption to the materials under the assumption that all the dithionite-citrate-bicarbonate extractable iron oxide was present as ferrihydrite. Further experiments with the Oak Ridge soil as a function of carbonate and U(VI) concentration indicated that the model could predict pH-dependent U(VI) adsorption to within a root mean square error of 0.163-0.408, even under conditions outside of those for which the model was developed. These results indicate that this model could be used as a first approximation in predicting U(VI) adsorption and transport in the subsurface. U(VI) adsorption also decreased at pH >10, even in the absence of carbonate, which is of potential importance to U(VI) mobility in extreme environments present in the subsurface at some DOE facilities. The pH-dependent adsorption of U(VI) was fundamentally different in systems with a constant CO2 partial pressure as compared to a constant total carbonate concentration. Experiments at constant CO2 partial pressure may not be representative of the conditions present in the subsurface, and a constant carbonate concentration does not always result in decreased U(VI) adsorption at higher pH values.     

Role of soil health in maintaining environmental sustainability of surface coal mining

Mountaintop coal mining (MCM) in the Southern Appalachian forest region greatly impacts both soil and aquatic ecosystems. Policy and practice currently in place emphasize water quality and soil stability but do not consider upland soil health. Here we report soil organic carbon (SOC) measurements and other soil quality indicators for reclaimed soils in the Southern Appalachian forest region to quantify the health of the soil ecosystem. The SOC sequestration rate of the MCM soils was 1.3 MgC ha(-1) yr(-1) and stocks ranged from 1.3 ± 0.9 to 20.9 ± 5.9 Mg ha(-1) and contained only 11% of the SOC of surrounding forest soils. Comparable reclaimed mining soils reported in the literature that are supportive of soil ecosystem health had SOC stocks 2.5-5 times greater than the MCM soils and sequestration rates were also 1.6-3 times greater. The high compaction associated with reclamation in this region greatly reduces both the vegetative rooting depth and infiltration of the soil and increases surface runoff, thus bypassing the ability of soil to naturally filter groundwater. In the context of environmental sustainability of MCM, it is proposed that the entire watershed ecosystem be assessed and that a revision of current policy be conducted to reflect the health of both water and soil.