Stability of hydrotalcites formed from Bayer refinery environmental control processes

Bauxite refinery residues (red mud) are derived from the Bayer process by the digestion of crushed bauxite in concentrated sodium hydroxide at elevated temperatures and pressures. This slurry residue, if untreated, is unsuitable for discharge directly into the environment and is usually stored in tailing dams. The liquid portion has the potential for discharge, but requires pre-treatment before this can occur. The seawater neutralisation treatment facilitates a significant reduction in pH and dissolved metal concentrations, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. The hydrotalcite-like compounds, precipitated during seawater neutralisation, also remove a range of transition metals, oxy-anions and other anionic species through a combination of intercalation and adsorption reactions: smaller anions are intercalated into the hydrotalcite matrix, while larger molecules are adsorbed on the particle surfaces. A phenomenon known as ‘reversion’ can occur if the seawater neutralisation process is not properly controlled. Reversion causes an increase in the pH and dissolved impurity levels of the neutralised effluent, rendering it unsuitable for discharge. It is believed that slow dissolution of components of the red mud residue and compounds formed during the neutralisation process are responsible for reversion. This investigation looked at characterising natural hydrotalcite (Mg6Al2(OH)16(CO3)∙4H2O) and ‘Bayer’ hydrotalcite (synthesised using the seawater neutralisation process) using a variety of techniques including X-ray diffraction, infrared and Raman spectroscopy, and thermogravimetric analysis. This investigation showed that Bayer hydrotalcite is comprised of a mixture of 3:1 and 4:1 hydrotalcite structures and exhibited similar chemical characteristic to the 4:1 synthetic hydrotalcite. Hydrotalcite formed from the seawater neutralisation of Bauxite refinery residues has been found not to cause reversion. Other components in red mud were investigated to determine the cause of reversion and this investigation found three components that contributed to reversion: 1) tricalcium aluminate, 2) hydrocalumite and 3) calcium hydroxide. Increasing the amount of magnesium in the neutralisation process has been found to be successful in reducing reversion.

ATR-FTIR measurement of biomass components in phosphonium ionic liquids

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO 4), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO 4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed -aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO 4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm 1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process. © 2012 Copyright Taylor and Francis Group, LLC.

Microcosm study of ion mobilization and greenhouse gas evolution in soils of a plantation-forested subtropical coastal catchment

This study examined the potential for Fe mobilization and greenhouse gas (GHG, e.g. CO2, and CH4) evolution in SEQ soils associated with a range of plantation forestry practices and water-logged conditions. Intact, 30-cm-deep soil cores collected from representative sites were saturated and incubated for 35 days in the laboratory, with leachate and headspace gas samples periodically collected. Minimal Fe dissolution was observed in well-drained sand soils associated with mature, first-rotation Pinus and organic Fe complexation, whereas progressive Fe dissolution occurred over 14 days in clear-felled and replanted Pinus soils with low organic matter and non-crystalline Fe fractions. Both CO2 and CH4 effluxes were relatively lower in clear-felled and replanted soils compared with mature, first-rotation Pinus soils, despite the lack of statistically significant variations in total GHG effluxes associated with different forestry practices. Fe dissolution and GHG evolution in low-lying, water-logged soils adjacent to riparian and estuarine, native-vegetation buffer zones were impacted by mineral and physical soil properties. Highest levels of dissolved Fe and GHG effluxes resulted from saturation of riparian loam soils with high Fe and clay content, as well as abundant organic material and Fe-metabolizing bacteria. Results indicate Pinus forestry practices such as clear-felling and replanting may elevate Fe mobilization while decreasing CO2 and CH4 emissions from well-drained, SEQ plantation soils upon heavy flooding. Prolonged water-logging accelerates bacterially mediated Fe cycling in low-lying, clay-rich soils, leading to substantial Fe dissolution, organic matter mineralization, and CH4 production in riparian native-vegetation buffer zones.

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe - DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe 2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide-rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well-drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Preparation, characterisation and in vivo osteogenesis of mesoporous bioactive glasses

Bone defects, especially large bone defects, remain a major challenge in orthopaedic surgery. Autologous bone transplantation is considered the most effective treatment, but insufficient donor tissue, coupled with concerns about donor site morbidity, has hindered this approach in large-scale applications. Alternative approaches include implanting biomaterials such as bioactive glass (BG), which has been widely used for bone defect healing, due to having generally good biocompatibility, and can be gradually biodegraded during the process of new bone formation. Mesoporous bioactive glass (MBG) is a newly developed bioactive glass which has been proven to have enhanced in-vitro bioactivity; however the in-vivo osteogenesis has not been studied. A critical problem in using the bone tissue engineering approach to restore large bone defects is that the nutrient supply and cell viability at the centre of the scaffold is severely hampered since the diffusion distance of nutrients and oxygen for cell survival is limited to 150-200µm. Cobalt ions has been shown to mimic hypoxia, which plays a pivotal role in coupling angiogenesis with osteogenesis in-vivo by activating hypoxia inducing factor-1α (HIF-1α) transcription factor, subsequently initiating the expression of genes associated with tissue regeneration. Therefore, one aim of this study is to investigate the in-vivo osteogenesis of MBG by comparison with BG and β-TCP, which are widely used clinically. The other aim is to explore hypoxia-mimicking biomaterials by incorporating Cobalt into MBG and β-TCP. MBG and β-TCP incorporated with 5% cobalt (5Co-MBG and 5CCP) have also been studied in-vivo to determine whether the hypoxic effect has a beneficial effect on the bone formation. The composition and microstructure of synthesised materials (BG, MBG, 5Co-MBG, 5CCP) were characterised, along with the mesopore properties of the MBG materials. Dissolution and cytotoxicity of the Co-containing materials were also investigated. Femoral samples with defects harvested at 4 and 8 weeks were scanned using micro-CT followed by processing for histology (H&E staining) to determine bone formation. Histology of MBG showed a slower rate of bone formation at 4 weeks than BG, however at 8 weeks it could be clearly seen that MBG had more bone formation. The in-vivo results show that the osteogenesis of MBG reciprocates the enhanced performance shown in-vitro compared to BG. Dissolution study showed that Co ions can be efficiently released from MBG and β-TCP in a controllable way. Low amounts of Co incorporated into the MBG and β-TCP showed no significant cytotoxicity and the Co-MBG powders maintained a mesopore structure although not as highly ordered as pure MBG. Preliminary study has shown that Co incorporated samples showed little to no bone formation, instead incurring high lymphocyte activity. Further studies need to be done on Co incorporated materials to determine the cause for high lymphocyte activity in-vivo, which appear to hinder bone formation. In conclusion, this study demonstrated the osteogenic activity of MBG and provided some valuable information of tissue reaction to Co-incorporated MBG and TCP materials.

Preparation, characterization, and in vitro bioactivity of nagelschmidtite bioceramics

The aim of this study is to prepare Ca, P and Si-containing ternary oxide nagelschmidtite (NAGEL, Ca7Si2P2O16) bioceramics and explore their in vitro bioactivity for potential bone tissue regeneration. We prepared dense NAGEL ceramics through high-temperature sintering of NAGEL ceramic powders. The apatite-mineralization ability, dissolution rate, and human osteoblast response (including cytotoxicity analysis, attachment, morphology, proliferation, and bone-related gene expression) to NAGEL ceramics have been systematically studied by comparing with conventional β-tricalcium phosphate (β-TCP) ceramics. The results showed that NAGEL ceramics possessed more obvious apatite mineralization and dissolution (degradation) and stimulated bone-related gene expression (OCN and OPN) of osteoblasts than β-TCP ceramics. NAGEL ceramics also showed no significant cytotoxicity. NAGEL ceramics supported osteoblast attachment, proliferation, and osteogenic gene expression, with a comparable cell proliferation activity with β-TCP ceramics. These results indicate that novel NAGEL bioceramics with the specific composition of Ca7Si2P2O16, are a promising biomaterial for bone tissue regeneration application.

Ionic liquid pre-treatment and fractionation of sugarcane bagasse for the production of bioethanol

Pretretament is an essential and expensive processing step for the manufacturing of ethanol from lignocellulosic raw materials. Ionic liquids are a new class of solvents that have the potential to be used as pretreatment agents. The attractive characteristics of ionic liquid pretreatment of lignocellulosics such as thermal stability, dissolution properties, fractionation potential, cellulose decrystallisation capacity and saccharification impact are investigated in this thesis. Dissolution of bagasse with 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) at high temperatures (110 �‹C to 160 �‹C) is investigated as a pretreatment process. Material balances are reported and used along with enzymatic saccharification data to identify optimum pretreatment conditions (150 �‹C for 90 min). At these conditions, the dissolved and reprecipitated material is enriched in cellulose, has a low crystallinity and the cellulose component is efficiently hydrolysed (93 %, 3 h, 15 FPU). At pretreatment temperatures < 150 �‹C, the undissolved material has only slightly lower crystallinity than the starting. At pretreatment temperatures . 150 �‹C, the undissolved material has low crystallinity and when combined with the dissolved material has a saccharification rate and extent similar to completely dissolved material (100 %, 3h, 15 FPU). Complete dissolution is not necessary to maximize saccharification efficiency at temperatures . 150 �‹C. Fermentation of [C4mim]Cl-pretreated, enzyme-saccharified bagasse to ethanol is successfully conducted (85 % molar glucose-to-ethanol conversion efficiency). As compared to standard dilute acid pretreatment, the optimised [C4mim]Cl pretreatment achieves substantially higher ethanol yields (79 % cf. 52 %) in less than half the processing time (pretreatment, saccharification, fermentation). Fractionation of bagasse partially dissolved in [C4mim]Cl to a polysaccharide rich and a lignin rich fraction is attempted using aqueous biphasic systems (ABSs) and single phase systems with preferential precipitation. ABSs of ILs and concentrated aqueous inorganic salt solutions are achievable (e.g. [C4mim]Cl with 200 g L-1 NaOH), albeit they exhibit a number of technical problems including phase convergence (which increases with increasing biomass loading) and deprotonation of imidazolium ILs (5 % - 8 % mol). Single phase fractionation systems comprising lignin solvents / cellulose antisolvents, viz. NaOH (2M) and acetone in water (1:1, volume basis), afford solids with, respectively, 40 % mass and 29 % mass less lignin than water precipitated solids. However, this delignification imparts little increase in saccharification rates and extents of these solids. An alternative single phase fractionation system is achieved simply by using water as an antisolvent. Regulating the water : IL ratio results in a solution that precipitates cellulose and maintains lignin in solution (0.5 water : IL mass ratio) in both [C4mim]Cl and 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc)). This water based fractionation is applied in three IL pretreatments on bagasse ([C4mim]Cl, 1-ethyl-3-methyl imidazolium chloride ([C2mim]Cl) and [C2mim]OAc). Lignin removal of 10 %, 50 % and 60 % mass respectively is achieved although only 0.3 %, 1.5 % and 11.7 % is recoverable even after ample water addition (3.5 water : IL mass ratio) and acidification (pH . 1). In addition the recovered lignin fraction contains 70 % mass hemicelluloses. The delignified, cellulose-rich bagasse recovered from these three ILs is exposed to enzyme saccharification. The saccharification (24 h, 15 FPU) of the cellulose mass in starting bagasse, achieved by these pretreatments rank as: [C2mim]OAc (83 %)>>[C2mim]Cl (53 %)=[C4mim]Cl(53%). Mass balance determinations accounted for 97 % of starting bagasse mass for the [C4mim]Cl pretreatment , 81 % for [C2mim]Cl and 79 %for [C2mim]OAc. For all three IL treatments, the remaining bagasse mass (not accounted for by mass balance determinations) is mainly (more than half) lignin that is not recoverable from the liquid fraction. After pretreatment, 100 % mass of both ions of all three ILs were recovered in the liquid fraction. Compositional characteristics of [C2mim]OAc treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are opposite to those of chloride IL treated solids. The former biomass characteristics resemble those imparted by aqueous alkali pretreatment while the latter resemble those of aqueous acid pretreatments. The 100 % mass recovery of cellulose in [C2mim]OAc as opposed to 53 % mass recovery in [C2mim]Cl further demonstrates this since the cellulose glycosidic bonds are protected under alkali conditions. The alkyl chain length decrease in the imidazolium cation of these ILs imparts higher rates of dissolution and losses, and increases the severity of the treatment without changing the chemistry involved.

Fresh water and acid sensitivity of authigenic clays in sandstone reservoirs

Authigenic illite-smectite and chlorite in reservoir sandstones from several Pacific rim sedimentary basins in Australia and New Zealand have been examined using an Electroscan Environmental Scanning Electron Microscope (ESEM) before, during, and after treatment with fresh water and HCl, respectively. These dynamic experiments are possible in the ESEM because, unlike conventional SEMs that require a high vacuum in the sample chamber (10-6 torr), the ESEM will operate at high pressures up to 20 torr. This means that materials and processes can be examined at high magnifications in their natural states, wet or dry, and over a range of temperatures (-20 to 1000 degrees C) and pressures. Sandstones containing the illite-smectite (60-70% illite interlayers) were flushed with fresh water for periods of up to 12 hours. Close examination of the same illite-smectite lines or filled pores, both before and after freshwater treatments, showed that the morphology of the illite-smectite was not changed by prolonged freshwater treatment. Chlorite-bearing sandstones (Fe-rich chlorite) were reacted with 1M to 10M HCl at temperatures of up to 80 degrees C and for periods of up to 48 hours. Before treatment the chlorites showed typically platy morphologies. After HCl treatment the chlorite grains were coated with an amorphous gel composed of Ca, Cl, and possibly amorphous Si, as determined by EDS analyses on the freshly treated rock surface. Brief washing in water removed this surface coating and revealed apparently unchanged chlorite showing no signs of dissolution or acid attack. However, although the chlorite showed no morphological changes, elemental analysis only detected silicon and oxygen.

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.

The role of randomly mixed-layered chlorite/smectite in the transformation of smectite to chlorite

Vesicular and groundmass phyllosilicates in a hydrothermally altered basalt from the Point Sal ophiolite, California, have been studied using transmission electron microscopy (TEM). Pore-filling phyllosilicates are texturally characterized as having coherent, relatively thick and defect-free crystals of chlorite (14 Å) with occasional 24-Å periodicities. Groundmass phyllosilicates are texturally characterized as 1) randomly oriented crystals up to 200 Å in width and 2) larger, more coherent crystals up to 1000 Å in width. Small crystallites contain predominantly 14-Å layers with some 24-Å units. Large crystals show randomly interlayered chlorite/smectite (C/S), with approximately 50% chlorite on average. Adjacent smectite-like layers are not uncommon in the groundmass phyllosilicates. Electron microprobe analyses show that Fe/Mg ratios of both groundmass and vesicular phyllosilicates are fairly constant. Termination of brucite-like interlayers has been identified in some of the TEM images. The transformation mechanisms represented by these layer terminations are 1) growth of a brucite-like interlayer within smectite interlayer regions and 2) the dissolution and reprecipitation of elements to form chlorite layers. Both mechanisms require an increase in volume as smectite transforms to chlorite. The data, combined with that from previously published reports, suggest that randomly interlayered C/S is a metastable phase formed in microenvironments with low water/rock ratios. Chlorite forms in microenvironments in the same sample dominated by higher water/rock ratios. The relatively constant number of Mg's in the structure (Mg#) of both structures indicates that in both microenvironments the bulk rock composition has influence over the composition of phyllosilicates.

Microstructural characterization of quenched melt-textured YBa2Cu3O7-δ materials

The microstructure of YBa2Cu3O7-δ (YBCO) materials, melt-textured in air and quenched from the temperature range 900-990°C, has been characterized using a combination of x-ray diffractometry, optical microscopy, scanning electron microscopy, transmission electron microscopy, and energy dispersive x-ray spectrometry. BaCu2O2 and BaCuO2 were found to coexist in samples quenched from the temperature range 920-960°C. The formation of BaCu2O2 preceded the formation of YBCO. Once the YBCO had formed, BaCu2O2 was present at the solidification front filling the space between nearly parallel platelets of YBCO. Large Y2BaCuO5 particles at the solidification front appeared divided into smaller ones as a result of their dissolution in the liquid that quenched as BaCu2O2.

ESEM study of authigenic chlorite acid sensitivity in sandstone reservoirs

The effect of HCl on authigenic chlorite in three different sandstones has been examined uisng an Environmental Scanning Electron Microscope (ESEM), together with conventional analytical techniques. The ESEM enabled chlorites to be directly observed in situ at high magnifications during HCl treatment, and was particularly effective in allowing the same chlorite areas to be closely compared before and after acid treatment. Chlorites were reacted with 1M to 10M HCl at temperatures up to 80°C and for periods up to five months. After all treatments, chlorites show extensive leaching of iron, magnesium and aluminum, and their crystalline structure is destroyed. However, despite these major compositional and structural changes, chlorites show little or no visible evidence of acid attack, with precise morphological detail of individual plates preserved in all samples following acid treatments. Chlorite dissolution, sensu stricto, did not occur as a result of acidization of the host sandstones. Acid-treated chlorides are likely to exits in a structurally weakened state that may make them susceptible to physical disintegration during fluid flow. Accordingly, fines migration may be a significant engineering problem associated with the acidization of chlorite-bearing sandstones. © 1993.

Removal of epoxy-attached thin-sections from glass slides by plasma-etching

Thin-sectioned samples mounted on glass slides with common petrographic epoxies cannot be easily removed (for subsequent ion-milling) by standard methods such as heating or dissolution in solvents. A method for the removal of such samples using a radio frequency (RF) generated oxygen plasma has been investigated for a number of typical petrographic and ceramic thin sections. Sample integrity and thickness were critical factors that determined the etching rate of adhesive and the survivability of the sample. Several tests were performed on a variety of materials in order to estimate possible heating or oxidation damage from the plasma. Temperatures in the plasma chamber remained below 138°C and weight changes in mineral powders etched for 76 hr were less than ±4%. A crystal of optical grade calcite showed no apparent surface damage after 48 hr of etching. Any damage from the oxygen plasma is apparently confined to the surface of the sample, and is removed during the ion-milling stage of transmission electron microscopy (TEM) sample preparation.

Neutralization of acid sulfate solutions using bauxite refinery residues and its derivatives

This investigation has shown that by transforming free caustic in red mud (RM) to Bayer hydrotalcite (during the seawater neutralization (SWN) process) enables a more controlled release mechanism for the neutralization of acid sulfate soils. The formation of hydrotalcite has been confirmed by X-ray diffraction (XRD) and differential thermalgravimetric analysis (DTG), while the dissolution of hydrotalcite and sodalite has been observed through XRD, DTG, pH plots, and ICP-OES. Coupling of all techniques enabled three neutralization mechanisms to be determined: (1) free alkali, (2) hydrotalcite dissolution, and (3) sodalite dissolution. The mechanisms are determined on the basis of ICP-OES and kinetic information. When the mass of RM or SWN-RM is greater than 0.08 g/50 mL, the pH of solution increases to a suitable value for plant life with aluminum leaching kept at a minimum. To obtain a neutralization pH greater than 6 in 10 min, the following ratio of bauxite residue (g) in 50 mL with a known iron sulfate (Fe2(SO4)3) concentration can be determined as follows: 0.04 g:50 mL:0.1 g/L of Fe2(SO4)3.

Carbonate cementation in sandstones of the Plover Formation, North West Shelf, W.A

Ancient sandstones include important reservoirs for hydrocarbons (oil and gas), but, in many cases, their ability to serve as reservoirs is heavily constrained by the effects of carbonate cements on porosity and permeability. This study investigated the controls on distribution and abundance of carbonate cements within the Jurassic Plover Formation, Browse Basin, North West Shelf, Australia. Samples were analysed petrographically with point counting of 59 thin sections and mineralogically with x-ray diffraction from two wells within the Torosa Gas Field. Selected samples were also analysed for stable isotopes of O and C. Sandstones are classified into eleven groups. Most abundant are quartzarenites and then calcareous quartzarenites. Lithology ranged between sandstones consisting of mostly quartz with scant or no carbonate in the form of cement or allochems, to sandstones with as much as 40% carbonate. The major sources of carbonate cement in Torosa 1 and Torosa 4 sandstones were found to be early, shallow marine diagenetic processes (including cementation), followed by calcite cementation and recrystallisation of cements and allochems during redistribution by meteoric waters. Blocky and sparry calcite cements, indicative of meteoric environments on the basis of stable isotope values and palaeotemperature assessment, overprinted the initial shallow marine cement phase in all cases and meteoric cements are dominant. Torosa 4 was influenced more by marine settings than Torosa 1, and thus has the greater potential for calcite cement. The relatively low compaction of calcite-cemented sandstones and the stable isotope data suggest deep burial cementation was not a major factor. Insufficient volcanic rock fragments or authigenic clay content infers alteration of feldspars was not a major source of calcite. Very little feldspar is present, altered or otherwise. Hence, increased alkalinity from feldspar dissolution is not a contributing factor in cement formation. Increased alkalinity from bacterial sulphate reduction in organic–rich fine sediments may have driven limited cementation in some samples. The main definable and significant source of diagenetic marine calcite cement originated from original marine cements and the nearby dissolution of biogenic sources (allochems) at relatively shallow depths. Later diagenetic fluids emplaced minor dolomite, but this cement did not greatly affect the reservoir quality in the samples studied.