Combined single-pass conversion of methane via oxidative coupling and dehydro-aromatization

A single-pass process with the combination of oxidative coupling (OCM) and dehydro-aromatization (MDA) for the direct conversion of methane is carried out. With the assistance of the OCM reaction over the SrO-La2O3/CaO catalyst loaded on top of the catalyst bed, the duration of the dehydro-aromatization reaction catalyzed by a 6Mo/HMCM-49 catalyst shows a significant improvement, and. the initial deactivation rate constant of the overall process revealed about 1.5 x 10(-6) s(-1). Up to 72 h on stream, the yield of aromatics was still maintained at 5.0% with a methane conversion of 9.6%, which is obviously higher than that reported for the conventional MDA process with single catalyst. Upon the TPR results, this wonderful enhancement would be attributed to an in-situ formation of CO2 and H2O through the OCM reaction, which serves as a scavenger for actively removing the coke formed during the MDA reaction via a reverse Boudouard reaction and the water gas reaction as well.

Welsh Water: role model or special case?

Thomas, D. (2001). Welsh Water: role model or special case?. Utilities Policy, 10 (2), 99-114. RAE2008

Physical and economic potential of geological CO2 storage in saline aquifers.

Carbon sequestration in sandstone saline reservoirs holds great potential for mitigating climate change, but its storage potential and cost per ton of avoided CO2 emissions are uncertain. We develop a general model to determine the maximum theoretical constraints on both storage potential and injection rate and use it to characterize the economic viability of geosequestration in sandstone saline aquifers. When applied to a representative set of aquifer characteristics, the model yields results that compare favorably with pilot projects currently underway. Over a range of reservoir properties, maximum effective storage peaks at an optimal depth of 1600 m, at which point 0.18-0.31 metric tons can be stored per cubic meter of bulk volume of reservoir. Maximum modeled injection rates predict minima for storage costs in a typical basin in the range of $2-7/ ton CO2 (2005 U.S.$) depending on depth and basin characteristics in our base-case scenario. Because the properties of natural reservoirs in the United States vary substantially, storage costs could in some cases be lower or higher by orders of magnitude. We conclude that available geosequestration capacity exhibits a wide range of technological and economic attractiveness. Like traditional projects in the extractive industries, geosequestration capacity should be exploited starting with the low-cost storage options first then moving gradually up the supply curve.

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing.

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH(4) L(-1) (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L(-1) (P < 0.05; n = 34). Average δ(13)C-CH(4) values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ(13)C-CH(4) data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ(2)H-CH(4) values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and-possibly-regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use.

Analysis of ocean power extraction capabilites of a rotary wave energy conversion system

Gemstone Team WAVES (Water and Versatile Energy Systems)

Conversion of natural forests to managed forest plantations decreases tree resistance to prolonged droughts

© 2015 Published by Elsevier B.V.Throughout the southern US, past forest management practices have replaced large areas of native forests with loblolly pine plantations and have resulted in changes in forest response to extreme weather conditions. However, uncertainty remains about the response of planted versus natural species to drought across the geographical range of these forests. Taking advantage of a cluster of unmanaged stands (85-130year-old hardwoods) and managed plantations (17-20year-old loblolly pine) in coastal and Piedmont areas of North Carolina, tree water use, cavitation resistance, whole-tree hydraulic (Ktree) and stomatal (Gs) conductances were measured in four sites covering representative forests growing in the region. We also used a hydraulic model to predict the resilience of those sites to extreme soil drying. Our objectives were to determine: (1) if Ktree and stomatal regulation in response to atmospheric and soil droughts differ between species and sites; (2) how ecosystem type, through tree water use, resistance to cavitation and rooting profiles, affects the water uptake limit that can be reached under drought; and (3) the influence of stand species composition on critical transpiration that sets a functional water uptake limit under drought conditions. The results show that across sites, water stress affected the coordination between Ktree and Gs. As soil water content dropped below 20% relative extractable water, Ktree declined faster and thus explained the decrease in Gs and in its sensitivity to vapor pressure deficit. Compared to branches, the capability of roots to resist high xylem tension has a great impact on tree-level water use and ultimately had important implications for pine plantations resistance to future summer droughts. Model simulations revealed that the decline in Ktree due to xylem cavitation aggravated the effects of soil drying on tree transpiration. The critical transpiration rate (Ecrit), which corresponds to the maximum rate at which transpiration begins to level off to prevent irreversible hydraulic failure, was higher in managed forest plantations than in their unmanaged counterparts. However, even with this higher Ecrit, the pine plantations operated very close to their critical leaf water potentials (i.e. to their permissible water potentials without total hydraulic failure), suggesting that intensively managed plantations are more drought-sensitive and can withstand less severe drought than natural forests.

The CO2 microalgae biorefinery: high value products and biofuels using halophilic microalgae in the “D-Factory”

Fuel-only algal systems are not economically feasible because yields are too low and costs too high for producing microalgal biomass compared to using agricultural residues e.g. straw. Biorefineries which integrate biomass conversion processes and equipment to produce fuels, power and chemicals from biomass, offer a solution. The CO2 microalgae biorefinery (D-Factory) is a 10 million Euro FP7-funded project which will cultivate the microalga Dunaliella in highly saline non-potable waters in photobioreactors and open raceways and apply biorefinery concepts and European innovations in biomass processing technologies to develop a basket of compounds from Dunaliella biomass, including the high value nutraceutical, β-carotene, and glycerol. Glycerol now finds markets both as a green chemical intermediate and as a biofuel in CHP applications as a result of novel combustion technology. Driving down costs by recovering the entire biomass of Dunaliella cells from saline cultivation water poses one of the many challenges for the D-Factory because Dunaliella cells are both motile, and do not possess an external cell wall, making them highly susceptible to cell rupture. Controlling expression of desired metabolic pathways to deliver the desired portfolio of compounds flexibly and sustainably to meet market demand is another. The first prototype D-Factory in Europe will be operational in 48 months, and will serve as a robust manifestation of the business case for global investment in algae biorefineries and in large-scale production of microalgae.

Modelling of saline intrusion in marine outfalls

Since their introduction in the 1950s, marine outfalls with diffusers have been prone to saline intrusion, a process in which seawater ingresses into the outfall. This can greatly reduce the dilution and subsequent dispersion of wastewater discharged, sometimes resulting in serious deterioration of coastal water quality. Although long aware of the difficulties posed by saline intrusion, engineers still lack satisfactory methods for its prediction and robust design methods for its alleviation. However, with recent developments in numerical methods and computer power, it has been suggested that commercially available computational fluid dynamics (CFD) software may be a useful aid in combating this phenomenon by improving understanding through synthesising likely behaviour. This document reviews current knowledge on saline intrusion and its implications and then outlines a model-scale investigation of the process undertaken at Queen's University Belfast, using both physical and CFD methods. Results are presented for a simple outfall configuration, incorporating several outlets. The features observed agree with general observations from full-scale marine outfalls, and quantify the intricate internal flow mechanisms associated with saline intrusion. The two-dimensional numerical model was found to represent saline intrusion, but in a qualitative manner, not yet adequate for design purposes. Specific areas requiring further development were identified. The ultimate aim is to provide a reliable, practical and cost effective means by which engineers can minimise saline intrusion through optimised outfall design.

Water quality impacts and palaeohydrogeology in the East Yorkshire Chalk Aquifer, UK

A large hydrochemical data-set for the East Yorkshire Chalk has been assessed. Controls on the distribution of water qualities within this aquifer reflect: water-rock interactions (affecting especially the carbonate system and associated geochemistry); effects of land-use change (especially where the aquifer is unconfined); saline intrusion and aquifer refreshening (including ion exchange effects); and aquifer overexploitation (in the semi-confined and confined zones of the aquifer). Both Sr and I prove useful indicators of groundwater ages, with I/Cl ratios characterising two sources of saline waters. The hydrochemical evidence clearly reveals the importance of both recent management decisions and palaeohydrogeology in determining the evolution and distribution of groundwater salinity within the artesian and confined zones of the aquifer. Waters currently encountered in the aquifer are identified as complex (and potentially dynamic) mixtures between modern recharge waters, modern seawater, and old seawaters which entered the aquifer many millennia ago.

RESONANCE RAMAN INVESTIGATION OF PH-DEPENDENT EQUILIBRIA OF WATER-SOLUBLE IRON PORPHYRINS

Resonance Raman spectroscopy has been used to probe the structures of; tetrakis(1-methylpyridinium-4-yl)-porphinatoiron(III), FeIII (T4MPyP); tetrakis(1-methylpyridium-2-yl)porphinatoiron(III), FeIII (T2MPyP); tetrakis(4-sulphonatophkenyl)porphinatoir(III), FeIII(TSPP); and tetrakis(4-carboxylatophenyl)porphinatoiron(III), FeIII(TCPP), over a wide pH range. The anionic complexes FeIII (TSPP) and FeIII (TCPP) contain high-spin iron(III) at all pHs. Both these complexes exhibit marked spectral changes at ca. pH 6 which correspond to conversion from the diaquo species, in acid solution, to hydroxy- or mu-oxo dimer complexes. Both cationic complexes show similar diaquo to high-spin hydroxy, or mu-oxo dimer, transitions at ca. pH 6. However, at pH > 11.5 for FeIII (T4MPyP) and pH > 9 for FeIII (T2MPyP) a second equilibrium process is observed, leading to two new species. One of these is readily assigned as the low-spin iron(III) dihydroxy complex by analogy with spectra of the dicyano complex. The second species is assigned to the hydroxy iron(II) complex by comparison with photo-chemically generated FeII (T4MPyP) (OH). The formation of iron(II) species in alkaline solutions of FeIII (T4MPyP) and FeIII (T2MPyP) is entirely unexpected and the significance of the observation to previous investigations of the pH-dependent behaviour of these complexes is discussed.

Levels of cadmium and zinc in soil and plants following the toxic spill from a pyrite mine, Aznalcollar, Spain

On 25 April 1998, a breach of the tailings dam of the Los Frailes pyrite mine in southwestern Spain resulted in the release of 6 million m(3) of acidic water and toxic sludge high in heavy metals. Contaminated material extended 40 km downstream, affecting agricultural land and parts of the wildlife-rich Donana Natural and National Parks, including the Entremuros, a very important area for birds. We report on the concentrations, distributions and bioavailability of zinc and cadmium in soil and vegetation from the Entremuros in November 1998 and October 1999, following 2 'cleanup' operations. Levels of Zn and Cd in soil increased significantly over this period, although this was not reflected consistently in metal concentrations in emergent macrophytes. We recommend monitoring of further cleanup attempts in order to develop means of minimizing potential impacts to wildlife in the area.

Selenium in higher plants: understanding mechanisms for biofortification and phytoremediation:understanding mechanisms for biofortification and phytoremediation

Selenium (Se) is an essential micronutrient for many organisms, including plants, animals and humans. As plants are the main source of dietary Se, plant Se metabolism is therefore important for Se nutrition of humans and other animals. However, the concentration of Se in plant foods varies between areas, and too much Se can lead to toxicity. As we discuss here, plant Se uptake and metabolism can be exploited for the purposes of developing high-Se crop cultivars and for plant-mediated removal of excess Se from soil or water. Here, we review key developments in the current understanding of Se in higher plants. We also discuss recent advances in the genetic engineering of Se metabolism, particularly for biofortification and phytoremediation of Se-contaminated environments.

Uptake kinetics of arsenic species in rice plants

Arsenic (As) finds its way into soils used for rice (Oryza sativa) cultivation through polluted irrigation water, and through historic contamination with As-based pesticides. As is known to be present as a number of chemical species in such soils, so we wished to investigate how these species were accumulated by rice. As species found in soil solution from a greenhouse experiment where rice was irrigated with arsenate contaminated water were arsenite, arsenate, dimethylarsinic acid, and monomethylarsonic acid. The short-term uptake kinetics for these four As species were determined in 7-d-old excised rice roots. High-affinity uptake (0-0.0532 mM) for arsenite and arsenate with eight rice varieties, covering two growing seasons, rice var. Boro (dry season) and rice var. Aman (wet season), showed that uptake of both arsenite and arsenate by Boro varieties was less than that of Aman varieties. Arsenite uptake was active, and was taken up at approximately the same rate as arsenate. Greater uptake of arsenite, compared with arsenate, was found at higher substrate concentration (low-affinity uptake system). Competitive inhibition of uptake with phosphate showed that arsenite and arsenate were taken up by different uptake systems because arsenate uptake was strongly suppressed in the presence of phosphate, whereas arsenite transport was not affected by phosphate. At a slow rate, there was a hyperbolic uptake of monomethylarsonic acid, and limited uptake of dimethylarsinic acid.