Coal seam gas waters - their geochemical signature and potential environmental implications

Coal Seam Gas (CSG) is a form of natural gas (mainly methane) sorbed in underground coal beds. To mine this gas, wells are drilled directly into an underground coal seam and groundwater (CSG water) is pumped out to the surface. This lowers the downhole piezometric pressure and enables gas desporption from the coal matrix. In the United States, this gas has been extracted commercially since the 1980s. The economic success of US CSG projects has inspired exploration and development in Australia and New Zealand. In Australia, Queensland’s Bowen and Surat basins have been the subject of increased CSG development over the last decade. CSG growth in other Australian basins has not matured to the same level but exploration and development are taking place at an accelerated pace in the Sydney Basin (Illawarra and the Hunter Valley, NSW) and in the Gunnedah Basin. Similarly, CSG exploration in New Zealand has focused in the Waikato region (Maramarua and Huntly), in the West Coast region (Buller, Reefton, and Greymouth), and in Southland (Kaitangata, Mataura, and Ohai). Figure 1 shows a Shcoeller diagram with CSG samples from selected basins in Australia, New Zealand, and the USA. CSG water from all of these basins exhibit the same geochemical signature – low calcium, low magnesium, high bicarbonate, low sulphate and, sometimes, high chloride. This water quality is a direct result of specific biological and geological processes that have taken part in the formation of CSG. In general, these processes include the weathering of rocks (carbonates, dolomite, and halite), cation exchange with clays (responsible for enhanced sodium and depleted calcium and magnesium), and biogenic processes (accounting for the presence of high bicarbonate concentrations). The salinity of CSG waters tends to be brackish (TDS < 30000 mg/l) with a fairly neutral pH. These particular characteristics need to be taken into consideration when assessing water management and disposal alternatives. Environmental issues associated with CSG water disposal have been prominent in developed basins such as the Powder River Basin (PRB) in the United States. When disposed on the land or used for irrigation, water having a high dissolved salts content may reduce water availability to crops thus affecting crop yield. In addition, the high sodium, low calcium and low magnesium concentrations increase the potential to disperse soils and significantly reduce the water infiltration rate. Therefore, CSG waters need to be properly characterised, treated, and disposed to safeguard the environment without compromising other natural resources.

Synthesis and characterisation of nanoscale magnesium oxide powders and their application in thick films of Bi2Sr2CaCu2O8

Nanoscale MgO powder was synthesized from magnesite ore by a wet chemical method. Acid dissolution was used to obtain a solution from which magnesium containing complexes were precipitated by either oxalic acid or ammonium hydroxide, The transformation of precipitates to the oxide was monitored by thermal analysis and XRD and the transformed powders were studied by electron microscopy. The MgO powders were added as dopants to Bi2SrCa2CuO8 powders and high temperature superconductor thick films were deposited on silver. Addition of suitable MgO powder resulted in increase of critical current density, J(c), from 8,900 Acm(-2) to 13,900 Acm(-2) measured at 77 K and 0 T. The effect of MgO addition was evaluated by XRD, electron microscopy and critical current density measurements. (C) 1998 Elsevier Science B.V.

Tetraaquabis(3,5-dinitrobenzoato-kO')magnesium tetrahydrate

In the structure of the title compound, [Mg(C7H3N2O6)2(H2O)4] . 4H2O), the slightly distorted octahedral MgO6 coordination polyhedron comprises two trans-related carboxyl O-atom donors from mononodentate 3,5-dinitrobenzoate ligands, and four water molecules. The coordinated water molecules and the four water molecules of solvation give both intra- and inter-unit O-H...O hydrogen-bonding interactions with carboxyl, water and nitro O-atom acceptors, giving a three-dimensional structure.

Metallic and Carbon Nanotube-Catalyzed Coupling of Hydrogenation in Magnesium

Synergistic effect of metallic couple and carbon nanotubes on Mg results in an ultrafast kinetics of hydrogenation that overcome a critical barrier of practical use of Mg as hydrogen storage materials. The ultrafast kinetics is attributed to the metal−H atomic interaction at the Mg surface and in the bulk (energy for bonding and releasing) and atomic hydrogen diffusion along the grain boundaries (aggregation of carbon nanotubes) and inside the grains. Hence, a hydrogenation mechanism is presented.

Water absorption, permeability, and resistance to chloride-ion penetration of lightweight aggregate concrete

This paper presents an experimental study to evaluate effect of cumulative lightweight aggregate (LWA) content (including lightweight sand) in concrete [water/cement ratio (w/c) = 0.38] on its water absorption, water permeability, and resistance to chloride-ion penetration. Rapid chloride penetrability test (ASTM C 1202), rapid migration test (NT Build 492), and salt ponding test (AASHTO T 259) were conducted to evaluate the concrete resistance to chloride-ion penetration. The results were compared with those of a cement paste and a control normal weight aggregate concrete (NWAC) with the same w/c and a NWAC (w/c = 0.54) with 28-day compressive strength similar to some of the lightweight aggregate concrete (LWAC). Results indicate that although the total charge passed, migration coefficient, and diffusion coefficient of the LWAC were not significantly different from those of NWAC with the same w/c of 0.38, resistance of the LWAC to chloride penetration decreased with increase in the cumulative LWA content in the concretes. The water penetration depth under pressure and water sorptivity showed, in general, similar trends. The LWAC with only coarse LWA had similar water sorptivity, water permeability coefficient, and resistance to chloride-ion penetration compared to NWAC with similar w/c. The LWAC had lower water sorptivity, water permeability and higher resistance to chloride-ion penetration than the NWAC with similar 28-day strength but higher w/c. Both the NWAC and LWAC had lower sorptivity and higher resistance to chloride-ion penetration than the cement paste with similar w/c.

Development of lightweight concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the influence of coarse lightweight aggregate (LWA), fine LWA and the quality of the paste matrix on water absorption and permeability, and resistance to chloride-ion penetration in concrete. The results indicate that incorporation of pre-soaked coarse LWA in concrete increases water sorptivity and permeability slightly compared to normal weight concrete (NWC) of similar water-to-cementitious materials ratio (w/cm). Furthermore, resistance of the sand lightweight concrete (LWC) to water permeability and chloride-ion penetration decreases with an increase in porosity of the coarse LWA. The use of fine LWA including a crushed fraction <1.18 mm reduced resistance of the all-LWC to water and chloride-ion penetration compared with the sand-LWC which has the same coarse LWA. Overall, the quality of the paste matrix was dominant in controlling the transport properties of the concrete, regardless of porosity of the aggregates used. With low w/cm and silica fume, low unit weight LWC (_1300 kg/m3) was produced with a higher resistance to water and chloride-ion penetration compared with NWC and LWC of higher unit weights.

Effect of cumulative lightweight aggregate volume in concrete on its resistance to chloride-ion penetration

This paper presents an experimental study on the resistance of lightweight aggregate concretes to chloride-ion penetration in comparison to that of normal weight concrete of similar w/c. Salt ponding test (based on AASHTO T 259), rapid chloride permeability test (ASTM C 1202) and rapid migration test (NT Build 492) were carried out to evaluate the concrete resistance to the chloride-ion penetration. Results indicate that in general the resistance of the LWAC to the chloride-ion penetration was in the same order as that of NWAC of similar w/c. However, the increase in cumulative LWA volume and the incorporation of finer LWA particles led to higher charge passed, migration coefficient, and diffusion coefficient. Since the LWACs had lower 28-day compressive strength compared with that of the NWAC of similar w/c, the LWACs may have equal or better resistance to the chloride-ion penetration compared with the NWAC of equivalent strength. The trend of the resistance of concretes to chloride-ion penetration determined by the three test methods was reasonably consistent although there were some discrepancies due to different test methods.

Estimation Of concrete resistance To chloride-ion penetration based On water accessible porosity and unit weight Of concrete

To ensure better concrete quality and long-term durability, there has been an increasing focus in recent years on the development of test methods for quality control of concrete. This paper presents a study to evaluate the effect of water accessible porosity and oven-dry unit weight on the resistance of concrete to chloride-ion penetration. Based on the experimental results and regression analyses, empirical relationships of the charge passed (ASTM C 1202) and chloride migration coefficient (NT Build 492) versus the water accessible porosity and oven dry unit weight of the concrete are established. Using basic physical properties of water accessible porosity and oven dry unit weight which can be easily determined, total charge passed and migration coefficient of the concrete can be estimated for quality control and for estimating durability of concrete.

Water and chloride ion penetration resistance of highstrength ultra lightweight cement composite

Durability is a significant issue to focus on for newly developed structural lightweight cement composite (ULCC). This paper presents an experimental study to evaluate the resistance of ULCC to water and chloride ion penetration. Chloride penetrability and sorptivity were evaluated for ULCC (unit weight about 1450 kg/m3) and compared with those of a normal weight concrete (NWC), a lightweight aggregate concrete (LWC), and an ultra lightweight composite with proprietary cementitious binder (DB) (unit weight about 1450 kg/m3) at similar compressive strength of about 60 MPa. Rapid chloride penetrability test, rapid migration test, water absorption (sorptivity) test, and water permeability test were conducted on these mixtures. Results indicate that ULCC and DB had comparable performance. Compared with control LWC and NWC at similar strength level, the ULCC and DB mixtures had higher resistance to chloride ion penetration, lower water absorption and virtually impermeable to water penetration.

Development of lightweight aggregate concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the effect of coarse and fine LWA in concrete on its water absorption and permeability, and resistance to chloride-ion penetration. In additions, LWC with lower unit weight of about 1300 kg/m3 but high resistance to water and chloride-ion penetration was developed and evaluated. The results indicate that the incorporation of coarse LWA in concrete increases water sorptivity and permeability slightly compared to NWC of similar w/c. The resistance of the sand-LWC to chloride-ion penetration depends on porosity of the coarse LWA. Fine LWA has more influence on the transport proper-ties of concrete than coarse LWA. Use of lightweight crushed sand <1.18 mm reduced the resistance of the LWC to water and chloride-ion penetration to some extent. With low w/cm and silica fume, low unit weight LWC (~1300 kg/m3) was produced with higher resistance to water and chloride ion penetration compared with concretes of higher unit weights.

First-principle studies of the formation and diffusion of hydrogen vacancies in magnesium hydride

Ab initio density functional theory (DFT) calculations are performed to study the formation and diffusion of hydrogen vacancies on MgH2(110) surface and in bulk. We find that the formation energies for a single H-vacancy increase slightly from the surface to deep layers. The energies for creating adjacent surface divancacies at two inplane sites and at an inplane and a bridge site are even smaller than that for the formation of a single H-vacancy, a fact that is attributed to the strong vacancy−vacancy interactions. The diffusion of an H-vacancy from an in-plane site to a bridge site on the surface has the smallest activation barrier calculated at 0.15 eV and should be fast at room temperature. The activation barriers computed for H-vacancy diffusion from the surface into sublayers are all less than 0.70 eV, which is much smaller than the activation energy for desorption of hydrogen on the MgH2(110) surface (1.78−2.80 eV/H2). This suggests that surface desorption is more likely than vacancy diffusion to be rate determining, such that finding effective catalyst on the MgH2 surface to facilitate desorption will be very important for improving overall dehydrogenation performance.

Ab initio studies of hydrogen desorption from low index magnesium hydride surface

The low index Magnesium hydride surfaces, MgH2(0 0 1) and MgH2(1 1 0), have been studied by ab intio Density Functional Theory (DFT) calculations. It was found that the MgH2(1 1 0) surface is more stable than MgH2(0 0 1) surface, which is in good agreement with the experimental observation. The H2 desorption barriers vary depending on the crystalline surfaces that are exposed and also the specific H atom sites involved – they are found to be generally high, due to the thermodynamic stability of the MgH2 system, and are larger for the MgH2(0 0 1) surface. The pathway for recombinative desorption of one in-plane and one bridging H atom from the MgH2(1 1 0) surface was found to be the lowest energy barrier amongst those computed (172 KJ/mol) and is in good agreement with the experimental estimates.

Atomic hydrogen diffusion in novel magnesium nanostructures : the impact of incorporated subsurface carbon atoms

Ab initio Density Functional Theory (DFT) calculations are performed to study the diffusion of atomic hydrogen on a Mg(0001) surface and their migration into the subsurface layers. A carbon atom located initially on a Mg(0001) surface can migrate into the sub-surface layer and occupy a fcc site, with charge transfer to the C atom from neighboring Mg atoms. The cluster of postively charged Mg atoms surrounding a sub-surface C is then shown to facilitate the dissociative chemisorption of molecular hydrogen on the Mg(0001) surface, and the surface migration and subsequent diffusion into the subsurface of atomic hydrogen. This helps rationalize the experimentally-observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

The role of V2O5 on the dehydrogenation and hydrogenation in magnesium hydride : An ab initio study

Ab initio density functional theory calculations are performed to study the experimentally observed catalytic role of V2O5 in the recycling of hydrogen in magnesium hydride. We find that the Mg–H bond length becomes elongated when MgH2 clusters are positioned on single, two, and three coordinated oxygen sites (O1, O2, and O3) on the V2O5(001) surface. Molecular hydrogen is predicted to spontaneously form at the hole site on the V2O5(001) surface. Additionally, the activation barrier for the dissociation of hydrogen on V-doped Mg(0001) surface is 0.20 eV, which is only 1/5 of that on pure Mg(0001) surface. Our results indicate that oxygen sites on the V2O5(001)surface and the V dopant in Mg may be important facilitators for dehydrogenation and rehydrogenation, respectively. The understanding gained here will aid in the rational design and development of Mg-based hydrogen storage materials.

Synthesis and spectroscopic characterization of magnesium oxalate nano-crystals

Synthesis of MgC2O4⋅2H2O nano particles was carried out by thermal double decomposition of solutions of oxalic acid dihydrate (C2H2O4⋅2H2O) and Mg(OAc)2⋅4H2O employing CATA-2R microwave reactor. Structural elucidation was carried out by employing X-ray diffraction (XRD), particle size and shape were studied by transmission electron microscopy (TEM) and nature of bonding was investigated by optical absorption and near-infrared (NIR) spectral studies. The powder resulting from this method is pure and possesses distorted rhombic octahedral structure. The synthesized nano rod is 80 nm in diameter and 549 nm in length.