Adsorption of heavy metals by road deposited solids

The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic study and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electro negativity and high charge density of trivalent cation (Cr3+). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.

Airborne concentration of Volatile Organic Compounds in school environment in Brisbane

Traffic emissions are considered as a major source of pollutants, particularly ultrafine particles, in the urban environment. There is an increased concern about airborne particles not only because of their environmental effects but also due to their potential adverse health effects on humans. There have been a number of studies related to the number concentration and size distribution of these particles but studies on the chemical composition of aerosols, especially in the school environment, are very limited. Mejia et. al (2011) reviewed studies on the exposure to and impact of air pollutants on school children and found that there were only a handful of studies on this topic. Therefore, the main focus of this research is on an analysis of the chemical composition of airborne particles, as well as source apportionment and the quantification of ambient concentrations of organic pollutants in the vicinity of schools, as a part of “Ultrafine Particles from Traffic Emissions on Children’s Health” (UPTECH) project. The aim of the present study was to find out the concentrations of different Volatile Organic Compounds (VOCs) in both outdoor and indoor locations from six different schools in Brisbane.

Selective reductions using visible light photocatalysts of supported gold nanoparticles

Photocatalytic synthesis using visible light is a desirable chemical process because of its potential to utilize sunlight. Supported gold nanoparticles (Au-NPs) were found to be efficient photocatalysts and the effects of the supports were identified including CeO2, TiO2, ZrO2, Al2O3, and zeolite Y. In particular Au/CeO2 exhibited the high catalytic activity to reduce nitroaromatics to azo compounds, hydrogenate azobenzene to hydroazobenzene, reduce ketones to alcohols, and deoxygenate epoxides to alkenes at ambient temperatures, under irradiation of visible light (or simulated sunlight). The reac-tive efficiency depends on two primary factors: one is the light adsorption of catalysts and another is the driving ability of catalysts corresponding to the reactants. The light absorption by Au-NPs is due to surface plasmon resonance effect or inter-band electron transition; this is related to the reduction ability of the photocatalysts. Irradiation with shorter wavelengths can excite the conduction electrons in Au-NPs to higher energy levels and as a result, induce reduction with more negative reduction potentials. It is known when irradiated with light the Au-NPs can abstract hydrogen from isopropanol forming Au-H species on the Au-NP surface. Hence, we proposed that the active Au-H species will react with the N=O, N=N, C=O double bonds or epoxide bonds, which are weakened by the interaction with the excited electrons in the Au-NPs, and yield the final reductive products. The reacting power of the Au-H species depends on the energy of the excited electrons in Au-NPs: the higher the electronic energy, the stronger the reduction ability of the Au-H species. This finding demonstrates that we can tune the reduction ability of the photocatalysts by manipulating the irradiation wavelength.

Synthesis and characterisation of organo-beidellite

Today, there are growing concerns about the presence of environmental pollutants in many parts of the world. In particular, a lot of attention has been drawn to the levels of water and soil contaminants (de Paiva et al., 2008). The majority of these contaminants consist of NOCs (non-ionic organic compounds) and can enter our waterways through industrial activities, mining operations, crop and animal production, waste disposal and accidental leakage (de Paiva et al., 2008; Park et al., 2011). Therefore, there is an increased interest in the synthesis of new materials that can be used to remove potentially carcinogenic and toxic water contaminants. Smectite type organoclays are widely used in numerous applications, such as sorbent agents for environmental remediation, due to their unique properties (Jiunn-Fwu et al., 1990; Sheng et al., 1996; Zhou et al., 2007; Bektas et al., 2011; Park et al., 2011). This investigation focuses on beidellite (SBId-1), which belongs to the smectite clay family. Their properties include high cation exchange capacity (CEC), swelling properties, porous, high surface area and consequential strong adsorption/absorption capacity (Xi et al., 2007). However, swelling clays in general are not an effective sorbent agent in nature due to their hydrophilic properties. The hydrophilic properties of the clay can be changed to organophilic by intercalating a cationic surfactant. Many applications of organoclays are strongly dependent on their structural properties and hence, a better understanding of the configuration and structural change of organoclay is crucial. Organoclays were synthesised through ion exchange of 21CODTMA (MW: 392.5 g mol-1) and characterised using XRD and FTIR spectroscopy. This study investigates the structural and conformational changes of beidellite intercalated with octadecyltrimethylammonium bromide.

Recovery and reuse of ammonium from wastewater treatment plants : an application for agriculture

In wastewater treatment plants based on anaerobic digestion, supernatant and outflows from sludge dewatering systems contain significantly high amount of ammonium. Generally, these waters are returned to the head of wastewater treatment plant (WWTP), thereby increasing the total nitrogen load of the influent flow. Ammonium from these waters can be recovered and commercially utilised using novel ion-exchange materials. Mackinnon et al. have described an approach for removal and recovery of ammonium from side stream centrate returns obtained from anaerobic digester of a typical WWTP. Most of the ammonium from side streams can potentially be removed, which significantly reduces overall inlet demand at a WWTP. However, the extent of reduction achieved depends on the level of ammonium and flow-rate in the side stream. The exchange efficiency of the ion-exchange material, MesoLite, used in the ammonium recovery process deteriorates with long-term use due to mechanical degradation and use of regenerant. To ensure that a sustainable process is utilised a range of potential applications for this “spent” MesoLite have been evaluated. The primary focus of evaluations has been use of ammonium-loaded MesoLite as a source of nitrogen and growth medium for plants. A MesoLite fertiliser has advantage over soluble fertilisers in that N is held on an insoluble matrix and is gradually released according to exchange equilibria. Many conventional N fertilisers are water-soluble and thus, instantly release all applied N into the soil solution. Loss of nutrient commonly occurs through volatilisation and/or leaching. On average, up to half of the N delivered by a typical soluble fertiliser can be lost through these processes. In this context, use of ammonium-loaded MesoLite as a fertiliser has been evaluated using standard greenhouse and field-based experiments for low fertility soils. Rye grass, a suitable test species for greenhouse trials, was grown in 1kg pots over a period of several weeks with regular irrigation. Nitrogen was applied at a range of rates using a chemical fertiliser as a control and using two MesoLite fertilisers. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks, and dry plant mass and N concentrations were determined. At all nitrogen application rates, ammonium-loaded MesoLite produced higher plant mass than plants fertilised by the chemical fertiliser. The lower fertiliser effectiveness of the chemical fertliser is attributed to possible loss of some N through volatilisation. The MesoLite fertilisers did not show any adverse effect on availability of macro and trace nutrients, as shown by lack of deficiency symptoms, dry matter yield and plant analyses. Nitrogen loaded on to MesoLite in the form of exchanged ammonium is readily available to plants while remaining protected from losses via leaching and volatilisation. Spent MesoLite appears to be a suitable and effective fertiliser for a wide range of soils, particularly sandy soils with poor nutrient holding capacity.

Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion

Small-angle and ultra-small-angle neutron scattering (SANS and USANS), low-pressure adsorption (N2 and CO2), and high-pressure mercury intrusion measurements were performed on a suite of North American shale reservoir samples providing the first ever comparison of all these techniques for characterizing the complex pore structure of shales. The techniques were used to gain insight into the nature of the pore structure including pore geometry, pore size distribution and accessible versus inaccessible porosity. Reservoir samples for analysis were taken from currently-active shale gas plays including the Barnett, Marcellus, Haynesville, Eagle Ford, Woodford, Muskwa, and Duvernay shales. Low-pressure adsorption revealed strong differences in BET surface area and pore volumes for the sample suite, consistent with variability in composition of the samples. The combination of CO2 and N2 adsorption data allowed pore size distributions to be created for micro–meso–macroporosity up to a limit of �1000 Å. Pore size distributions are either uni- or multi-modal. The adsorption-derived pore size distributions for some samples are inconsistent with mercury intrusion data, likely owing to a combination of grain compression during high-pressure intrusion, and the fact that mercury intrusion yields information about pore throat rather than pore body distributions. SANS/USANS scattering data indicate a fractal geometry (power-law scattering) for a wide range of pore sizes and provide evidence that nanometer-scale spatial ordering occurs in lower mesopore–micropore range for some samples, which may be associated with inter-layer spacing in clay minerals. SANS/USANS pore radius distributions were converted to pore volume distributions for direct comparison with adsorption data. For the overlap region between the two methods, the agreement is quite good. Accessible porosity in the pore size (radius) range 5 nm–10 lm was determined for a Barnett shale sample using the contrast matching method with pressurized deuterated methane fluid. The results demonstrate that accessible porosity is pore-size dependent.

In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

Characterization of tight gas reservoir pore structure using USANS/SANS and gas adsorption analysis

Small-angle and ultra-small-angle neutron scattering (SANS and USANS) measurements were performed on samples from the Triassic Montney tight gas reservoir in Western Canada in order to determine the applicability of these techniques for characterizing the full pore size spectrum and to gain insight into the nature of the pore structure and its control on permeability. The subject tight gas reservoir consists of a finely laminated siltstone sequence; extensive cementation and moderate clay content are the primary causes of low permeability. SANS/USANS experiments run at ambient pressure and temperature conditions on lithologically-diverse sub-samples of three core plugs demonstrated that a broad pore size distribution could be interpreted from the data. Two interpretation methods were used to evaluate total porosity, pore size distribution and surface area and the results were compared to independent estimates derived from helium porosimetry (connected porosity) and low-pressure N2 and CO2 adsorption (accessible surface area and pore size distribution). The pore structure of the three samples as interpreted from SANS/USANS is fairly uniform, with small differences in the small-pore range (<2000 Å), possibly related to differences in degree of cementation, and mineralogy, in particular clay content. Total porosity interpreted from USANS/SANS is similar to (but systematically higher than) helium porosities measured on the whole core plug. Both methods were used to estimate the percentage of open porosity expressed here as a ratio of connected porosity, as established from helium adsorption, to the total porosity, as estimated from SANS/USANS techniques. Open porosity appears to control permeability (determined using pressure and pulse-decay techniques), with the highest permeability sample also having the highest percentage of open porosity. Surface area, as calculated from low-pressure N2 and CO2 adsorption, is significantly less than surface area estimates from SANS/USANS, which is due in part to limited accessibility of the gases to all pores. The similarity between N2 and CO2-accessible surface area suggests an absence of microporosity in these samples, which is in agreement with SANS analysis. A core gamma ray profile run on the same core from which the core plug samples were taken correlates to profile permeability measurements run on the slabbed core. This correlation is related to clay content, which possibly controls the percentage of open porosity. Continued study of these effects will prove useful in log-core calibration efforts for tight gas.

Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid : ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH4+·C7H5O6S-·H2O, (I), the 5-SSA- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R44(20). The first involves both carboxylic acid O-HOwater and water O-HOsulfonate hydrogen bonds at one end, and ammonium N-HOsulfonate and N-HOcarboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O-HOsulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N-HO and water O-HO hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate, 3NH4+·C7H4O6S2-·C7H5O6S-, (II), is unusual, having both dianionic 5-SSA2- and monoanionic 5-SSA- species. These are linked by a carboxylic acid O-HO hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R33(8) association which, together with extensive peripheral N-HO hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA2- species of which there are only a few examples in the crystallographic literature.

Proton-transfer compounds with 4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (sulfamethazine): the structures and hydrogen-bonding in the salts with 5-nitrosalicylic acid and picric acid

The structures of the anhydrous proton-transfer compounds of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate, C12H15N4O2S(+)·C7H4NO4(-), (I), and 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate, C12H15N4O2S(+)·C6H2N3O7(-), (II), respectively, have been determined. In the asymmetric unit of (I), there are two independent but conformationally similar cation-anion heterodimer pairs which are formed through duplex intermolecular N(+)-H...Ocarboxylate and N-H...Ocarboxylate hydrogen-bond pairs, giving a cyclic motif [graph set R2(2)(8)]. These heterodimers form separate and different non-associated substructures through aniline N-H...O hydrogen bonds, one one-dimensional, involving carboxylate O-atom acceptors, the other two-dimensional, involving both carboxylate and hydroxy O-atom acceptors. The overall two-dimensional structure is stabilized by π-π interactions between the pyrimidinium ring and the 5-nitrosalicylate ring in both heterodimers [minimum ring-centroid separation = 3.4580 (8) Å]. For picrate (II), the cation-anion interaction involves a slightly asymmetric chelating N-H...O R2(1)(6) hydrogen-bonding association with the phenolate O atom, together with peripheral conjoint R1(2)(6) interactions between the same N-H groups and O atoms of the ortho-related nitro groups. An inter-unit amine N-H...Osulfone hydrogen bond gives one-dimensional chains which extend along a and inter-associate through π-π interactions between the pyrimidinium rings [centroid-centroid separation = 3.4752 (9) Å]. The two structures reported here now bring to a total of four the crystallographically characterized examples of proton-transfer salts of sulfamethazine with strong organic acids.

Adsorption of heavy metals by road deposited solids

The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic studies and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electro negativity and high charge density of trivalent cation (Cr3+). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.

Adsorption and dissociation of ammonia borane outside and inside single-walled carbon nanotubes : A density functional theory study

Amonia borane (AB) has been identified as a potential candidate highcapacity hydrogen storage material. This work probes the adsorption and dissociation of AB inside and outside single-walled carbon nanotubes (SWCNTs) within the framework of density functional theory. The dissociation barriers of AB have been calculated and compared with that of the isolated AB molecule. On the basis of the present calculations, no notable improvement results from SWCNT confinement; on the contrary, the dissociation barrier slightly increases with respect to isolated AB.

A density functional theory study of CO2 and N2 adsorption on aluminium nitride single walled nanotubes

Strong binding of isolated carbon dioxide (CO2) on aluminium nitride (AlN) single walled nanotubes is verified using two different functionals. Two optimized configurations corresponding to physisorption and chemisorption are linked by a low energy barrier, such that the chemisorbed state is accessible and thermodynamically favored at low temperatures. In contrast, N2 is found only to form a physisorbed complex with the AlN nanotube, suggesting the potential application of aluminium nitride based materials for CO2 fixation. The effect of nanotube diameter on gas adsorption properties is also discussed. The diameter is found to have an important effect on the chemisorption of CO2, but has little effect on the physisorption of either CO2 or N2.

Adsorption of carbon dioxide and nitrogen on single-layer aluminum nitride nanostructures studied by density functional theory

The adsorption of carbon dioxide and nitrogen molecules on aluminum nitride (AlN) nanostructures has been explored using first-principle computational methods. Optimized configurations corresponding to physisorption and, subsequentially, chemisorption of CO2 are identified, in contrast to N2, for which only a physisorption structure is found. Transition-state searches imply a low energy barrier between the physisorption and chemisorption states for CO2 such that the latter is accessible and thermodynamically favored at room temperature. The effective binding energy of the optimized chemisorption structure is apparently larger than those for other CO2 adsorptive materials, suggesting the potential for application of aluminum nitride nanostructures for carbon dioxide capture and storage.