The bimodal composition of carbonatites: Reality or misconception?

The concept of compositional bimodality in carbonatites has become widely accepted and has been used to impose restrictions on the composition of carbonatite magmas. We agree that mineralogical bimodality exists in carbonatites (most are either calcitic or dolomitic/ankeritic), but we argue that there is no compositional bimodality. The idea of bimodality is based on the interpretation of a variety of element distribution diagrams which were compiled only from chemical analyses in which SiO₂ is < 10 wt.%. All others were rejected. Even with such a restricted data set the case for compositional bimodality is extremely weak, but the inclusion of analyses with higher SiO₂ content destroys it completely. Yet these more siliceous compositions must be included, for many carbonatites contain substantial amounts of Fe–Mg silicates which are an essential part of the magmatic mineralogy of the rocks. They account for much of the Mg in carbonatites that are otherwise calcitic. Many such carbonatites contain well in excess of 10 wt.% SiO₂. Supporters of the bimodality concept argue that liquids having compositions between calcite and dolomite can precipitate neither calcite nor dolomite because the minimum on the solid solution loops in the system calcite–dolomite permits only a carbonate of intermediate composition. Therefore, it is argued, liquids of such intermediate composition cannot be parental to calcitic and dolomitic carbonatites; their parent magmas must be calcitic and dolomitic. This deduction is incorrect. It is well established that dolomitic liquids have calcite as the liquidus phase over substantial temperature intervals, and that this is followed by dolomite precipitation. Mixed calcite–dolomite carbonatites are explicable in this way. Therefore, dolomitic liquids can be parental to calcitic carbonatites. However, dolomitic carbonatites cannot crystallize from a calcitic liquid. We suggest that intermediate composition carbonatite magmas are probably common. Bimodality in carbonatites is solely mineralogical, not compositional.     

Elastic behavior of weakly cemented contact

We investigate the elastic behavior of weakly cemented contact. We show that the radial distribution of stresses and the stiffnesses of a cemented contact are governed by the ratio a/RΛ, where R, a, and Λ are, respectively, the grain radius, the contact size, and the ratio of the elastic moduli of cement and grains. Moreover, we show that a cemented contact is always less stiff than a Hertzian contact having a similar size. Finally, we propose accurate approximate expressions of the contact stiffnesses. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemo‐mechanics of cemented granular solids subjected to precipitation and dissolution of mineral species

This paper studies the chemo‐mechanics of cemented granular solids in the context of continuum thermodynamics for fluid‐saturated porous media. For this purpose, an existing constitutive model formulated in the frame of the Breakage Mechanics theory is augmented to cope with reactive processes. Chemical state variables accounting for the reactions between the solid constituents and the solutes in the pore fluid are introduced to enrich the interactions among the microstructural units simulated by the model (i.e., grains and cement bonds). Two different reactive processes are studied (i.e., grain dissolution and cement precipitation), using the chemical variables to describe the progression of the reactions and track changes in the size of grains and bonds. Finally, a homogenization strategy is used to derive the energy potentials of the solid mixture, adopting probability density functions that depend on both mechanical and chemical indices. It is shown that the connection between the statistics of the micro‐scale attributes and the continuum properties of the solid enables the mathematical capture of numerous mechanical effects of lithification and chemical deterioration, such as changes in stiffness, expansion/contraction of the elastic domain, and development of inelastic strains during reaction. In particular, the model offers an interpretation of the plastic strains generated by aggressive environments, which are here interpreted as an outcome of chemically driven debonding and comminution. As a result, the model explains widely observed macroscopic signatures of geomaterial degradation by reconciling the energetics of the deformation/reaction processes with the evolving geometry of the microstructural attributes. Copyright © 2015 John Wiley & Sons, Ltd.     

A numerical study of mechanical behavior of a cement paste under mechanical loading and chemical leaching

Based on relevant experimental data of a petroleum cement paste under mechanical loading and chemical leaching, an elastic‐plastic model is first proposed by taking into account plastic shearing and pore collapse. The degradation of mechanical properties induced by the chemical leaching is characterized by a chemical damage variable which is defined as the increase of porosity. Both elastic and plastic properties of the cement paste are affected by the chemical damage. The proposed model is calibrated from and applied to describe mechanical responses in triaxial compression tests respectively on sound and fully leached samples. In the second part, a phenomenological chemical model is defined to establish the relationship between porosity change and calcium dissolution process. The dissolution kinetics is governed by a diffusion law taking into account the variation of diffusion coefficient with calcium concentration. The chemical model is coupled with the mechanical model, and both are applied to describe mechanical response of cement paste samples subjected to progressive chemical leaching and compressive stresses. Comparisons between experimental data and numerical results are presented.     

Retention of cosmogenic 3He in calcite

Cosmogenic ³He can be used to date a wide range of mineral phases because it is produced from all target elements and can be readily measured above atmospheric contamination. Calcite is a particularly attractive target mineral due to its natural abundance, large crystal size (>1 mm), and low He closure temperature (<70 °C), which limit non-cosmogenic ³He components (Copeland et al., 2007). However, several recent studies have shown that some calcite may not be retentive to helium, even under surface temperatures (Cros et al., 2014; Copeland et al., 2007). This study thus explores ³He retention and production in natural calcite samples at four different sites. Samples from two high elevation sites appear retentive to ³He over 10 kyr timescales, whereas two additional sites clearly suffer from diffusive loss of ³He. Step-degassing experiments suggest that diffusion in calcite is controlled by multiple diffusion domains, with an apparent activation energy of 25–27 kcal mol⁻¹. Although minor ³He loss is expected from the smallest diffusion domains, the observed kinetics cannot explain the poor retention at all sites. We thus propose that opaque (non-transparent) calcite may be more retentive due to the presence of imperfections in the crystal lattice. We conclude that ³He dating of calcite shows promise in some settings. However, because retention depends on crystallographic variability it must be evaluated on a case-by-case basis until robust criteria for retention can be identified.     

Free allocation in the 3rd EU ETS period: assessing two manufacturing sectors

This article provides an analysis of the EU Emissions Trading Scheme (ETS) and the harmonized benchmark-based allocation procedures by comparing two energy-intensive sectors with activities in three Member States. These sectors include the cement industry (CEI) and the pulp and paper industry (PPI) in the UK, Sweden, and France. Our results show that the new procedures are better suited for the more homogeneous CEI, in which the outcome of stricter allocation of emissions allowances is consistent between Member States. For the more heterogeneous PPI – in terms of its product portfolios, technical infrastructures, and fuel mixes – the allocation procedures lead to diverse outcomes. It is the lack of product benchmark curves, and the alternative use of benchmark values that are biased towards a fossil fuel-mix and are based on specific energy use rather than emission intensity, which leads to allocations to the PPI that do not represent the average performance of the top 10% of GHG-efficient installations. Another matter is that grandfathering is still present via the historically based production volumes. How to deal with structural change and provisions regarding capacity reductions and partial cessation is an issue that is highly relevant for the PPI but less so for the CEI.

Policy relevance

After an unprecedented amount of consultation with industrial associations and other stakeholders, a harmonized benchmark-based allocation methodology was introduced in the third trading period of the EU ETS. Establishing a reliable and robust benchmark methodology for free allocation that shields against high direct carbon costs, is perceived as fair and politically acceptable, and still incentivizes firms to take action, is a significant challenge. This article contributes to a deeper understanding of the challenges in effectively applying harmonized rules in industrial sectors that are heterogeneous. This is essential for the debate on structural reformation of the EU ETS, and for sharing experiences with other emerging emissions trading systems in the world that also consider benchmark methodologies.     

Stabilisation/solidification and bioaugmentation treatment of petroleum drill cuttings

Petroleum drill cuttings are usually treated by techniques suitable for particular contaminant groups. The significance of this study consists in the development of a treatment technology that can simultaneously handle the hydrocarbon and metal constituents of drill cuttings. Bioaugmentation is combined with stabilisation/solidification (S/S), within S/S monoliths and in granulated S/S monoliths. Portland cement was used for S/S treatment at 30% binder dosage. Bioaugmentation treatment involved two bacterial densities of a mixed culture bio-preparation. The effects of inclusion of compost, fertiliser and activated carbon were also evaluated. After 28 days, the combined S/S and bioaugmentation treatments recorded up to 15% higher total petroleum hydrocarbon (TPH) loss than control S/S treatment without bioaugmentation. Embedding fertiliser, activated carbon and higher bacterial density within S/S monoliths resulted in the highest (99%) TPH reduction but higher concentrations of metals. The addition of compost and lower bacterial density to granulated S/S monoliths led to similar (98%) TPH degradation and lower amounts of metals. The results suggest that with better mixture optimisation, combining S/S and bioaugmentation could engender more sustainable treatment of drill cuttings.     

Diagenesis and origin of calcite cement in the Flemish Pass Basin sandstone reservoir (Upper Jurassic): Implications for porosity development

The Flemish Pass Basin is a deep-water basin located offshore on the continental passive margin of the Grand Banks, eastern Newfoundland, which is currently a hydrocarbon exploration target. The current study investigates the petrographic characteristics and origin of carbonate cements in the Ti-3 Member, a primary clastic reservoir interval of the Bodhrán Formation (Upper Jurassic) in the Flemish Pass Basin.The Ti-3 sandstones with average Q_86.0F_3.1R_10.9 contain various diagenetic minerals, including calcite, pyrite, quartz overgrowth, dolomite and siderite. Based on the volume of calcite cement, the investigated sandstones can be classified into (1) calcite-cemented intervals (>20% calcite), and (2) poorly calcite-cemented intervals (porous). Petrographic analysis shows that the dominant cement is intergranular poikilotopic (300–500 μm) calcite, which stared to form extensively at early diagenesis. The precipitation of calcite occured after feldspar leaching and was followed by corrosion of quartz grains. Intergranular calcite cement hosts all-liquid inclusions mainly in the crystal core, but rare primary two-phase (liquid and vapor) fluid inclusions in the rims ((with mean homogenization temperature (T_h) of 70.2 ± 4.9 °C and salinity estimates of 8.8 ± 1.2 eq. wt.% NaCl). The mean δ¹⁸O and δ¹³C isotopic compositions of the intergranular calcite are −8.3 ± 1.2‰, VPDB and −3.0 ± 1.3‰, VPDB, respectively; whereas, fracture-filling calcite has more depleted δ¹⁸O but similar δ¹³C values. The shale normalized rare earth element (REE_SN) patterns of calcite are generally parallel and exhibit slightly negative Ce anomalies and positive Eu anomalies. Fluid-inclusion gas ratios (CO₂/CH₄ and N₂/Ar) of calcite cement further confirms that diagenetic fluids originated from modified seawater. Combined evidence from petrographic, microthermometric and geochemical analyses suggest that (1) the intergranular calcite cement precipitated from diagenetic fluids of mixed marine and meteoric (riverine) waters in suboxic conditions; (2)the cement was sourced from the oxidation of organic matters and the dissolution of biogenic marine carbonates within sandstone beds or adjacent silty mudstones; and (3) the late phases of the intergranular and fracture-filling calcite cements were deposited from hot circulated basinal fluids.Calcite cementation acts as a main controlling factor on the reservoir quality in the Flemish Pass reservoir sandstones. Over 75% of initial porosity was lost due to the early calcite cementation. The development of secondary porosity (mostly enlarged, moldic pores) and throats by later calcite dissolution due to maturation of organic matters (e.g., hydrocarbon and coals), was the key process in improving the reservoir quality.     

The diagenetic history of Oligocene-Miocene sandstones of the Austrian north Alpine foreland basin

Diagenesis is an essential tool to reconstruct the development of reservoir rocks. Diagenetic processes - precipitation and dissolution - have an influence on pore space. The present paper aims to study the diagenetic history of deep-marine sandstones of the Austrian Alpine Foreland Basin. To reach that goal, sediment petrology and diagenetic features of more than 110 sandstone samples from water- and gas-bearing sections from gas fields within the Oligocene-Miocene Puchkirchen Group and Hall Formation has been investigated. Special emphasis was put on samples in the vicinity of the gas-water contact (GWC). The sediment petrography of sandstones of Puchkirchen Group and Hall Formation is similar; hence their diagenesis proceeded the same way. In fact, primary mineralogy was controlled by paleo-geography with increasing transport distance and diverse detrital input.Sediment petrographically, investigated sandstones from the water-bearing horizon seemed quite comparable to the gas-bearing sediments. In general, they can be classified as feldspatic litharenites to litharenites and display porosities of up to 30% and permeabilities of up to 1300 mD. The carbon and oxygen isotopic composition of bulk carbonate cements from these sandstones range from−3.8 to +2.2 and from −7.5 to +0.2‰ [VPDB]. However, near the Gas-Water Contact (GWC) a horizon with low porosities (<3%) and permeabilities (<0.1 mD) is present. This zone is completely cemented with calcite, which has a blocky/homogenous morphology. A slight, but significant negative shift in δ18O isotopy (−2.5‰) is evident.During early diagenesis the first carbonate generations formed. First a fibrous calcite and afterwards a micritic calcite precipitated. Further siliciclastic minerals, such as quartz and feldspar (K-feldspar and minor plagioclase), exhibit corroded grains. Occasionally, clay minerals (illite; smectite, chlorite) formed as rims around detrital grains. Late diagenesis is indicated by the formation of a low permeable zone at the GWC.     

红河油田低压易漏地层水平段固井技术

为提高红河油田水平井固井质量,满足后期分段压裂需求,对红河油田水平井固井技术进行了研究。针对红河油田水平段固井技术难点,通过室内和现场试验,优选出了GSJ水泥浆体系,基于实测地层压力与地层破裂压力,进行平衡压力固井设计确定了环空浆体结构,为提高顶替效率,优化了扶正器类型与加放位置,专业软件模拟表明套管居中度＞73%,良好的井眼准备和套管漂浮措施确保了管柱的顺利下入;加长胶塞、树脂滚轮刚性旋流扶正器和关井阀等附件的使用,保证了固井质量。现场应用53口水平井,水泥浆全部返至地面,CBL测井结果表明,固井优良率达81.13%。该固井技术成功应用于红河油田水平井中,保证了固井质量,满足了后期分段压裂的需要。