Vertical variability of PCE sorption in the lacustrine clays of Mexico City

 A surficial clay aquitard extends through the urban area where Mexico City is located. It has been assumed to function as a protective layer to the underlying aquifer that provides 42 m³/s out of 63 m³/s of water used by 18 million inhabitants. To provide such protection, the aquitard must be impermeable to water flow and, ideally, have a significant capacity to sorb contaminants. The latter aspect was addressed, studying the vertical variability of sorption of perchloroethylene (PCE), a widely used organic compound considered to pose health risks in groundwater. Batch sorption tests were used and the clay-rich strata in the depth interval from 8 to 75 m were studied. The results suggest that sorption depends mainly on the fraction of organic carbon (f_oc) present in the clayey materials. The sorption data were fit to the linear and Freundlich models; many strata could be fit well by either model, while some strata were distinctly non-linear. The linear isotherms showed a mean value of 32.8 ml/g, and the Freundlich isotherm 96.6 ml/g, confirming that the clay-rich media have significant sorption capacity for PCE. From the environmental perspective the clay-rich materials are serving as protection to the groundwater system. Received: 2 November 1998 · Accepted: 15 February 1999     

Experimental investigation of cephapirin adsorption to quartz filter sands and dune sands

Batch experiments were performed to investigate cephapirin (a widely used veterinary antibiotic) adsorption on various size sands of low total organic carbon content (0.08–0.36 wt%). In the aqueous concentration range investigated (11–112 μmol/L cephapirin), adsorption to nearly pure quartz filter sands (0.50–3.35 mm diameter) is low. Isotherms are S-shaped and most display a region of minimum adsorption, where decreased adsorption occurs with increasing solution concentration, followed by increased adsorption at higher concentrations. Cephapirin adsorption to quartz-rich, feldspar-bearing dune sands (0.06–0.35 mm diameter), and the smallest quartz filter sand investigated (0.43–0.50 mm), can be described by linear sorption isotherms over the range of concentrations investigated. Distribution coefficients (K _d) range from 0.94 to 3.45 L/kg. No systematic relationship exists between grain size and amount of adsorption for any of the sands investigated. Cephapirin adsorption is positively correlated to the feldspar ratio (K-feldspar/(albite + Ca-plagioclase). Feldspar-ratio normalization of distribution coefficients was more effective than organic carbon normalization at reducing variability of K _d values in the dune sands investigated.     

Organic fraction of the total carbon burial flux deduced from carbon isotopes across the Permo-Triassic boundary at Meishan,Zhejiang Province,China

By combining the carbon cycle model with the records of carbonate and organic (kerogen) carbon isotope, this paper presents the calculation of the fraction of organic carbon burial (f _org) of beds 23–40 at the global boundary stratotype section and point (GSSP) of the Permian-Triassic boundary at Meishan, Zhejiang Province. The resulting calculation produces two episodes of f _org maxima observed to occur at beds 23–24 and 27–29, which respectively corresponds to the two episodic anoxic events indicated by the flourish of green sulfur bacteria. Two episodic f _org minima occurred at beds 25–26 and 32–34, generally coincident with the flourish of cyanobacteria (bed 26 and upper part of beds 29 to 34) as shown by the high value of 2-melthyhopnoanes. It appears that the f _org is related to the redox conditions, with greater f _org values observed under the reductive condition. The relationship between f _org and the total organic carbon (TOC) content was complex. The f _org value was low at some beds with a high TOC content (such as bed 26), while high observed at some beds with a low TOC content (e.g. bed 27). This association infers the important contribution of primary productivity to the TOC content. The original organic burial could be thus calculated through the configuration of the function of the primary productivity and f _org, which can be used to correct the residual TOC measured today. This investigation indicates that compiling the organic-inorganic carbon isotopes with the carbon cycle model favors to understand the fraction of organic carbon burial, providing information for the reconstruction of the coupling among biota, environments and organic burial. Journal of China University of Geosciences, 2007, 32(6): 767–773 [译自: 地球科学—中国地质大学学报]     

Determination of retardation coefficients of sulfolane and thiolane on soils by Kow–Koc and solubility parameter, batch and column experiments

 Retardation parameters (R_f) for sulfolane and thioalne were estimated using reference values and experimentally as they were mainly observed at an aquifer underneath a waste disposal site near Brisbane, Australia. Three soil aquifer materials e.g. clay, silty clay and sand were used as sorbents. At first, R_f was obtained employing K_oc–K_ow and solubility parameter, respectively, while experimental coefficients were determined from both batch and flow-through column tests. Additionally, R_f was observed at a single- and bi-solute system through the column test. There was not found any significant difference in R_f between K_oc–K_ow and solubility parameters, but the retardation coefficient was significantly dependent on organic carbon content for solubility parameter. In contrast, using K_oc–K_ow, the coefficient correspondingly varied with an amount of clay content contained in each soil. In the same manner, the batch-determined parameters were more subject to clay content. On the other hand, the column-determined parameters can be comparable with the desk-derived values. In a bi-solute system, they did not influence each other concerning retardation coefficients while they flew though the column simultaneously. It was concluded that there was a large discrepancy in retardation coefficient of batch- against both reference-oriented estimation and column-determined values. Received: 20 August 1998 · Accepted: 17 May 1999     

Sorption characteristics of ethyl <Emphasis Type="Italic">tert</Emphasis>-butyl ether to Chinese reference soils

As a gasoline additive, ethyl tert-butyl ether (ETBE) has great market potential and its utilization might cause groundwater contamination problem. However, little research has been done on its sorption in soil. In this study, the sorption characteristics of ETBE to Chinese reference soils were studied in batch experiments. The results showed that the ETBE sorption to six soils can be described by linear sorption isotherm. The temperature influences the sorption process of ETBE to soils. The negative sorption enthalpy (ΔH < 0) indicated that the sorption process was exothermic. Furthermore, ΔH is in a range from −8 to −32 kJ/mol. This showed that van der Waals forces and other specific interactions happened simultaneously in the sorption process. With the increasing ionic strength, content of ETBE sorption to all soils decreased, which is probably also an indication of other sorption mechanisms besides ETBE partitioning into soil organic carbon.     

Phosphorus transport in shallow groundwater in peri-urban Kampala, Uganda: results from field and laboratory measurements

To understand Phosphorus (P) sources and transport processes in the subsurface in Bwaise III Parish, Kampala, P attenuation and adsorption capacities of soils were studied in situ and from laboratory measurements. Relationships between sorption parameters and soil matrix properties, rates and mechanism of the adsorption process and soil P fractions were also investigated. P was generally higher in the wet than the dry season, but for both seasons, the maximum was 5 mgP/l. P transport mechanisms appeared to be a combination of adsorption, precipitation, leaching from the soil media and by colloids with the latter two playing an important role in the wet season. The sorption process comprised two phases with the first stage rate constants being about fourfold those of the second stage. The Langmuir isotherm described the sorption data well (R ² ≥ 0.95) with the second soil layer exhibiting the highest sorption maximum (C _max) (average value 0.6 ± 0.17 mgP/gDW). The best prediction of C _max had organic carbon, Ca, available P and soil pH. Residual P consisting mostly of organics was the main fraction in all the layers followed by inorganic HCl-P and NaOH-P in the top and middle layers, respectively. Loosely bound P (NH₄Cl-P) was the least fraction (<0.4% of total P) in all layers indicating the high binding capacity of P by the soils. The study results suggest that P dynamics is related to Ca, Fe and organic carbon content of the soils.     

Vertical transport of polycyclic aromatic hydrocarbons in different particle-size fractions of sandy soils

Vertical transport of selected polycyclic aromatic hydrocarbons (PAHs) in different particle-size fractions of sandy soils was investigated by simulation experiments in soil columns. Tested soil samples were fractionized into three particle-sizes including sand, coarse silt and fine silt (2,000–50, 50–20 and <20 μm). Rainfall simulations were conducted in artificially PAHs contaminated soil columns with 30 cm length and 5 cm diameter in 40 days. PAHs were extracted from soil samples and determined by high performance liquid chromatography (HPLC). Results showed that the residue level of PAHs in fine silt fraction reached 35.85 mg/kg, which was significantly higher than those in sand and coarse silt fraction (16.28 and 11.80 mg/kg, respectively), probably because PAHs in macroporous fractions were prone to volatilize or degrade compared with that in microporous fractions. Linear relationship between the residue levels of individual PAH (R _PAHs) and the value of partition coefficient (log K _oc) was regressed as R _PAHs = 1.55 × log K _oc − 5.86, R ² = 0.91, n = 9. These results indicated that vertical transport of the mixed PAHs in soils were controlled both by the nature of PAHs (i.e. log K _oc, molecular weight), soil particle size and soil organic contents, which could influence the transport of PAHs.     

Methane and carbon dioxide sorption on a set of coals from India

Complete sorption isotherm characteristics of methane and CO₂ were studied on fourteen sub-bituminous to high-volatile bituminous Indian Gondwana coals. The mean vitrinite reflectance values of the coal samples are within the range of 0.64% to 1.30% with varying maceral composition. All isotherms were conducted at 30 °C on dry, powdered coal samples up to a maximum experimental pressure of ~ 7.8 MPa and 5.8 MPa for methane and CO₂, respectively.The nature of the isotherms varied widely within the experimental pressure range with some of the samples remained under-saturated while the others attained saturation. The CO₂ to methane adsorption ratios decreased with the increase in experimental pressure and the overall variation was between 4:1 and 1.5:1 for most of the coals. For both methane and CO₂, the lower-ranked coal samples generally exhibited higher sorption affinity compared to the higher-ranked coals. However, sorption capacity indicates a U-shaped trend with rank. Significant hysteresis was observed between the ad/desorption isotherms for CO₂. However, with methane, hysteresis was either absent or insignificant. It was also observed that the coal maceral compositions had a significant impact on the sorption capacities for both methane and CO₂. Coals with higher vitrinite contents showed higher capacities while internite content indicated a negative impact on the sorption capacity.     

Halogen-bearing minerals in syenites and high-grade marbles of Dronning Maud Land,Antarctica: monitors of fluid compositional changes during late-magmatic fluid-rock interaction processes

Meta-sedimentary rocks including marbles and calcsilicates in Central Dronning Maud Land (CDML) in East Antarctica experienced a Pan-African granulite facies metamorphism with peak metamorphic conditions around 830 ± 20 °C at 6.8 ± 0.5 kbar which was accompanied by the post-kinematic intrusion of huge amounts of syenitic (charnockitic) magmas at 4.5 ± 0.7 kbar. The marbles and calcsilicates may represent meta-evaporites as indicated by the occurrence of metamorphic gypsum/anhydrite and Cl-rich scapolite that formed in the presence of saline fluids with X _NaCl in the range 0.15–0.27. The marbles and calcsilicates bear biotite, tremolite and/or hornblende and humite group minerals (clinohumite, chondrodite and humite) which are inferred to have crystallized at about 650 °C and 4.5 kbar. The syenitic intrusives contain late-magmatic biotite and amphibole (formed between 750 and 800 °C) as well as relictic magmatic fayalite, orthopyroxene and clinopyroxene. Two syenite and two calcsilicate samples contain fluorite. Corona textures in the marbles and calcsilicates suggest very low fluid-rock ratios during the formation of the retrograde (650 °C) assemblages. Biotite in all but two syenite samples crystallized at log(f _{H 2 O}/f _HF) ratios of 2.9 ± 0.4, while in the calcsilicates, both biotite and humite group minerals indicate generally higher log(f _{H 2 O}/f _HF) values of up to 5.2. A few samples, though, overlap with the syenite values. Log(f _{H 2 O}/f _HCl) derived from biotite covers the range 0.5–2.6 in all rock types. Within a single sample, the calculated values for both parameters vary typically by 0.1 to 0.8 log units. Water and halogen acid fugacities calculated from biotite-olivine/orthopyroxene-feldspar-quartz equilibria and the above fugacity ratios are 1510–2790 bars for H₂O, 1.3–5.3 bars for HF and 7–600 bars for HCl. The results are interpreted to reflect the reaction of relatively homogeneous magmatic fluids [in terms of log(f _{H 2 O} /f _HF)] derived from the late-magmatic stages of the syenites with both earlier crystallized, still hotter parts of the syenites and with adjacent country rocks during down-temperature fluid flow. Fluorine is successively removed from the fluid and incorporated into F-bearing minerals (close to the syenite into metamorphic fluorite). In the course of this process log(f _{H 2 O} /f _HF) increases significantly. Chlorine preferably partitions into the fluid and hence log(f _{H 2 O} /f _HCl) does not change markedly during fluid-rock interaction. Received: 28 November 1997 / Accepted: 27 April 1998     

Standard thermodynamic data for Rhodochrosite from equilibrium decomposition curve

Hydrothermal equilibrium decomposition curve for MnCO₃⇌MnO + CO₂ in the total CO₂ pressure range of 100–1700 bars and temperature range of 500–800°C was studied. The standard thermodynamic data obtained are: ΔH⁰ _f= − 894.382 ± 0.74 kj/mol and ΔG⁰ _f = − 822.170 ± 0.74 kj/mol. These values are more negative than the reported calorimetric data.     

Relationships among geochemical indices of coal and carbonaceous materials and implication for hydrocarbon potential evaluation

A worldwide dataset of organic material from 553 samples belonging to coal and carbonaceous materials was used to analyze the evolution of hydrogen index (HI) and bitumen index (BI) with increasing thermal maturity. Basic statistical analyses were applied to detect the boundary lines of HI_max and BI_max in delineating the upper and lower limits of the HI and BI bands for the majority of samples. In addition, cross-plots of HI or BI versus maturity (Ro% and T _max) also provide criteria for defining the HI_max and BI_max boundary lines. The constructed HI and BI bands are broad at low maturities and become narrower with increasing thermal maturities. The petroleum generation potential is completely exhausted at the vitrinite reflectance of 2.0–2.2% or T _max of 510–520°C. An increase in HI implies extra petroleum generation which was related to changes in structure of organic materials. A declining BI means that the oil expulsion window starts to occur at the vitrinite reflectance range of 0.75–1.05%. The petroleum potential can be divided into four different areas based on the cross-plot of HI versus Ro%. The highest petroleum potential area is located in section II with Ro = 0.6–1.0% and HI > 100. The oil generation potential is rapidly exhausted at section III with Ro > 1.0%. This result is also in accordance with the result of curve regression of HI versus Ro% based on 80 samples with Ro = 1.02–3.43% (R ² = 0.72). Overall, the total oil window can be extended up to Ro = ~1.25–1.95%. Finally, in the cross-plots of S1 versus S2, shale or C-shale exhibits a higher and slowly decreased slope, compared with a lower and then sharply increased slope of coal samples, which is attributable to their compositional difference in organic material.     

Single and binary adsorption of lead and cadmium ions from aqueous solution using the clay mineral beidellite

Beidellite, a low-cost, locally available and natural mineral was used as an adsorbent for the removal of lead and cadmium ions from aqueous solutions in batch experiments. The kinetics of adsorption process was tested for the pseudo first-order, pseudo second-order reaction and intra-particle diffusion models. The rate constants of adsorption for all these kinetic models were calculated. Comparison amongst the models showed that the sorption kinetics was best described by the pseudo second-order model. Langmuir and Freundlich isotherm models were applied to the experimental equilibrium data for different temperatures. The adsorption capacities (Q°) of beidellite for lead and cadmium ions were calculated from the Langmuir isotherm. It was found that adsorption capacity was in the range of 83.3–86.9 for lead and 42–45.6 mg/g for cadmium at different temperatures. Thermodynamic studies showed that the metal uptake reaction by beidellite was endothermic in nature. Binary metal adsorption studies were also conducted to investigate the interactions and competitive effects in binary adsorption process. Based on the optimum parameters found, beidellite can be used as adsorbent for metal removal processes.     

Displacement behavior of CH4 adsorbed on coals by injecting pure CO2, N2, and CO2–N2 mixture

Gas adsorption isotherms of Akabira coals were established for pure carbon dioxide (CO₂), methane (CH₄), and nitrogen (N₂). Experimental data fit well into the Langmuir model. The ratio of sorption capacity of CO₂, CH₄, and N₂ is 8.5:3.5:1 at a lower pressure (1.2 MPa) regime and becomes 5.5:2:1 when gas pressure increases to 6.0 MPa. The difference in sorption capacity of these three gases is explained by differences in the density of the three gases with increasing pressure. A coal–methane system partially saturated with CH₄ at 2.4 MPa adsorption pressure was experimentally studied. Desorption behavior of CH₄ by injecting pure CO₂ (at 3.0, 4.0, 5.0, and 6.0 MPa), and by injecting the CO₂–N₂ mixture and pure N₂ (at 3.0 and 6.0 MPa) were evaluated. Results indicate that the preferential sorption property of coal for CO₂ is significantly higher than that for CH₄ or N₂. CO₂ injection can displace almost all of the CH₄ adsorbed on coal. When modeling the CH₄–CO₂ binary and CH₂–CO₂–N₂ ternary adsorption system by using the extended Langmuir (EL) equation, the EL model always over-predicted the sorbed CO₂ value with a lower error, while under-predicting the sorbed CH₄ with a higher error. A part of CO₂ may dissolve into the solid organic structure of coal, besides its competitive adsorption with other gases. According to this explanation, the EL coefficients of CO₂ in EL equation were revised. The revised EL model proved to be very accurate in predicting sorbed ratio of multi-component gases on coals.     

Experimental measurements of the graphite C−O equilibrium and CO2 fugacities at high temperature and pressure

Thef _{o 2} of the equilibrium between graphite and C−O fluid has been determined from 15–30 kbar and 1100–1400°C using a sliding redox sensor consisting of (Ni, Mn) O+Ni metal. The equilibrium composition of oxide coexisting with metal was approached from both directions in each experiment with convergence to within 1 mol% NiO. Since, in theP−T range of the experiments, C−O fluids are >90% CO₂ our measurements off _{o 2} translate into determinations of CO₂ fugacity with an uncertainty of ±0.1 log units. These new determinations of theP−T−f _{o 2} plane of GCO equilibrium are in excellent agreement with the mainly unreversed measurements of Ulmer and Luth (1991) using pure metal-metal oxide sensors and with the equation of state of Saxena and Fei (1987). Modified forms of the Redlich-Kwong (MRK) equation of state (Holloway 1977; Flowers 1979; Kerrick and Jacobs 1981) predict higher values off _{o 2} for the GCO equilibrium than determined experimentally. This implies that CO₂ is more compressible than the MRK predicts. Editorial responsibility: V. Trommsdorff     

Biogeochemistry of Major Redox Elements and Mercury in a Tropical Reservoir Lake (Petit Saut,French Guiana)

The hydroelectric reservoir of Petit Saut, French Guiana, was created in 1994–1995 by flooding 350 km² of tropical forest. When sampled in 1999, the lake exhibited a permanent stratification separating the 3–5 m thick, oxygenated epilimnion from the anoxic hypolimnion. The rate of anaerobic organic carbon mineralization below the oxycline was on the order of 1 μmol C m⁻² s⁻¹ and did not show a pronounced difference between wet and dry seasons. Methanogenesis accounted for 76–83% of anaerobic carbon mineralization, with lesser contributions of sulfate reduction and dissimilatory iron reduction. Upward mixing of reduced inorganic solutes explained 90% of the water column O ₂ demand during the dry season, while most O ₂ consumption during the wet season was coupled to aerobic respiration of organic matter synthesized in the surface waters. Inorganic mercury species represented 10–40% of total dissolved mercury in the epilimnion, but were of relatively minor importance (≤10%) in the anoxic portion of the water column. Net production of soluble organic mercury compounds in the flooded soils and anoxic water column did not vary significantly between wet and dry seasons. Methylmercury accounted for about 15% of total dissolved mercury below the oxycline. Its estimated net production rate, 0.04 mg m⁻² yr⁻¹, is of the same order of magnitude as values reported for contaminated lakes and flooded terrestrial ecosystems.     

Study of mango biomass (Mangifera indica L) as a cationic biosorbent

Unfertilizable fruiting buds of mango plant Mangifera Indica L, an agrowaste, is used as a biomass in this study. The efficacy of the biosorbent was tested for the removal of lead, copper, zinc and nickel metal ions using batch experiments in single and binary metal solution under controlled experimental conditions. It is found that metal sorption increases when the equilibrium metal concentration rises. At highest experimental solution concentration used (150 mg/L), the removal of metal ions were 82.76 % for lead, 76.60 % for copper, 63.35 % for zinc and 59.35 % for nickel while at lowest experimental solution concentration (25 mg/L), the removal of metal ions were 92.00% for lead, 86.84 % for copper, 83.96 % for zinc and 82.29 % for nickel. Biosorption equilibrium isotherms were plotted for metal uptake capacity (q) against residual metal concentrations (C_f) in solution. The q versus C_f sorption isotherm relationship was mathematically expressed by Langmuir and Freundlich models. The values of separation factor were between zero and one indicating favourable sorption for four tested metals on the biosorbent. The surface coverage values were approaching unity with increasing solution concentration indicating effectiveness of biosorbent under investigation. The non-living biomass of Mangifera indica L present comparable biosorption capacity for lead, copper, zinc and nickel metal ions with other types of biosorbent materials found in literature and is effective to remove metal ions from single metal solutions as well as in the presence of other co-ions with the main metal of solution.     

Biogeochemical characteristics of the lower Mississippi River, USA, during June 2003

During June 2003, a period of mid level discharge (17,400 m⁻³ s⁻¹), a parcel of water in the lower Mississippi River was sampled every 2 h during its 4-d transit from river km 362 near Baton Rouge to km 0 at Head of Passes, Louisiana, United States. Properties measured at the surface during each of the 48 stations were temperature, salinity, dissolved organic carbon (DOC), total dissolved nitrogen, dissolved macronutrients (NO₃+NO₂, PO₄, Si(OH)₄), chlorophylla (chla; three size fractions: < 5 μm, 5–20 μm, and > 20 μm) pigment composition by HPLC, total suspended matter (TSM), particulate organic carbon (POC), and particulate nitrogen (PN). Air-water CO₂ flux was calculated from surface water dissolved inorganic carbon and pH. During the 4 d transit, large particles appeared to be settling out of the surface water. Concentrations of chla containing particles > 20 μm declined 37%, TSM declined 43%, POC declined 42% and PN declined 57%. Concentrations of the smaller chla containing particles did not change suggesting only large particulate materials were settling. There was no measurable loss of dissolved NO₃, PO₄, or Si(OH)₄, consistent with the observation that chla did not increase during the 4-d transit. DOC declined slightly (3%). These data indicate there was little autotrophic or heterotrophic activity in the lower Mississippi River at this time, but the system was slightly net heterotrophic.     

Hydrothermal synthesis of pumpellyite–okhotskite series minerals

Summary ?Hydrothermal experiments to synthesize pumpellyite group minerals of the pumpellyite–okhotskite series and to investigate their stability have been carried out at 200, 300 and 400 MPa P _fluid and 250–500 °C by using cold-seal pressure vessels and solid buffers of MnO₂–Mn₂O₃, Cu₂O–CuO and Cu₂O–Cu buffer assemblages. Okhotskite and pumpellyite rich in the okhotskite component crystallized from an oxide mixture starting material of Ca₄MgMn³⁺ ₃Al₂Si₆O_24.5-oxide+excess H₂O at P _fluid of 200, 300 and 400 MPa and temperatures of 300 and 400 °C. However, a single phase of okhotskite was not produced, and associated piemontite, hausmannite, wollastonite, clinopyroxene, corundum, braunite–neltnerite solid solution and alleghanyite also formed. Mn-pumpellyite of the okhotskite–pumpellyite join occurs as aggregates of needle crystals, rounded grains or flaky crystals. Chemical compositions are variable and range from pumpellyite-(Mn²⁺) to okhotskite: 31–36 SiO₂, 13–21 Al₂O₃, 12–25 total Mn₂O₃, 0.6–4 MgO and 20–24 wt.% CaO. Reconnaissance experiments using a starting material of synthetic Ca₂Mn³⁺Al₂Si₃O₁₂(OH)-piemontite at 300 MPa and temperatures of 250, 300, 400 and 500 °C indicate that Mn-rich pumpellyite can crystallize from piemontite at lower temperatures than the stability field of piemontite. The Mn-rich pumpellyite was accompanied by garnet, wollastonite and alleghanyite. The chemical compositions of the Mn-pumpellyites are 32–36 SiO₂, 18–27 Al₂O₃, 8–18 total Mn₂O₃ and 20–23 wt.% CaO. This study shows that the stability fields of piemontite, piemontite+Mn-pumpellyite, and Mn-pumpellyite range in this order with decreasing temperature under high fO₂ conditions. The maximum stability temperature of Mn-rich pumpellyite lies between 400 and 500 °C at 200–400 MPa in high fO₂ conditions. Received March 3, 2000; revised version accepted December 28, 2001     

Methane and CO2 sorption and desorption measurements on dry Argonne premium coals: pure components and mixtures

Sorption and desorption behaviour of methane, carbon dioxide, and mixtures of the two gases has been studied on a set of well-characterised coals from the Argonne Premium Coal Programme. The coal samples cover a maturity range from 0.25% to 1.68% vitrinite reflectance. The maceral compositions were dominated by vitrinite (85% to 91%). Inertinite contents ranged from 8% to 11% and liptinite contents around 1% with one exception (Illinois coal, 5%). All sorption experiments were performed on powdered (−100 mesh), dry coal samples.Single component sorption/desorption measurements were carried out at 22 °C up to final pressures around 51 bar (5.1 MPa) for CO₂ (subcritical state) and 110 bar (11 MPa) for methane.The ratios of the final sorption capacities for pure CO₂ and methane (in molar units) on the five coal samples vary between 1.15 and 3.16. The lowest ratio (1.15) was found for the North Dakota Beulah-Zap lignite (VR_r=0.25%) and the highest ratios (2.7 and 3.16) were encountered for the low-rank coals (VR_r 0.32% and 0.48%) while the ratio decreases to 1.6–1.7 for the highest rank coals in this series.Desorption isotherms for CH₄ and CO₂ were measured immediately after the corresponding sorption isotherms. They generally lie above the sorption isotherms. The degree of hysteresis, i.e. deviation of sorption and desorption isotherms, varies and shows no dependence on coal rank.Adsorption tests with CH₄/CO₂ mixtures were conducted to study the degree of preferential sorption of these two gases on coals of different rank. These experiments were performed on dry coals at 45 °C and pressures up to 180 bar (18 MPa). For the highest rank samples of this sequence preferential sorption behaviour was “as expected”, i.e. preferential adsorption of CO₂ and preferential desorption of CH₄ were observed. For the low rank samples, however, preferential adsorption of CH₄ was found in the low pressure range and preferential desorption of CO₂ over the entire pressure range.Follow-up tests for single gas CO₂ sorption measurements consistently showed a significant increase in sorption capacity for re-runs on the same sample. This phenomenon could be due to extraction of volatile coal components by CO₂ in the first experiment. Reproducibility tests with methane and CO₂ using fresh sample material in each experiment did not show this effect.     

Relationships between carbon isotope evolution and variation of microbes during the Permian–Triassic transition at Meishan Section, South China

This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ¹³C_carb-kero = δ ¹³C_carb − δ ¹³C_kero) and the difference between carbonate and n-C₁₉ alkane compound-specific carbon isotopes (Δ¹³C_carb-n-C19 = δ ¹³C_carb − δ ¹³C _n-C19) during the Permian–Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23–25 and 26–29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ¹³C_carb-kero and Δ¹³C_carb-n-C19, which are mainly affected by CO₂-fixing enzyme and pCO₂, oscillated frequently during the Permian–Triassic transition. Both the variations of Δ¹³C_carb-n-C19 and Δ¹³C_carb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ¹³C_carb-n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ¹³C_carb-n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian–Triassic crisis.