A Late Pleistocene hominin footprint site on the North African coast of Morocco.

Footprints represent a relevant vestige providing direct information on the biology, locomotion, and behaviour of the individuals who left them. However, the spatiotemporal distribution of hominin footprints is heterogeneous, particularly in North Africa, where no footprint sites were known before the Holocene. This region is important in the evolution of hominins. It notably includes the earliest currently known Homo sapiens (Jebel Irhoud) and the oldest and richest African Middle Stone Age hominin sites. In this fragmented ichnological record, we report the discovery of 85 human footprints on a Late Pleistocene now indurated beach surface of about 2800 m2 at Larache (Northwest coast of Morocco). The wide range of sizes of the footprints suggests that several individuals from different age groups made the tracks while moving landward and seaward across a semi-dissipative bar-trough sandy beach foreshore. A geological investigation and an optically stimulated luminescence dating of a rock sample extracted from the tracksite places this hominin footprint surface at 90.3 ± 7.6 ka (MIS 5, Late Pleistocene). The Larache footprints are, therefore, the oldest attributed to Homo sapiens in Northern Africa and the Southern Mediterranean.

Mineral and Heavy Metal Composition of Oil Shale Ash from Oxyfuel Combustion.

Oxyfuel combustion can reduce CO2 emissions from fossil fuels. Hence, it is currently being investigated for potential use in oil shale-fired power plants, which currently produce most of Estonia's electricity. Here, experiments were performed with kukersite oil shale for both oxyfuel and conventional combustion in a 60 kWth circulating fluidized bed combustor. In this paper, we provide data on the ash composition including mineral compositions and heavy metal concentrations. Oxyfuel conditions did not noticeably influence the concentrations of heavy metals in the ash but did have significantly lower amounts of free lime because of inhibition of the carbonate decomposition reactions. The results suggest that oxyfuel combustion would produce no significant problems in terms of the behavior of the ash or the fate of heavy metals contained in the ash.

Long-term sediment decline causes ongoing shrinkage of the Mekong megadelta, Vietnam.

Since the 1990s the Mekong River delta has suffered a large decline in sediment supply causing coastal erosion, following catchment disturbance through hydropower dam construction and sand extraction. However, our new geological reconstruction of 2500-years of delta shoreline changes show that serious coastal erosion actually started much earlier. Data shows the sandy coast bounding river mouths accreted consistently at a rate of +2 to +4 km2/year. In contrast, we identified a variable accretion rate of the muddy deltaic protrusion at Camau; it was < +1 km2/year before 1400 years ago but increased drastically around 600 years ago, forming the entire Camau Peninsula. This high level of mud supply had sharply declined by the early 20th century after a vast canal network was built on the delta. Since then the Peninsula has been eroding, promoted by the conjunction of mud sequestration in the delta plain driven by expansion of rice cultivation, and hysteresis of long-term muddy sedimentation that left the protrusion exposed to wave erosion. Natural mitigation would require substantial increases in sediment supply well above the pre-1990s levels.

Long-term mineral transformation of Ca-rich oil shale ash waste.

Power generation and other industries using solid fossil fuels like coal, lignite, oil shale and peat are responsible for producing large quantities of solid residues that are often chemically reactive and/or unstable and are disposed in holding ponds and deposition sites. Stability and long-term behaviour of such deposits are typically studied in short-term laboratory experiments that cannot describe nor predict long-term changes taking place in these materials. Here, we study long-term (>40 years) transformations, in highly alkaline conditions, of the Ca-rich ash deposit in Estonia composed of oil shale processing residues from the Eesti power plant. Detailed mineralogical, chemical and micromorphological analyses using X-ray diffraction, X-ray fluorescence, 29Si nuclear magnetic resonance, scanning electron microscopy and other methods were applied in order to identify the composition of the waste with a focus on formation and transformation of semicrystalline phases in the deposit. The results show progressive formation of calcium-silicate-hydrate (C-S-H) type phase at the expense of silicate minerals and amorphous glass phases with increasing depth and age of the sediments, from about 25% in the upper part of the depository to over 60% in the oldest-deepest part. This demonstrates that over time the high alkalinity of the ash is responsible for initiating natural alkali-activation. The formation of C-S-H-type phases increases the mechanical strength of the sediment and ensures long-term stability of waste deposits. These findings may encourage the use of these ashes in binder or other construction material production or as construction aggregates.

Probabilistic performance assessment of complex energy process systems - The case of a self-sustained sanitation system.

A probabilistic modelling approach was developed and applied to investigate the energy and environmental performance of an innovative sanitation system, the "Nano-membrane Toilet" (NMT). The system treats human excreta via an advanced energy and water recovery island with the aim of addressing current and future sanitation demands. Due to the complex design and inherent characteristics of the system's input material, there are a number of stochastic variables which may significantly affect the system's performance. The non-intrusive probabilistic approach adopted in this study combines a finite number of deterministic thermodynamic process simulations with an artificial neural network (ANN) approximation model and Monte Carlo simulations (MCS) to assess the effect of system uncertainties on the predicted performance of the NMT system. The joint probability distributions of the process performance indicators suggest a Stirling Engine (SE) power output in the range of 61.5-73 W with a high confidence interval (CI) of 95%. In addition, there is high probability (with 95% CI) that the NMT system can achieve positive net power output between 15.8 and 35 W. A sensitivity study reveals the system power performance is mostly affected by SE heater temperature. Investigation into the environmental performance of the NMT design, including water recovery and CO2/NOx emissions, suggests significant environmental benefits compared to conventional systems. Results of the probabilistic analysis can better inform future improvements on the system design and operational strategy and this probabilistic assessment framework can also be applied to similar complex engineering systems.

Operation of a 25 KWth Calcium Looping Pilot-plant with High Oxygen Concentrations in the Calciner.

Calcium looping (CaL) is a post-combustion CO2 capture technology that is suitable for retrofitting existing power plants. The CaL process uses limestone as a cheap and readily available CO2 sorbent. While the technology has been widely studied, there are a few available options that could be applied to make it more economically viable. One of these is to increase the oxygen concentration in the calciner to reduce or eliminate the amount of recycled gas (CO2, H2O and impurities); therefore, decreasing or removing the energy necessary to heat the recycled gas stream. Moreover, there is a resulting increase in the energy input due to the change in the combustion intensity; this energy is used to enable the endothermic calcination reaction to occur in the absence of recycled flue gases. This paper presents the operation and first results of a CaL pilot plant with 100% oxygen combustion of natural gas in the calciner. The gas coming into the carbonator was a simulated flue gas from a coal-fired power plant or cement industry. Several limestone particle size distributions are also tested to further explore the effect of this parameter on the overall performance of this operating mode. The configuration of the reactor system, the operating procedures, and the results are described in detail in this paper. The reactor showed good hydrodynamic stability and stable CO2 capture, with capture efficiencies of up to 70% with a gas mixture simulating the flue gas of a coal-fired power plant.

Effect of SO2 and steam on CO2 capture performance of biomass-templated calcium aluminate pellets.

Four types of synthetic sorbents were developed for high-temperature post-combustion calcium looping CO2 capture using Longcal limestone. Pellets were prepared with: lime and cement (LC); lime and flour (LF); lime, cement and flour (LCF); and lime, cement and flour doped with seawater (LCFSW). Flour was used as a templating material. All samples underwent 20 cycles in a TGA under two different calcination conditions. Moreover, the prepared sorbents were tested for 10 carbonation/calcination cycles in a 68 mm-internal-diameter bubbling fluidized bed (BFB) in three environments: with no sulphur and no steam; in the presence of sulphur; and with steam. When compared to limestone, all the synthetic sorbents exhibited enhanced CO2 capture performance in the BFB experiments, with the exception of the sample doped with seawater. In the BFB tests, the addition of cement binder during the pelletisation process resulted in the increase of CO2 capture capacity from 0.08 g CO2 per g sorbent (LF) to 0.15 g CO2 per g sorbent (LCF) by the 10th cycle. The CO2 uptake in the presence of SO2 dramatically declined by the 10th cycle; for example, from 0.22 g CO2 per g sorbent to 0.05 g CO2 per g sorbent in the case of the untemplated material (LC). However, as expected all samples showed improved performance in the presence of steam, and the decay of reactivity during the cycles was less pronounced. Nevertheless, in the BFB environment, the templated pellets showed poorer CO2 capture performance. This is presumably because of material loss due to attrition under the FB conditions. By contrast, the templated materials performed better than untemplated materials under TGA conditions. This indicates that the reduction of attrition is critical when employing templated materials in realistic systems with FB reactors.

Review of the scientific evidence to support environmental risk assessment of shale gas development in the UK.

Interest in the development of shale gas resources using hydraulic fracturing techniques is increasing worldwide despite concerns about the environmental risks associated with this activity. In the United Kingdom (UK), early attempts to hydraulically fracture a shale gas well resulted in a seismic event that led to the suspension of all hydraulic fracturing operations. In response to this occurrence, UK regulators have requested that future shale gas operations that use hydraulic fracturing should be accompanied by a high-level environmental risk assessment (ERA). Completion of an ERA can demonstrate competency, communicate understanding, and ultimately build trust that environmental risks are being managed properly, however, this assessment requires a scientific evidence base. In this paper we discuss how the ERA became a preferred assessment technique to understand the risks related to shale gas development in the UK, and how it can be used to communicate information between stakeholders. We also provide a review of the evidence base that describes the environmental risks related to shale gas operations, which could be used to support an ERA. Finally, we conclude with an update of the current environmental risks associated with shale gas development in the UK and present recommendations for further research.

Linking rapid erosion of the Mekong River delta to human activities.

As international concern for the survival of deltas grows, the Mekong River delta, the world's third largest delta, densely populated, considered as Southeast Asia's most important food basket, and rich in biodiversity at the world scale, is also increasingly affected by human activities and exposed to subsidence and coastal erosion. Several dams have been constructed upstream of the delta and many more are now planned. We quantify from high-resolution SPOT 5 satellite images large-scale shoreline erosion and land loss between 2003 and 2012 that now affect over 50% of the once strongly advancing >600 km-long delta shoreline. Erosion, with no identified change in the river's discharge and in wave and wind conditions over this recent period, is consistent with: (1) a reported significant decrease in coastal surface suspended sediment from the Mekong that may be linked to dam retention of its sediment, (2) large-scale commercial sand mining in the river and delta channels, and (3) subsidence due to groundwater extraction. Shoreline erosion is already responsible for displacement of coastal populations. It is an additional hazard to the integrity of this Asian mega delta now considered particularly vulnerable to accelerated subsidence and sea-level rise, and will be exacerbated by future hydropower dams.

Effect of pelletization and addition of steam on the cyclic performance of carbon-templated, CaO-based CO2 sorbents.

In this work, we report the development of a synthetic CO2 sorbent that possesses a high cyclic CO2 uptake capacity and, in addition, sufficient mechanical strength to allow it to be used in fluidized-bed reactors. To overcome the problem of elutriation of the original powdered material, the synthetic CO2 sorbent was pelletized. An important aspect of this work was to assess the effect of steam on the cyclic CO2 capture capacity of the original, powdered CO2 sorbent and the pelletized material. After 30 cycles of repeated calcination and carbonation reactions conducted in a fluidized bed, the CO2 uptake of the pellets was 0.29 g of CO2/g of sorbent, a value that is 45% higher than that measured for the reference limestone. For the case that carbonation/calcination cycles were conducted in a thermogravimetric analyzer under steam-free carbonation conditions, the CO2 uptake of the best sorbent was 0.33 g of CO2/g of sorbent (after 10 cycles). Importantly, it should be noted that, after 10 cycles using wet carbonation conditions, the CO2 uptake of this material increased by 55% when compared to dry conditions. This observation was attributed to enhanced solid-state diffusion in the CaCO3 product layer under wet conditions. However, independent of the reaction conditions, the pelletized material showed a lower cyclic CO2 uptake when compared to the original powder. A detailed morphological characterization of the pellets indicated that the destruction of the primary, hollow micrometer-sized spheres during pelletization was responsible for the lower cyclic CO2 uptake of the pellets.

High-purity hydrogen via the sorption-enhanced steam methane reforming reaction over a synthetic CaO-based sorbent and a Ni catalyst.

Sorbent-enhanced steam methane reforming (SE-SMR) is an emerging technology for the production of high-purity hydrogen from hydrocarbons with in situ CO2 capture. Here, SE-SMR was studied using a mixture containing a Ni-hydrotalcite-derived catalyst and a synthetic, Ca-based, calcium aluminate supported CO2 sorbent. The fresh and cycled materials were characterized using N2 physisorption, X-ray diffraction, and scanning and transmission electron microscopy. The combination of a Ni-hydrotalcite catalyst and the synthetic CO2 sorbent produced a stream of high-purity hydrogen, that is, 99 vol % (H2O- and N2-free basis). The CaO conversion of the synthetic CO2 sorbent was 0.58 mol CO2/mol CaO after 10 cycles, which was more than double the value achieved by limestone. The favorable CO2 capture characteristics of the synthetic CO2 sorbent were attributed to the uniform dispersion of CaO on a stable nanosized mayenite framework, thus retarding thermal sintering of the material. On the other hand, the cycled limestone lost its nanostructured morphology completely over 10 SE-SMR cycles due to its intrinsic lack of a support component.

Spray water reactivation/pelletization of spent CaO-based sorbent from calcium looping cycles.

This paper presents a novel method for reactivation of spent CaO-based sorbents from calcium looping (CaL) cycles for CO(2) capture. A spent Cadomin limestone-derived sorbent sample from a pilot-scale fluidized bed (FBC) CaL reactor is used for reactivation. The calcined sorbent is sprayed by water in a pelletization vessel. This reactivation method produces pellets ready to be used in FBC reactors. Moreover, this procedure enables the addition of calcium aluminate cement to further enhance sorbent strength. The characterization of reactivated material by nitrogen physisorption (BET, BJH) and scanning electron microscopy (SEM) confirmed the enhanced morphology of sorbent particles for reaction with CO(2). This improved CO(2) carrying capacity was demonstrated in calcination/carbonation tests performed in a thermogravimetric analyzer (TGA). Finally, the resulting pellets displayed a high resistance to attrition during fluidization in a bubbling bed.

Influence of high-temperature steam on the reactivity of CaO sorbent for CO2 capture.

Calcium looping is a high-temperature CO(2) capture technology applicable to the postcombustion capture of CO(2) from power station flue gas, or integrated with fuel conversion in precombustion CO(2) capture schemes. The capture technology uses solid CaO sorbent derived from natural limestone and takes advantage of the reversible reaction between CaO and CO(2) to form CaCO(3); that is, to achieve the separation of CO(2) from flue or fuel gas, and produce a pure stream of CO(2) suitable for geological storage. An important characteristic of the sorbent, affecting the cost-efficiency of this technology, is the decay in reactivity of the sorbent over multiple CO(2) capture-and-release cycles. This work reports on the influence of high-temperature steam, which will be present in flue (about 5-10%) and fuel (∼20%) gases, on the reactivity of CaO sorbent derived from four natural limestones. A significant increase in the reactivity of these sorbents was found for 30 cycles in the presence of steam (from 1-20%). Steam influences the sorbent reactivity in two ways. Steam present during calcination promotes sintering that produces a sorbent morphology with most of the pore volume associated with larger pores of ∼50 nm in diameter, and which appears to be relatively more stable than the pore structure that evolves when no steam is present. The presence of steam during carbonation reduces the diffusion resistance during carbonation. We observed a synergistic effect, i.e., the highest reactivity was observed when steam was present for both calcination and carbonation.

Integration of calcium and chemical looping combustion using composite CaO/CuO-based materials.

Calcium looping cycles (CaL) and chemical looping combustion (CLC) are two new, developing technologies for reduction of CO(2) emissions from plants using fossil fuels for energy production, which are being intensively examined. Calcium looping is a two-stage process, which includes oxy-fuel combustion for sorbent regeneration, i.e., generation of a concentrated CO(2) stream. This paper discuss the development of composite materials which can use copper(II)-oxide (CuO) as an oxygen carrier to provide oxygen for the sorbent regeneration stage of calcium looping. In other words, the work presented here involves integration of calcium looping and chemical looping into a new class of postcombustion CO(2) capture processes designated as integrated CaL and CLC (CaL-CLC or Ca-Cu looping cycles) using composite pellets containing lime (CaO) and CuO together with the addition of calcium aluminate cement as a binder. Their activity was tested in a thermogravimetric analyzer (TGA) during calcination/reduction/oxidation/carbonation cycles. The calcination/reduction typically was performed in methane (CH(4)), and the oxidation/carbonation stage was carried out using a gas mixture containing both CO(2) and O(2). It was confirmed that the material synthesized is suitable for the proposed cycles; with the very favorable finding that reduction/oxidation of the oxygen carrier is complete. Various schemes for the Ca-Cu looping process have been explored here that would be compatible with these new composite materials, along with some different possibilities for flow directions among carbonator, calciner, and air reactor.

Lime-based sorbents for high-temperature CO2 capture--a review of sorbent modification methods.

This paper presents a review of the research on CO(2) capture by lime-based looping cycles undertaken at CanmetENERGY's (Ottawa, Canada) research laboratories. This is a new and very promising technology that may help in mitigation of global warming and climate change caused primarily by the use of fossil fuels. The intensity of the anticipated changes urgently requires solutions such as more cost-effective technologies for CO(2) capture. This new technology is based on the use of lime-based sorbents in a dual fluidized bed combustion (FBC) reactor which contains a carbonator-a unit for CO(2) capture, and a calciner-a unit for CaO regeneration. However, even though natural materials are cheap and abundant and very good candidates as solid CO(2) carriers, their performance in a practical system still shows significant limitations. These limitations include rapid loss of activity during the capture cycles, which is a result of sintering, attrition, and consequent elutriation from FBC reactors. Therefore, research on sorbent performance is critical and this paper reviews some of the promising ways to overcome these shortcomings. It is shown that reactivation by steam/water, thermal pre-treatment, and doping simultaneously with sorbent reforming and pelletization are promising potential solutions to reduce the loss of activity of these sorbents over multiple cycles of use.

Enhancement of indirect sulphation of limestone by steam addition.

The effect of water (H2O(g)) on in situ SO2 capture using limestone injection under (FBC) conditions was studied using a thermobalance and tube furnace. The indirect sulphation reaction was found to be greatly enhanced in the presence of H2O(g). Stoichiometric conversion of samples occurred when sulphated with a synthetic flue gas containing 15% H2O(g) in under 10 h, which is equivalent to a 45% increase in conversion as compared to sulphation without H2O(g). Using gas pycnometry and nitrogen adsorption methods, it was shown that limestone samples sulphated in the presence of H2O(g) undergo increased particle densification without any significant changes to pore area or volume. The microstructural changes and observed increase in conversion were attributed to enhanced solid-state diffusion in CaO/CaSO4 in the presence of H2O(g). Given steam has been shown to have such a strong influence on sulphation, whereas it had been previously regarded as inert, may prompt a revisiting of the classically accepted sulphation models and phenomena. These findings also suggest that steam injection may be used to enhance sulfur capture performance in fluidized beds firing low-moisture fuels such as petroleum coke.

High CO(2) storage capacity in alkali-promoted hydrotalcite-based material: in situ detection of reversible formation of magnesium carbonate.

Alkali-promoted hydrotalcite-based materials showed very high CO(2) storage capacity, exceeding 15 mmol g(-1) when the carbonation reaction was carried out at relatively high temperature (300-500 °C) and high partial pressure of steam and CO(2). In situ XRD experiments have allowed correlation of high CO(2) capacity to the transformation of magnesium oxide centres into magnesium carbonate in alkali-promoted hydrotalcite-based material. Moreover, it has been clearly shown that crystalline magnesium carbonate may be reversibly formed at temperatures above 300 °C in the presence of sufficient partial pressure of steam in the gas phase, conditions that are prevalent in pre-combustion CO(2) capture. The role of steam appears to be of utmost importance for the formation of the bulk carbonate phase and for its reversibility. It is proposed that a high partial pressure of steam keeps the magnesium oxide periclase phase sufficiently hydroxylated to allow magnesium carbonate formation if a relatively high partial pressure CO(2) is present in the gas phase.

Competition of sulphation and carbonation reactions during looping cycles for CO2 capture by CaO-based sorbents.

Two types of sorbents are investigated here (natural limestone and highly reactive calcium aluminate pellets) to elucidate their reactivity in terms of sulphation and carbonation and determine the resulting effect on looping cycles for CO(2) capture. The sorbents are tested in a thermogravimetric analyzer (TGA) apparatus using typical synthetic flue gas mixtures containing 15% CO(2) and various concentrations of SO(2). The sulphation and carbonation conversions were determined during sulphation/carbonation/calcination cycles. The sorbent morphology and its changes were determined by means of a scanning electron microscope (SEM). The results showed that sulphation, that is, the formation of CaSO(4) at the sorbent surface, is a cumulative process with increasing numbers of reaction cycles, which hinders sorbent ability to capture CO(2). In the case of high sorbent reactivity, as determined by its morphology, the unfavorable effect of sulphation is more pronounced. Unfortunately, any increase in the temperature in the carbonation stage accelerates sulphation more than carbonation as a result of higher activation energy for the sulphation reaction. The SEM analyses showed that although sulphation and carbonation occur during cycles involving calcination, an unreacted core/partially sulphated shell sorbent particle pattern is formed. The main outcomes of this research indicate that special attention should be paid to the sulphation when more reactive and more expensive, synthetic CaO-based sorbents are used for CO(2) capture looping cycles. Desulphurization of flue gas before CO(2) capture appears to be essential because CO(2) looping cycles are so strongly affected by the presence of SO(2).

CaO-based pellets supported by calcium aluminate cements for high-temperature CO2 capture.

The development of highly efficient CaO-based pellet sorbents, using inexpensive raw materials (limestones) or the spent sorbent from CO2 capture cycles, and commercially available calcium aluminate cements (CA-14, CA-25, Secar 51, and Secar 80), is described here. The pellets were prepared using untreated powdered limestones or their corresponding hydrated limes and were tested for their CO2 capture carrying capacities for 30 carbonation/calcination cycles in a thermogravimetric analyzer (TGA). Their morphology was also investigated by scanning electron microscopy (SEM) and their compositions before and after carbonation/calcination cycleswere determined by X-ray diffraction (XRD). Pellets prepared in this manner showed superior behavior during CO2 capture cycles compared to natural sorbents, with the highest conversions being > 50% after 30 cycles. This improved performance was attributed to the resulting substructure of the sorbent particles, i.e., a porous structure with nanoparticles incorporated. During carbonation/calcination cycles mayenite (Ca12Al14O33) was formed, which is believed to be responsible for the favorable performance of synthetic CaO-based sorbents doped with alumina compounds. An added advantage of the pellets produced here is their superior strength, offering the possibility of using them in fluidized bed combustion (FBC) systems with minimal sorbent loss due to attrition.

Thermal activation of CaO-based sorbent and self-reactivation during CO2 capture looping cycles.

In this study, the thermal activation of different types of CaO-based sorbents was examined. Pretreatments were performed at different temperatures (800--1300 degrees C) and different durations (6--48 h) using four Canadian limestones. Sieved fractions of the limestones, powders obtained by grinding, and hydroxides produced following multiple carbonation/calcination cycles achieved in a tube furnace were examined. Pretreated samples were evaluated using two types of thermogravimetric reactors/ analyzers. The most important result was that thermal pretreatment could improve sorbent performance. In comparison to the original, pretreated sorbents showed better conversions over a longer series of CO2 cycles. Moreover, in some cases, sorbent activity actually increased with cycle number, and this effectwas especially pronounced for powdered samples preheated at 1000 degrees C. In these experiments, the increase of conversion with cycle number (designated as self-reactivation) after 30 cycles produced samples that were approximately 50% carbonated for the four sorbents examined here, and there appeared to be the potential for additional increase. These results were explained with the newly proposed pore--skeleton model. This model suggests, in addition to changes in the porous structure of the sorbent, that changes in the pore--skeleton produced during pretreatment strongly influence subsequent carbonation/ calcination cycles.