Adsorption of pyridine by combusted oil shale

Large volumes of solid waste material will be produced during the commercial production of shale oil. An alternative to the disposal of the solid waste product is utilization. One potential use of spent oil shale is for the stabilization of hazardous organic compounds. The objective of this study was to examine the adsorption of pyridine, commonly found in oil shale process water, by spent oil shale. The adsorption of pyridine by fresh and weathered samples of combusted New Albany Shale and Green River Formation oil shale was examined. In general, pyridine adsorption can be classified as L-type and the isotherms modeled with the Langmuir and Freundlich equations. For the combusted New Albany Shale, weathering reduced the predicted pyridine adsorption maximum and increased the amount of pyridine adsorbed at low solution concentrations. For the combusted Green River Formation oil shales, weathering increased the predicted pyridine adsorption maximum. The pyridine adsorption isotherms were similar to those produced for a combusted Australian oil shale. Although adsorption can be mathematically described by empirical models, the reduction in solution concentrations of pyridine was generally less than 10 mg/l at an initial concentration of 100 mg/l. Clearly, the observed reduction in solution pyridine concentrations does not sufficiently justify using spent oil shale as a stabilizing medium. However, data in the literature suggest that other organic compounds can be effectively removed from solution by spent oil shale and that adsorption is dependent on process conditions and organic compound type.     

Adsorption of oxyanions by spent western oil shale: II. selenite

The adsorption and desorption behavior of selenite by processed Green River Formation oil shales were examined. The selenite adsorption data could be quantitatively described by both the Freundlich and Langmuir isotherms. However, greaterR ² values were obtained for the Freundlich isotherms. Furthermore, selenite adsorption was not a function of the extraction process. The adsorption of selenite by the processed oil shales was irreversible. Upon dilution of the equilibrium systems, additional selenite removal from solution occurred. A thermochemical analysis of the adsorption and desorption equilibrium solutions indicated that the solutions were undersaturated with respect to a number of metal selenite solids. This indicates that precipitation processes are not influencing selenite behavior. However, not all selenite minerals were examined in the evaluation because of the lack of thermochemical data. An insufficient equilibration period for the adsorption study or the alteration of processed oil shale solids as a result of hydration reactions may also have hastened the additional removal of selenite during the desorption studies.     

Trace element mineral transformations associated with hydration and recarbonation of retorted oil shale

A laboratory study was conducted to evaluate the influence of hydration and recarbonation on the solidphase distribution of trace elements in retorted oil shale. The oil shale samples were retorted by the Paraho direct heating process and equilibrated with deionized—distilled water under controlled carbon dioxide conditions. A sequential extraction technique was then used to fractionate trace elements into soluble, KNO₃-extractable (easily exchangeable), H₂O-extractable (easily adsorbed), NaOh-extractable (organic), EDTA-extractable (carbonate), HNO₃-extractable (sulfide), and residual (nonextractable silicate) phases. The chemical fractions present in retorted oil shale and hydrated and recarbonated retorted oil shale were compared to identify trace element mineralogical changes that may occur in retorted oil shale disposal environments.Trace elements examined in this study were found to reside predominantly in the HNO₃-extractable and residual fractions. Hydration of retorted oil shale resulted in a shift in the majority of trace elements from residual to extractable forms. Cobalt, nickel, and zinc extractabilities were not significantly influenced by hydration, whereas antimony increased in the residual fraction. Subjecting retorted oil shale to atmospheric (0.033%) and 10% CO₂(g) levels over a nine-month equilibration period resulted in partial and full recarbonation, respectively. As the influence of recarbonation increased, trace elements reverted to residual forms. Vanadium, choromium, copper, zinc, antimony, and molybdenum in the 10% CO₂(g) recarbonated material were more resistant to sequential extraction than in retorted oil shale, whereas strontium, barium, and manganese were less resistant to sequential extraction. The extractabilities of cobalt, nickel, and lead were not affected by recarbonation. Recarbonation did not result in a predicted increase in EDTA-extractable trace elements. In general, the amounts of trace elements extracted by EDTA (and correlated to carbonate forms) were invariant with respect to equilibrium CO₂(g) levels.A significant result of this study was that the mineralogical residencies of trace elements in retorted oil shale were altered in response to conditions that may be present in a disposal environment. Thus, the long-term release of trace elements in retorted oil shale disposal environments may not be adequately predicted by applying the toxicity characteristic leaching procedure (TCLP).     

Arsenate adsorption at the sediment–water interface: sorption experiments and modelling

Arsenate adsorption was studied in three clastic sediments, as a function of solution pH (4.0–9.0) and arsenate concentration. Using known mineral values, protolytic constants obtained from the literature and K _ads values (obtained by fitting experimental adsorption data with empirical adsorption model), the constant capacitance surface complexation model was used to explain the adsorption behavior. The experimental and modelling approaches indicate that arsenate adsorption increases with increased pH, exhibiting a maximum adsorption value before decreasing at higher pH. Per unit mass, sample S₃ (smectite–quartz/muscovite–illite sample) adsorbs more arsenate in the pH range 5–8.5, with 98% of sites occupied at pH 6. S₁ and S₂ have less adsorption capacity with maxima adsorption in the pH ranges of 6–8.5 and 4–6, respectively. The calculation of saturation indices by PHREEQC at different pH reveals that the solution was undersaturated with respect to aluminum arsenate (AlAsO₄2H₂O), scorodite (FeAsO₄2H₂O), brucite and silica, and supersaturated with respect to gibbsite, kaolinite, illite and montmorillonite (for S₃ sample). Increased arsenate concentration (in isotherm experiments) may not produce new solid phases, such as AlAsO₄2H₂O and/or FeAsO₄2H₂O.     

Kinetics of zinc and arsenate co-sorption at the goethite-water interface

Little or no information is available in the literature about reaction processes of co-sorbing metals and arsenate [As(V)] on variable-charged surfaces or factors influencing these reactions. Arsenic and metal contamination are, however, a common co-occurrence in many contaminated environments. In this study, we investigated the co-sorption kinetics of 250 μM As(V) and zinc [Zn(II)] in 10, 100, and 1000 mg goethite L⁻¹ 0.01 M NaCl solution at pH 7, collected complementary As and Zn K-edge extended X-ray absorption fine structure (EXAFS) data after various aging times, and performed a replenishment desorption/dissolution study at pH 4 and 5.5 after 6 months of aging time. Arsenate and Zn(II) formed adamite-like and koritnigite-like precipitates on goethite in 100- and 10-ppm goethite suspensions, respectively, whereas in 1000-ppm goethite suspensions, As(V) formed mostly double-corner sharing complexes and Zn(II) formed a solid solution on goethite according to EXAFS spectroscopic analyses. In all goethite suspension densities, surface adsorption reactions were part of the initial reaction processes. In 10- and 100-ppm goethite suspensions, a heterogeneous nucleation reaction occurred in which adamite-like precipitates began to form 48 h earlier than koritnigite-like surface precipitates. Arsenate and Zn(II) uptake from solution decreased after 4 weeks. Replenishment desorption studies showed that the precipitates and surface adsorbed complexes on goethite were susceptible to proton-promoted dissolution resulting in many cases in more than 80% loss of Zn(II) and ∼ 60% to 70% loss of arsenate. The molar Zn:As dissolution ratio was dependent on the structure of the precipitate and was cyclic for the adamite and koritnigite-like surface precipitates, reflecting the concentric and plane-layered structures of adamite and koritnigite, respectively.     

Response of oil shale to fragmentation by cylindrical charges

Summary This paper describes an experimental program that was conducted in 1981 through 1983 in the Anvil Points Oil Shale Mine near Rifle, Colorado. The objective was to examine the response of the kerogen rich oil shale to explosive charges in relatively large scale tests. Due to an alleged shortage of oil at that time the price per barrel of crude oil had reached nearly $40 and the United States was looking at oil shale as a possible source of hydrocarbon fuels.It was the intention of the fragmentation program to develop a modified in situ retort to recover the oil from the fragmented shale. Programs were already underway wherein the oil shale was being mined, transported to the surface, and retorted to remove the oil. This surface retorting resulted in a tremendous amount of spent shale (shale with the kerogen removed) which had to be handled and it was felt that this would lead to serious environmental problems. The scheme being investigated in the program at Anvil Points was one in which about 25% of the shale is mined, moved to the surface, and retorted. The remaining 75% of the shale was to be fragmented in place and an underground retort formed so that the oil could be removed without the necessity of transporting the shale to the surface.A successful method was not developed but the results of the program did provide information on the response of shale to both single hole and multiple hole explosive charges.     

Arsenate and antimonate adsorption competition on 6-line ferrihydrite monitored by infrared spectroscopy

Arsenate and antimonate are water-soluble toxic mining waste species which often occur together and can be sequestered with varying success by a hydrous ferric oxide known as ferrihydrite. The competitive adsorption of arsenate and antimonate to thin films of 6-line ferrihydrite has been investigated using primarily adsorption/desorption kinetics monitored by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy on flowed solutions containing 10⁻³ and 10⁻⁵ mol L⁻¹ of both species at pH 3, 5, and 7. ICP-MS analysis of arsenate and antimonate adsorbed to 6-line ferrihydrite from 10⁻³ mol L⁻¹ mixtures in batch adsorption experiments at pH 3 and 7 was carried out to calibrate the relative surface concentrations giving rise to the IR spectral absorptions. The kinetic data from 10⁻³ and 10⁻⁵ mol L⁻¹ mixtures showed that at pH 3 antimonate achieved a greater surface concentration than arsenate after 60 min adsorption on 6-line ferrihydrite. However, at pH 7, the adsorbed arsenate surface concentration remained relatively high while that of adsorbed antimonate was much reduced compared with pH 3 conditions. Both species desorbed slowly into pH 3 solution while at pH 7 most adsorbed arsenate showed little desorption and adsorbed antimonate concentration was too low to register its desorption behaviour. The nature of arsenate which is almost irreversibly adsorbed to 6-line ferrihydrite remains to be clarified.     

Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO₄)_1.5 solutions also containing 0.02-0.2 M Na₂HAsO₄. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO₄·4-7H₂O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH)₆ octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard ferrihydrite growth in the precipitates with molar Fe/As ratios of 1-4, whereas increased reaction gradually transforms two-line ferrihydrite to six-line ferrihydrite at Fe/As ratios of 5 and greater.     

油页岩对钴离子的吸附性能研究

油页岩中因含有大量的黏土矿物而对金属离子具有一定的吸附能力.采用静态吸附法对油页岩吸附钴离子的影响因素及吸附动力学进行了研究.结果表明,油页岩粒度、溶液浓度、溶液pH值、吸附时间等均对吸附性能有一定影响.油页岩对钴离子的吸附量随样品粒径的减小而增大;随着钴离子初始浓度的增加,油页岩对钴离子的吸附总量增加;溶液pH值在3~8范围内,油页岩对钴离子的吸附量和吸附率随着pH值的增大呈上升趋势.通过吸附动力学研究发现,油页岩对钴离子的吸附过程符合准二级动力学过程和粒子内扩散机理.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.     

Adsorption of copper and zinc by oil shale

 Oil shale is able to remove appreciable amounts of copper and zinc ions from aqueous solutions. It was noted that an increase in the adsorbent concentration with constant copper or zinc concentration resulted in greater metal removal from solution. An increase in the copper or zinc concentration with a constant sorbent concentration resulted in higher metal loading per unit weight of sorbent. For both metals, copper and zinc, equilibrium was attained after 24-h contact time. Increase in the initial pH or temperature of the metal solution resulted in an increase in the metal uptake per unit weight of the sorbent. Freundlich isotherm model was found to be applicable for the experimental data of Cu²⁺ and Zn²⁺. The results showed that oil shale could be used for the adsorption of the Cu²⁺ and Zn²⁺ with higher affinity toward Zn²⁺ ions. Addition of sodium salt to the metal solution influenced copper removal positively, but inhibited zinc removal. Received: 3 January 2000 · Accepted: 27 June 2000     

Effect of Shale Reservoir Characteristics on Shale Oil Movability in the Lower Third Member of the Shahejie Formation,Zhanhua Sag

To reveal the effect of shale reservoir characteristics on the movability of shale oil and its action mechanism in the lower third member of the Shahejie Formation(Es3l), samples with different features were selected and analyzed using N2 adsorption, high-pressure mercury injection capillary pressure(MICP), nuclear magnetic resonance(NMR), high-speed centrifugation, and displacement image techniques. The results show that shale pore structure characteristics control shale oil movability directly. Movable oil saturation has a positive relationship with pore volume for radius > 2 μm, as larger pores often have higher movable oil saturation, indicating that movable oil is present in relatively larger pores. The main reasons for this are as follows. The relatively smaller pores often have oil-wetting properties because of organic matter, which has an unfavorable effect on the flow of oil, while the relatively larger pores are often wetted by water, which is helpful to shale oil movability. The rich surface provided by the relatively smaller pores is beneficial to the adsorption of immovable oil. Meanwhile, the relatively larger pores create significant pore volume for movable oil. Moreover, the larger pores often have good pore connectivity. Pores and fractures are interconnected to form a complex fracture network, which provides a good permeability channel for shale oil flow. The smaller pores are mostly distributed separately;thus, they are not conducive to the flow of shale oil. The mineral composition and fabric macroscopically affect the movability of shale oil. Calcite plays an active role in shale oil movability by increasing the brittleness of shale and is more likely to form micro-cracks under the same stress background. Clay does not utilize shale oil flow because of its large specific surface area and its block effect. The bedding structure increases the large-scale storage space and improves the connectivity of pores at different scales, which is conducive to the movability of shale oil.     

Uranyl and arsenate cosorption on aluminum oxide surface

In this study, we examined the effects of simultaneous adsorption of aqueous arsenate and uranyl onto aluminum oxide over a range of pH and concentration conditions. Arsenate was used as a chemical analog for phosphate, and offers advantages for characterization via X-ray absorption spectroscopy. By combining batch experiments, speciation calculations, X-ray absorption spectroscopy, and X-ray diffraction, we investigated the uptake behavior of uranyl, as well as the local and long-range structure of the final sorption products. In the presence of arsenate, uranyl sorption was greatly enhanced in the acidic pH range, and the amount of enhancement is positively correlated to the initial arsenate and uranyl concentrations. At pH 4-6, U L_III- and As K-edge EXAFS results suggest the formation of surface-sorbed uranyl and arsenate species as well as uranyl arsenate surface precipitate(s) that have a structure similar to trögerite. Uranyl polymeric species or oxyhydroxide precipitate(s) become more important with increasing pH values. Our results provide the basis for predictive models of the uptake of uranyl by aluminum oxide in the presence of arsenate and (by analogy) phosphate, which can be especially important for understanding phosphate-based uranium remediation systems.     

Removal of selected heavy metals from aqueous solutions using a solid by-product from the Jordanian oil shale refining

 The potential use of treated solid by-product of oil shale to treat aqueous solutions containing several heavy metals, i.e., Cd(II), Cu(II), Cr(III), Ni(III), Pb(II) and Zn(II), was explored. Different experimental approaches including equilibrium batch mode experiments and X-ray fluorescence (XRF) were used to explore the feasibility of this material as a cheap adsorbent for the removal of these heavy metals from predetermined solutions. Results indicate that the solid by-product of oil shale removes Cd(II), Cu(II), Ni(II), and Pb(II), from aqueous solutions by adsorption, but did not remove the other heavy metals investigated in this study. Received: 20 April 1998 · Accepted: 20 November 1998     

Geotechnical properties of combusted western oil shale

The engineering properties of solid waste produced by the combustion of Western oil shale are evaluated and discussed. Index properties and their variability, moisture—density relationships, shear strength, stress—strain characteristics, and hydraulic conductivity were evaluated in laboratory tests. Cementation caused by the formation of hydrous cements when combusted oil shale is exposed to water was found to be the most significant factor affecting its engineering properties. With increasing initial water content, shear strength increases and hydraulic conductivity decreases significantly, primarily because of cementation. Implications for the design of waste disposal embankments are discussed.     

Bridging arsenate surface complexes on the hematite (0 1 2) surface

The fate of the oxoanion arsenate in diverse systems is strongly affected by its adsorption on the surfaces of iron (oxyhydr)oxide minerals. Predicting this behavior in the environment requires an understanding of the mechanisms of arsenate adsorption. In this study, the binding site and adsorption geometry of arsenate on the hematite (0 1 2) surface is investigated. The structure and termination of the hematite (0 1 2)-water interface were determined by high resolution X-ray reflectivity, revealing that two distinct terminations exist in a roughly 3:1 proportion. The occurrence of multiple terminations appears to be a result of sample preparation, and is not intrinsic to the hematite (0 1 2) surface. X-ray standing wave (XSW) measurements were used to determine the registry of adsorbed arsenate to the hematite structure, and thus the binding site and geometry of the resulting surface complex. Arsenate forms a bridging bidentate complex on two adjacent singly coordinated oxygen groups on each of the two distinct terminations present at the hematite surface. Although this geometry is consistent with that seen in past studies, the derived As-Fe distances are longer, the result of the topology of the FeO₆ octahedra on the (0 1 2) surface. As EXAFS-derived As-Fe distances are often used to determine the adsorption mechanism in environmental samples (e.g., mine tailings, contaminated sediments), this demonstrates the importance of considering the possible sorbent surface structures and arrangements of adsorbates when interpreting such data.As multiple functional groups are present and multiple binding geometries are possible on the hematite (0 1 2) surface, the XSW data suggest that formation of bridging bidentate surface complexes on singly coordinated oxygen sites is the preferred adsorption mechanism on this and most other hematite surfaces (provided those surfaces contain adjacent singly coordinated oxygen groups). These measurements also constrain the likely reaction stoichiometry, with only the protonation state of the surface complex undetermined. Although bridging bidentate inner-sphere surface complexes comprised the majority of the adsorbed arsenate present on the hematite (0 1 2) surface, there is an additional population of sorbed arsenate species that could not be characterized by the XSW measurements. These species are likely more disordered, and thus more weakly bound, than the bridging bidentate complexes, and may play a role in determining the fate, transport, and bioavailability of arsenate in the environment. Finally, the possibility of obtaining species-specific XSW measurements by tuning the incident beam energy to specific features in a XANES spectrum is described.     

The Norfolk oil-shale rush, 1916–1921

Oil shales are one of those naturally occurring resources that require so much costly treatment to convert them into useful products that they are only worked on a large scale at times when the availability of cheaper alternatives is restricted. The need to find secure UK supplies during the First World War led to attempts to exploit the potential oil reserves contained in the more organic-rich parts of the Jurassic Kimmeridge Clay Formation. The most costly of these was that carried out in west Norfolk by the privately funded English Oilfields Ltd. (EOL) in 1916–1921 under the direction of Dr. William Forbes-Leslie M.D., FGS. Extensive treatment works were constructed on the Kimmeridge Clay outcrop at Setchey, five miles south of King's Lynn, but very little oil shale was worked or retorted. An extensive drilling programme claimed to have proved sulphur-free oil shales, hundreds of millions of tons of free oil, a 21-m thick seam of natural paraffin wax (ozokerite), and an abundance of metalliferous minerals. At its peak in 1920, the stock-market value of the company was several hundred million pounds at present-day prices. The turning point came in 1921 when samples of shale oil from Setchey and the products derived from them by distillation were shown to have no commercial value because of their high sulphur contents. There was, at that time, no commercially viable method of reducing the sulphur contents to an acceptable level. The free oil, ozokerite and metalliferous minerals only existed in the reports to the shareholders.     

柳树河油页岩的热解特征及动力学

利用岩石-热解评价仪研究了200～600 ℃不同升温速率（10、15、20、25、30 ℃/min）下柳树河盆地油页岩热解生烃特征,利用Friedman法和Sestak反应机制,求出了油页岩的反应活化能和反应函数,建立了热解动力学模型,可用于计算热解生烃率和达到某一转化率所需要的时间。研究发现,油页岩的反应活化能并不是一个定值,随着反应温度的增加逐渐增大。这是因为油页岩热解是一个极其复杂的多步反应过程,在不同的温度区间内具有不同的反应机理。     

Sorption and desorption of arsenate and arsenite on calcite

The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were and . The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated retardation factors for arsenate in carbonate aquifers range from 25 to 200.     

松南上白垩统青山口组一段不同赋存状态页岩油定量评价

松辽盆地南部青山口组一段页岩油资源丰富,多口井试油获得工业及高产油流,具有较大的勘探开发潜力。本文以青山口组一段下段为研究对象,以页岩油赋存状态为切入点,重点针对研究区页岩油富集优质岩相,即高有机质薄片状页岩和中有机质纹层状页岩中溶胀油、吸附油以及游离油量进行定量评价,揭示页岩油在地下页岩层系储层中的赋存特征。青山口组一段页岩油主要以干酪根溶胀态、干酪根吸附态、有机质孔隙游离态、无机矿物吸附态及无机孔隙游离态等5种赋存形式存在于页岩层系储层中。其中：高有机质薄片状页岩中页岩油赋存状态以干酪根溶胀油、干酪根吸附油和有机质孔隙游离油等有机赋存油为主,有机赋存油量可高达253.0 mg/g TOC,以TY1井页岩油赋存量最大,其次为CY8井,H238井页岩油量最低;中有机质纹层状页岩中页岩油赋存状态以无机矿物吸附油、无机孔隙游离油等无机赋存油为主,可达167.0 mg/g TOC,CY8井页岩油赋存量最大,H258井次之,H238井页岩油量最低。TY1井、CY8井位于半深湖—深湖区,发育大套泥页岩;H238井位于三角洲外前缘,离物源区较近,导致其页岩油赋存量明显低于半深湖—深湖区。因此,沉积环境是导致不同工区页岩油赋存量差异的主要原因。