Physical properties of selected block Argonne Premium bituminous coal related to CO2, CH4, and N2 adsorption

CO₂, CH₄, and N₂ adsorption and gas-induced swelling were quantified for block Blind Canyon, Pittsburgh #8 and Pocahontas Argonne Premium coals that were dried and structurally relaxed at 75 °C in vacuum. Strain measurements were made perpendicular and parallel to the bedding plane on ~ 7 × 7 × 7 mm³ coal blocks and gravimetric sorption measurements were obtained simultaneously on companion coal blocks exposed to the same gaseous environment. The adsorption amount and strain were determined after equilibration at P  ≤ 1.8 MPa. There is a strong non-linear correlation between strain and the quantity of gas adsorbed and the results for all gases and coals studied follow a common pattern. The dependence of the coal matrix shrinkage/swelling coefficient (C_gc) on the type and quantity of gas adsorbed is seen by plotting the ratio between the strain and the adsorbate concentration against the adsorbate concentration. In general, C_gc increases with increasing adsorbate concentration over the range of ~ 0.1 to 1.4 mmol/g. Results from the dried block coals are compared to CO₂ experiments using native coals with an inherent level of moisture as received. The amount of CO₂ adsorbed using native coals (assuming no displacement of H₂O by CO₂) is significantly less than the dried coals. The gas-induced strain (S) and adsorption amount (M) were measured as a function of time following step changes in CO₂, CH₄, and N₂ pressure from vacuum to 1.8 MPa. An empirical diffusion equation was applied to the kinetic data to obtain the exponent (n) for time dependence for each experiment. The data for all coals were pooled and the exponent (n) evaluated using an ANOVA statistical analysis method. Values for (n) near 0.5 were found to be independent on the coal, the gas or type of measurement (e.g., parallel strain, perpendicular strain, and gas uptake). These data support the use of a Fickian diffusion model framework for kinetic analysis. The kinetic constant k was determined using a unipore diffusion model for each experiment and the data were pooled for ANOVA analysis. For dry coal, statistically significant differences for k were found for the gases (CO₂ > N₂ > CH₄) and coals (Pocahontas >Blind Canyon > Pittsburgh #8) but not for the method of the kinetic measurement (e.g., strain or gas uptake). For Blind Canyon and Pittsburgh #8 coal, the rate of CO₂ adsorption and gas-induced strain for dry coal was significantly greater than that of the corresponding native coal. For Pocahontas coal the rates of CO₂ adsorption and gas-induced strain for dry and native coal were indistinguishable and may be related to its low native moisture and minimal amount of created porosity upon drying.     

The measurement of coal porosity with different gases

Sorption processes can be used to study different characteristics of coal properties, such as gas content (coalbed methane potential of a deposit), gas diffusion, porosity, internal surface area, etc. Coal microstructure (porosity system) is relevant for gas flow behaviour in coal and, consequently, directly influences gas recovery from the coalbed.This paper addresses the determination of coal porosity (namely micro- and macroporosity) in relation to the molecular size of different gases. Experiments entailed a sorption process, which includes the direct method of determining the “void volume” of samples using different gases (helium, nitrogen, carbon dioxide, and methane). Because gas behaviour depends on pressure and temperature conditions, it is critical, in each case, to know the gas characteristics, especially the compressibility factor.The experimental conditions of the sorption process were as follows: temperature in the bath 35 °C; sample with moisture equal to or greater than the moisture-holding capacity (MHC), particle size of sample less than 212 μm, and mass ca. 100 g.The present investigation was designed to confirm that when performing measurements of the coal void volume with helium and nitrogen, there are only small and insignificant changes in the volume determinations. Inducing great shrinkage and swelling effects in the coal molecular structure, carbon dioxide leads to “abnormal” negative values in coal void volume calculations, since the rate of sorbed and free gas is very high. In fact, when in contact with the coal structure, carbon dioxide is so strongly retained that the sorbed gas volume is much higher than the free gas volume. However, shrinkage and swelling effects in coal structure induced by carbon dioxide are fully reversible. Methane also induces shrinkage and swelling when in contact with coal molecular structure, but these effects, although smaller than those induced by carbon dioxide, are irreversible and increase the coal volume.     

Three-dimensional carbon dioxide-induced strain distribution within a confined bituminous coal

Sequestration of carbon dioxide in unmineable coal seams is an option to reduce carbon dioxide emissions. It is well known that the interaction of carbon dioxide with unconfined coal induces swelling. This paper contributes three-dimensional strain distribution in confined coal at microstructural level using high-resolution X-ray computerized tomography data and image analysis. Swelling and compression/compaction of regions in the coal matrix occurs with CO₂ uptake. Normal strain varies between ? 1.15% and 0.93%, ? 3.11% and 0.94%, ? 0.43% and 0.30% along x, y and z axes respectively. Volumetric strain varies between ? 4.25% and 1.25%. The positive strains reported are consistent with typical range for unconstrained swelling. However, the average volumetric strains value (? 0.34%) reflect overall volume reduction. Overall swelling is apparently influenced by the confining stresses. The magnitudes of normal strains are heterogeneous and anisotropic. The swelling vs. compression/compaction observed after CO₂ uptake is localized and likely lithotype dependant.     

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.     

煤基质中甲烷扩散特征及其对气井产能的影响

扩散是煤层甲烷运移的关键环节之一,而目前有关煤层中甲烷扩散特征的认识并不充分.以沁水盆地南部高煤阶煤层气藏为例,应用微纳渗流力学理论分析了煤基质中气体扩散模式及定量表征参数;应用Simed软件开展了扩散性能对不同煤体结构煤层气排采规律的影响数值研究.结果表明:煤层甲烷的扩散受化学势梯度的驱动,产气过程中体相扩散、努森扩散和构型扩散模式并存且呈动态变化;甲烷扩散性能受气体温度、压力、气体种类、水分以及基质孔隙结构共同影响,基质孔隙吸附甲烷会改变微孔孔径并影响扩散路径的空间形态;煤基质中甲烷的扩散是非热力平衡过程,扩散系数是吸附量的函数.基于拟稳态扩散的数值研究表明,扩散性能强弱对于长期累计产气量几乎没有影响,而对短期产气速率具有较大的影响;扩散性能弱的,产气速率峰值较低,但峰值之后的一段时间内产气速率相对较高;与高渗煤层相比,低渗构造煤层的产气速率对吸附时间常数更敏感.      

Chemical and physical properties of iron hydroxide precipitates associated with passively treated coal mine drainage in the Bituminous Region of Pennsylvania and Maryland

Changes in precipitate mineralogy, morphology, and major and trace element concentrations and associations throughout 5 coal mine drainage (CMD) remediation systems treating discharges of varying chemistries were investigated in order to determine the factors that influence the characteristics of precipitates formed in passive systems. The 5 passive treatment systems sampled in this study are located in the bituminous coal fields of western Pennsylvania and northern Maryland, and treat discharges from Pennsylvanian age coals. The precipitates are dominantly (>70%) goethite. Crystallinity varies throughout an individual system, and lower crystallinity is associated with enhanced sorption of trace metals. Degree of crystallinity (and subsequently morphology and trace metal associations) is a function of the treatment system and how rapidly Fe(II) is oxidized, forms precipitates, aggregates and settles. Precipitates formed earlier in the passive treatment systems tend to have the highest crystallinity and the lowest concentrations of trace metal cations. High surface area and cation vacancies within the goethite structure enable sorption and incorporation of metals from coal mine drainage-polluted waters. Sorption affinities follow the order of Zn > Co ≈ Ni > Mn. Cobalt and Ni are preferentially sorbed to Mn oxide phases when these phases are present. As pH increases in the individual CMD treatment systems toward the pH_pzc of goethite, As sorption decreases and transition metal (Co, Mn, Ni and Zn) sorption increases. Sulfate, Na and Fe(II) concentrations may all influence the sorption of trace metals to the Fe hydroxide surface. Results of this study have implications not only for solids disposal and resource recovery but also for the optimization of passive CMD treatment systems.     

Sorption of monoaromatic compounds to heated and unheated coals,humic acid,and biochar: Implication for using combustion method to quantify sorption contribution of carbonaceous geosorbents in soil

Batch sorption isotherms of two nonpolar compounds (1,3-dichlorobenzene and 1,3,5-trichlorobenzene) and two polar compounds (1,3-dinitrobenzene and 1,3,5-trinitrobenzene) to heated (at 375 °C for 24 h) and unheated coals (lignite and anthracite) were compared with those to a soil humic acid and a maize stalk derived biochar. For all test compounds, unheated lignite and anthracite exhibited much stronger sorption than humic substances (the organic carbon-normalized distribution coefficient was up to 2–3 orders of magnitude larger), but lower sorption than biochar. This sorption trend is consistent with the degree of sorbent condensation (biochar > coal > humic acid). The results indicate that sorption of the test sorbates (regardless of the difference in polarity) to soils would be dominated by carbonaceous geosorbents. Notably, the organic carbon contents of the coals were pronouncedly lowered by the heat treatment, from 47.4% to 7.3% for lignite, and from 80.1% to 58.1% for anthracite. Moreover, the heat treatment markedly decreased organic carbon-normalized distribution coefficient to coals (up to one order of magnitude), attributable to the decreased hydrophobicity of sorbents due to increased O-containing groups from oxidation. An important implication is that heat treatment, which is commonly used to quantify the content of carbonaceous geosorbents in soil and sediment, may cause significant underestimation of sorption contribution of carbonaceous geosorbents due to the combined effect of reduced organic carbon content and decreased hydrophobicity of less graphitized carbonaceous geosorbents (coals). This was illustrated using a widely adopted dual-component model that combines linear partition to humic substances (represented by humic acid) and nonlinear adsorption on condensed geosorbents (represented by biochar and coal).     

Modeling of Cs+ diffusion and retention in the DI-A2 experiment (Mont Terri). Uncertainties in sorption and diffusion parameters

In the DI-A2 experiment several non-reactive and reactive tracers were injected as a pulse in a packed-off borehole in the Opalinus Clay. Unlike the previous DI-A1 test, the design of the Teflon filter in the injection borehole forced the water to flow through the filter and the open space between the filter and the borehole wall (the filter itself did not act as a diffusion barrier between the circulating solution and the rock). The decrease in tracer concentration in the liquid phase was monitored during a period of a year. Afterwards, the borehole section was overcored and the tracer profiles in the rock were analyzed. A main interest of this experiment was to understand the chemical behavior of sorbing tracers: Cs⁺ (stable), ⁸⁵Sr²⁺, ⁶⁰Co²⁺ and Eu³⁺ (stable). The complete dataset (except for Eu³⁺ because of strong sorption to experimental equipment) was analyzed in a previous study with a 2D diffusion–reaction model and the derived diffusion and sorption parameters were compared with laboratory data. As in DI-A1, a difference by a factor of about 2 for sorption (magnitude of the Freundlich isotherm) was obtained between in situ and laboratory batch sorption experiments.Recent experimental and modeling studies have shown equivalent Cs⁺ sorption on intact and disaggregated Opalinus Clay samples. In view of these developments, new modeling of Cs⁺ diffusion and retention in the DI-A2 experiment has been performed using CrunchFlow. The calculations include transport by diffusion and a multisite cation exchange model to account for the retention of Cs⁺. The new results show that upscaling of Cs⁺ sorption from laboratory to field is no longer required. However, a difference in sorption by a factor of about 2 is still explained by the use of different versions of the same cation exchange model (a small difference in the selectivity coefficient for one type of site). This uncertainty in sorption leads to an uncertainty in the effective diffusion coefficient (D_e) for Cs⁺, also by a factor of 2 (2–4 × 10⁻¹⁰ m²/s). Clearly, the values of D_e obtained are correlated with the strength of sorption in the model, with stronger sorption leading to larger D_e values. Discrimination between the two versions of the exchange model is not possible when using only the results of the in situ test. Additionally, during early times (t < 10 days) the drop in Cs⁺ concentration in the circulation system is slower than expected. Due to the experimental setup, this slow decrease in concentration cannot be caused by the filter in the contact between borehole and rock. Poor mixing in the circulation system could explain this effect.     

水浸干燥后煤的孔隙结构及瓦斯吸附特性变化规律

在富含水煤系或水力措施后的煤层中,受水溶液的浸泡,煤的孔隙结构及吸附特性发生改变,为了深入研究其变化规律,在实验室利用蒸馏水对2种不同变质程度煤样进行了长时间(60d)浸泡,采用低温N2吸附实验和CO2吸附实验测试水浸前后煤样的孔隙结构变化规律,采用高压容量法测试水浸前后煤样的瓦斯吸附特性.结果表明,水浸干燥后煤体孔容...     

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH₄) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH₄ pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R_o. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R_o.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P_L) and maximum sorption capacity (Γ_max). The lowest maturity sample (%R_o = 0.56) displayed a Langmuir pressure (P_L) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R_o > 2.01) sample at 50 °C.The value of the Langmuir pressure (P_L) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH₄ adsorption on organic rich shales were determined based on the experimental CH₄ isotherms. For the adsorption of CH₄ on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs⁰) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.     

In situ investigations and reactive transport modelling of cement paste/argillite interactions in a saturated context and outside an excavated disturbed zone

The interactions between cementitious materials and a clayey deep formation were investigated by studying the specific in situ context of the Tournemire Underground Research Laboratory (URL) of the French Institute for Radioprotection and Nuclear Safety and by reactive transport modelling using the HYTEC code. The study forms part of the safety assessment framework for the deep geological disposal of high to intermediate level long-lived radioactive waste. The in situ context investigated in the Tournemire URL corresponds to an engineered cemented borehole crosscutting the Toarcian argillite formation. The argillite/CEM II cement paste contacts have been in place over 18 a and were sampled in a saturated context outside the excavated disturbed zone (EDZ). Studies of the mineralogy (XRD, carbonatometry, SEM and TEM), petrophysical properties (BET) and geochemistry (TOC, Sr contents, C, O and Sr isotopes, EDS analyses) were carried out both on the argillite and on the cement paste in contact. Alteration of the cement paste is clearly expressed by decalcification and the opening of macroporosity. These modifications are mainly due to the dissolution of portlandite. The neoformation of C–S–H phases was identified in the first few micrometre next to the argillite interface, along with secondary carbonates at the outermost contact. Geochemical measurements argue for the introduction of a sedimentary fluid into the macroporosity of the cement paste to explain the formation of part of these secondary phases. This hypothesis is considered and tested using the HYTEC code, which indicates that such transport could have occurred near the argillite/cement paste contact at a very early stage. After this stage, the transport was reversed and ‘cementitious’ fluids flowed from the cement paste to the argillite. The changes brought about by these fluids are observed over a thickness of 11–13 mm in a so-called ‘black rim’, in which carbonates and C–S–H secondary phases are identified in the matrix of the sediment. An illitization process may also be observed in this altered rim, reaching its maximum development towards the inner part. Geochemical analyses show that the argillite disturbances are strictly confined to the black rim. Theoretical mineralogical profiles based on thermodynamic equilibria defined by the HYTEC code are in good agreement with the observations, and are used to achieve a better understanding of transport processes.     

Charging time of tight gas in the Upper Paleozoic of the Ordos Basin,central China

The Upper Paleozoic section contains a tight gas sandstone reservoir (of 2.75 × 10¹² m³) in the Ordos Basin, central China. The measured porosities (< 10%) and permeabilities (generally < 1 mD) are the result of significant mechanical and chemical compaction and precipitation of carbonate, quartz and authigenic clay cements. Fluid inclusion geochemistry and kinetic modeling (generation of gaseous components and δ¹³C₁) were integrated to constrain the timing of gas charge into the tight reservoir. The modeling results indicate that the natural gases in the present reservoir are similar to gases liberated from quartz inclusions in both composition and stable carbon isotope values and also similar to gas generated from Upper Paleozoic coal. The similar geochemistry suggests that an important phase of quartz cementation must have occurred after gas emplacement in the reservoirs during regional uplift at the end of the Cretaceous. The latest carbonate cement, postdating quartz cementation, consumed most of the late CO₂ generated from coal at high maturity (R_O > 1.7%) and reduced the reservoir quality dramatically. On the contrary, tight sandstones from non-producing areas have fluid inclusions that were trapped in quartz cements much earlier. These data indicate that natural gas migrated into the Upper Paleozoic reservoir when it still retained high porosity and permeability. The reservoir continued to experience porosity and permeability reduction from continued quartz and carbonate cementation after gas charging due to low gas saturation. Comparison of the relative timing of gas charging with that of sandstone cementation can help to predict areas of risk during tight gas exploration and development.     

Regional evaluation of the coalbed-methane potential of the Foothills/Mountains of Alberta,Canada

Coal is present in the Alberta Foothills/Mountains in five zones: the Kootenay, Gething, Gates, Brazeau and Coalspur coal zones. For coalbed-methane (CBM) evaluation purposes, they can be divided into shallow (less than 1000 m depth) and deep (greater than 1000 m depth) coal zones. The potential gas content of all shallow coal zones totals about 878 × 10⁹ m³ (31 Tcf) of CBM, which is considered an inferred, initial, in-place, coalbed-methane resource estimate based on limited data. The limited amount of data on formation testing and measured gas content indicate that the inferred resource is bordering on the speculative category.The gas content of all deep coal zones (deeper than 1000 m) totals 2.8 × 10¹² m³ (about 99 Tcf) of in-place coalbed-methane gas. Consequently, the total ultimate coalbed-methane resource could be 3.7 × 10¹² m³ (130 Tcf). However, coalbed-methane recovery from deep coals is generally not attempted because of the high cost of drilling and the low permeability that results from high overburden load and stress.The only (limited) Foothills coalbed-methane production has been from the southern Alberta Kootenay Coal Zone, which is very prospective for coalbed-methane production. The shallow Gates Coal Zone in the central and northern Foothills is also prospective, but needs to be better tested. The best potential for coalbed methane in the Coalspur Coal Zone is in the Edson area (Entrance Syncline and Triangle Zone). The Kootenay and Gates coal zones are not well defined in the northern part of the Calgary (NTS 82O) map sheet.     

Investigations on Diffusion Characteristics of Granite and Chalk Rock Mass

Contaminant transport through fractured rock mass is predominated by diffusion. This is due to the continuous interaction of the mobile water present in the fracture network and relatively immobile pore water, which is adsorbed on the surface and in the rock matrix itself. Even though the advective flow through the fracture network is high, besides sorption of rock mass, the diffusive exchange into the rock mass leads to significant retardation of contaminant transport. Hence, for describing contaminant transport in fractured rock mass, more precisely, the effect of retardation attributed to the matrix diffusion must be taken in account. With this in view, a methodology, which can be employed for determination of the diffusion characteristics of the rock mass, has been developed and its details are presented in this paper. Validation of the methodology has been demonstrated with the help of Archie’s law.     

Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.     

Influence of humic acid on the sorption of pentachlorophenol by aged sediment amended with rice-straw biochar

Black carbon (BC), especially biochar, is a potential material for the remediation of hydrophobic organic compounds (HOCs) pollution in soils and sediments. Recent studies have reported that the adsorption capability of BC in sediment was reduced as time increased. It was hypothesised that this behaviour was caused by the presence of natural organic matter (NOM), but few systematic studies have examined the influence of NOM on the sorption ability of BC in sediment (S). The results of this study revealed that a humic acid (HA) coating changed the surface properties, blocked the micropores, and decreased the sorption capacity of rice-straw biochar (RBC) towards pentachlorophenol. With increasing aging time, the reductions in the sorption capacity of the S + RBC and S + HA + RBC systems occurred more rapidly than in the S + HA/RBC (HA-coated RBC) system, and the sorption curves became closer to that of the S + HA/RBC system, indicating that HA may play a primary role in reducing the sorption capacity of RBC in the sediment. With higher HA contents, the sorption capacity of the complex sediments was lower and decreased more rapidly.     

The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Influence of arsenic on iron sulfide transformations

The association of arsenate, As(V), and arsenite, As(III), with disordered mackinawite, FeS, was studied in sulfide-limited (Fe:S = 1:1) and excess-sulfide (Fe:S = 1:2) batch experiments. In the absence of arsenic, the sulfide-limited experiments produce disordered mackinawite while the excess-sulfide experiments yield pyrite with trace amounts of mackinawite. With increasing initially added As(V) concentrations the transformation of FeS to mackinawite and pyrite is retarded. At S:As = 1:1 and 2:1, elemental sulfur and green rust are the end products. As(V) oxidizes S(-II) in FeS and (or) in solution to S(0), and Fe(II) in the solid phase to Fe(III). Increasing initially added As(III) concentrations inhibit the transformation of FeS to mackinawite and pyrite and no oxidation products of FeS or sulfide, other than pyrite, were observed. At low arsenic concentrations, sorption onto the FeS surface may be the reaction controlling the uptake of arsenic into the solid phase. Inhibition of iron(II) sulfide transformations due to arsenic sorption suggests that the sorption sites are crucial not only as sorption sites, but also in iron(II) sulfide transformation mechanisms.