Extent Of Sorption Research Articles

Isothermal CO2 separation Enabled by redox-active mixed oxide sorbents

This study reports an isothermal CO2 capture strategy using redox-active perovskite oxides and demonstrates its application in sorption-enhanced hydrogen production. Using a thermodynamic analysis, we investigated the relationship between the equilibrium oxygen partial pressure and the extent of CO2 sorption as well as the theoretical hydrogen purity. To validate the concept, calcium and cobalt co-doped SrFeO3 (SrxCa1-xFeyCo1-yO3-δ) samples were screened experimentally to assess their (isothermal) CO2 sorption capacity and reducibility. The optimal sorbent, Sr0.6Ca0.4Fe0.7Co0.3O3-δ (SCFC-6473), underwent further characterizations and was used for isothermal sorption-enhanced steam reforming (iSESR) of glycerol to produce H2, achieving 93 vol% H2 purity. In addition, we present iSESR of biogas and isothermal sorption-enhanced gasification (iSEG) of pulverized pine by Sr0.875Ba0.125MnO3-δ (SBM 718) to validate the generalizability of the proposed concept for a variety of applications. Nearly 90 % syngas efficiency was demonstrated for iSEG of biomass while producing a hydrogen enriched (73 vol%) syngas product.

Thioarsenate sorbs to natural organic matter through ferric iron-bridged ternary complexation to a lower extent than arsenite

Understanding processes regulating thioarsenate (HxAsSnO4−n3−x; n = 1 – 3; x = 1 – 3) mobility is essential to predicting the fate of arsenic (As) in aquatic environments under anoxic conditions. Under such conditions, natural organic matter (NOM) is known to effectively sorb arsenite and arsenate due to metal cation-bridged ternary complexation with the NOM. However, the extent and mechanism of thioarsenate sorption onto NOM via similar complexation has not been investigated. By equilibrating monothioarsenate (representative of thioarsenate) with a peat (model NOM) with different Fe(III) loadings, this study shows that NOM can sorb monothioarsenate considerably via Fe(III)-bridging. Iron and As K-edge XAS analysis of the monothioarsenate-treated Fe-loaded peats revealed that monothioarsenate forms bidentate mononuclear edge-shared (1E) (RAs···Fe: 2.89 ± 0.02 Å) and bidentate binuclear corner-shared (2C) (RAs···Fe: 3.32 Å) complexes with organically bound Fe(O,OH)6 octahedra, in addition to direct covalent bonds with oxygen-containing functional groups (e.g., –COOH and –OH) (RAs···C: 2.74 ± 0.02 Å), upon equilibration with the Fe(III)-loaded peat. However, the extent of monothioarsenate sorption was considerably less than that of its precursor As species, arsenite, due to higher electrostatic repulsion between the negatively charged monothioarsenate and peat. This study implies that thioarsenate formation under anoxic conditions would increase As mobility by decreasing its sorption onto the NOM.

EDNA Adsorption onto Microplastics: Impacts of Water Chemistry and Polymer Physiochemical Properties.

Adsorption of biomacromolecules onto polymer surfaces, including microplastics (MPs), occurs in multiple environmental compartments, forming an ecocorona. Environmental DNA (eDNA), genetic material shed from organisms, can adsorb onto MPs which can potentially either (1) promote long-range transport of antibiotic resistant genes or (2) serve to gain insights into the transport pathways and origins of MPs by analyzing DNA sequences on MPs. However, little is known about the capacity of MPs to adsorb eDNA or the factors that influence sorption, such as polymer and water chemistries. Here we investigated the adsorption of extracellular linear DNA onto a variety of model MP fragments composed of three of the most environmentally prevalent polymers (polyethylene, polyethylene terephthalate, and polystyrene) in their pristine and photochemically weathered states. Batch adsorption experiments in a variety of water chemistries were complemented with nonlinear modeling to quantify the rate and extent of eDNA sorption. Ionic strength was shown to strongly impact DNA adsorption by reducing or inhibiting electrostatic repulsion. Polyethylene terephthalate exhibited the highest adsorption capacity when normalizing for MP specific surface area, likely due to the presence of ester groups. Kinetics experiments showed fast adsorption (majority adsorbed under 30 min) before eventually reaching equilibrium after 1-2 h. Overall, we demonstrated that DNA quickly binds to MPs, with pseudo-first- and -second-order models describing adsorption kinetics and the Freundlich model describing adsorption isotherms most accurately. These insights into DNA sorption onto MPs show that there is potential for MPs to act as vectors for genetic material of interest, especially considering that particle-bound DNA typically persists longer in the environment than dissolved DNA.

Intraparticle sorption and desorption of antibiotics

Intraparticle domains are the critical locations for storing contaminants and retarding contaminant transport in subsurface environments. While the kinetics and extent of antibiotics sorption and desorption in subsurface materials have been extensively studied, their behaviors in intraparticle domains have not been well understood. This study investigated the sorption and desorption of antibiotics (ATs) in the intraparticle domains using quartz grains and clay, and antibiotic tetracycline (TC) and levofloxacin (LEV) as examples that are commonly present in groundwater systems. Batch experiments coupled with the analyses using various microscopic and spectroscopic techniques were performed to investigate the sorption and desorption kinetics, and to provide insights into the intraparticle sorption and desorption of TC and LEV. Results indicated that both TC and LEV with different physiochemical properties can migrate into intraparticle domains that were consistent with sorptive diffusion. The rate and extent of the sorption are a function of intraparticle surface area and properties, pore volume and connectivity, and ionic properties of the ATs. The sorptive diffusion led to the slow desorption of both TC and LEV after their sorption, apparently showing an irreversible desorption behavior (with desorption percentage about 1.86–20.51%). These results implied that intraparticle domains can be important locations for storing ATs, retarding ATs transport, and may serve as a long-term secondary source for groundwater contamination.

Diffusion of HTO, 36Cl and 22Na in the Mesozoic rocks of northern Switzerland: I. Effective diffusion coefficients and capacity factors across the heterogeneous sediment sequences

Argillaceous rocks are currently being examined worldwide as potential host rocks for repositories for radioactive waste and spent fuel due to their favourable characteristics such as the self-sealing ability or limited diffusive transport of fluids, solutes or gases. In this study, through-diffusion experiments focused on rock samples with different mineralogical compositions taken from deep boreholes in the Mesozoic rock sequence of northern Switzerland, to determine diffusion parameters of HTO, 36Cl− and 22Na+ perpendicular to the bedding plane. Both effective diffusion coefficients and accessible porosities were calculated from the data obtained. In the Opalinus Clay, the primary selected host rock of the repository, the effective diffusion coefficients (De) and accessible porosity values (ε) of the neutral species HTO within and across all study areas are relatively consistent (De = 8.8 ± 1.9 × 10−12 m2 s−1; ε = 0.12 ± 0.02), indicating that the material can be considered homogeneous in terms of diffusion properties. Importantly, the chemical composition of the pore water has no effect on the values of the effective diffusion coefficients of HTO. On the other hand, the rocks above and below the Opalinus Clay, up to the next aquifer, consist of tight sedimentary units (carbonates, siliciclastics including argillaceous rocks) with a wider range of diffusion coefficients, indicating a higher level of heterogeneity. The diffusion coefficients of anions, such as 36Cl−, tend to be smaller due to anion exclusion effects, while those of cations, such as 22Na+, tend to be larger due to surface enhanced diffusion. The extent of these effects is largely determined by the composition of the pore water, and – in the case of cations – by the extent of sorption which depends also on the sorption capacity – indicated by the cation exchange capacity - of the solid. As a result, variations in the effective diffusion coefficient of 36Cl− and 22Na+ can be observed firstly between different rock types (i.e. composition, fabric), and secondly between the different study areas due to differences in the chemical composition of the pore waters in contact with the solid phase.Based on the analysis of around 130 samples, it has been observed that the diffusion coefficients of the Mesozoic units in northern Switzerland exhibit a significant correlation with the total clay content of the rocks. These findings pave the way for the establishment of a diffusion database for the relevant elements under consideration in the Swiss radioactive waste programme and the Safety Case.

Sorption affinity and mechanisms of per-and polyfluoroalkyl substances (PFASs) with commercial sorbents: Implications for passive sampling

Effective monitoring tools, including passive samplers, are essential for the wide range of per- and polyfluoroalkyl substances (PFASs) in aquatic matrices. However, knowledge of the extent and mechanisms of PFASs sorption with sorbents in a passive sampling context is limited. To address this, sorption behavior of 45 anionic, neutral and zwitterionic PFASs ranging in perfluorocarbon chain length (C3-C16) and functional groups with 11 different commercial sorbents (cross-linked β-cyclodextrin polymers, activated carbon, anion exchange (AE), cation exchange, hydrophilic-lipophilic balanced (HLB) and non-polar) was investigated. A broad range of equilibrium sorbent-MilliQ water (MQ) distribution coefficients (Kd) were observed (10−1.95 to 108.30 mL g−1). Similar sorbent types (e.g., various AE and HLB sorbents) exhibited very different sorption behavior, likely due to their different polymeric structures and relative importance of sorbate/sorbent interactions other than coulombic interactions. HLB and AE with hydroxyl functionalities are most effective for sampling of the full suite of PFASs. Reduced sorptive affinity was observed in the presence of matrix co-constituents in wastewater influent for most PFASs. HLB had the smallest reduction in log Kd in wastewater suggesting that these sorbents are appropriate for applications in complex matrices. Sufficient sorbent capacity was observed for linear uptake of many target analytes which facilitates passive sampling.

Monitoring microplastic-contaminant sorption processes in real-time using membrane introduction mass spectrometry.

Microplastics are environmentally ubiquitous and their role in the fate and distribution of trace contaminants is of emerging concern. We report the first use of membrane introduction mass spectrometry to directly monitor the rate and extent of microplastic-contaminant sorption. Target contaminant (naphthalene, anthracene, pyrene, and nonylphenol) sorption behaviours were examined at nanomolar concentrations with four plastic types: low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). Under the conditions employed here, short-term sorption kinetics were assessed using on-line mass spectrometry for up to one hour. Subsequent sorption was followed by periodically measuring contaminant concentrations for up to three weeks. Short-term sorption followed first order kinetics with rate constants that scaled with hydrophobicity for the homologous series of polycyclic aromatic hydrocarbons (PAHs). Sorption rate constants on LDPE for equimolar solutions of naphthalene, anthracene, and pyrene were 0.5, 2.0, and 2.2 h-1, respectively, while nonylphenol did not sorb to pristine plastics over this time period. Similar trends among contaminants were observed for other pristine plastics with 4- to 10-fold faster sorption rates associated with LDPE when compared to PS and PP. Sorption was largely complete after three weeks, with the percent analyte sorbed ranging from 40-100% across various microplastic-contaminant combinations. Photo-oxidative ageing of LDPE had little effect on PAH sorption. However, a marked increase in nonylphenol sorption was consistent with increased hydrogen-bonding interactions. This work provides kinetic insights into surface interactions and describes a powerful experimental platform to directly observe contaminant sorption behaviours in complex samples under a variety of environmentally relevant conditions.

Enhancement and Inhibition of Oxidation in Phenolic Compound Mixtures with Manganese Oxides

Phenolic compounds can be oxidized by manganese oxides in the subsurface or during passive treatment of stormwater runoff and wastewater effluent. Contaminated waters may contain a complex mixture of phenolic compounds, and these mixtures may have additive, synergistic, or antagonistic toxicological effects. However, the effects of such mixtures on the rates and mechanisms of phenol oxidation by manganese oxides are not well understood. This study addresses this knowledge gap by determining pseudo-first-order oxidation rates and oxidation mechanisms for four phenols reacted with δ-MnO2 in varying mixtures. Oxidation rates of electron transfer-limited phenols (i.e., triclosan, resorcinol, bisphenol A) are inhibited in mixtures. This inhibition, as well as the observed decrease in sorption, is consistent with competition between phenols occurring near the Mn surface. In contrast, the oxidation rate and extent of sorption for sorption-limited 4,4′-biphenol are enhanced in mixtures. The rate enhancement is partially driven by indirect oxidation through radical-mediated reactions, likely from phenoxy radicals produced when electron transfer-limited phenols react with δ-MnO2. These findings demonstrate that mixtures have a large impact on phenol oxidation by manganese oxides, as the electron transfer-limited phenols are inhibited due to competition interactions and the sorption-limited phenol has increased oxidation rates due to indirect oxidation by radicals and enhanced sorption.

Role of surfactants in improving release from higher drug loading amorphous solid dispersions

Amorphous solid dispersion formulations (ASD) are increasingly being used as a formulation strategy to improve bioavailability of poorly soluble drugs. One of the limitations of ASDs, in particular for high glass transition temperature (Tg) compounds, is the drug loading threshold (termed the limit of congruency, LoC) below which rapid, complete and congruent release of drug and polymer is achieved. In this study, several ionic and non-ionic surfactants were added to atazanavir-copovidone ASDs with the main goal of increasing the limit of congruency. Atazanavir (ATZ) is a relatively high Tg compound with a LoC of 5 % drug loading (DL). Surface normalized dissolution studies revealed that addition of 5 % w/w of surfactant, sodium dodecyl sulfate (SDS) or cetrimonium bromide (CTAB), to the binary copovidone-based ASD doubled the LoC (from 5 to 10 % DL), resulting in a more than 30-fold increase in total release compared to the corresponding binary ASD. Moreover, addition of 5 % of Span®80 increased the LoC to 15 % DL. ASD Tg was found to decrease upon addition of surfactants and water sorption extent was found to increase. We speculate that surfactants act as plasticizers, which may facilitate polymer release from ASDs containing a high Tg drug, providing a possible explanation for the observed enhancement in drug release from ternary ASDs and the increase in LoC.

Can aged microplastics be transport vectors for organic micropollutants? – Sorption and phytotoxicity tests

Microplastics have been investigated over the last decade as potential transport vectors for other pollutants. However, the specific role of plastic aging, in which plastics change their characteristics over time when exposed to environmental agents, has been overlooked. Therefore, sorption experiments were herein conducted using virgin and aged (by ozone treatment or rooftop weathering) microplastic particles of LDPE – low-density polyethylene, PET – poly(ethylene terephthalate), or uPVC – unplasticized poly(vinyl chloride). The organic micropollutants (OMPs) selected as sorbates comprise a diversified group of priority substances and contaminants of emerging concern, including pharmaceutical substances (florfenicol, trimethoprim, diclofenac, tramadol, citalopram, venlafaxine) and pesticides (alachlor, clofibric acid, diuron, pentachlorophenol), analyzed at trace concentrations (each ≤100 μg L−1). Sorption kinetics and equilibrium isotherms were obtained, as well as the confirmation that the aging degree of microplastics plays a major role in their sorption capacities. The results show an increased sorption of several OMPs on aged microplastics when compared to pristine samples, i.e. the sorption capacity increasing from one or two sorbed substances (maximum 3 μg g−1 per sorbate) up to nine after aging (maximum 10 μg g−1 per sorbate). The extent of sorption depends on the OMP, polymer and the effectiveness of the aging treatment. The modifications (e.g. in the chemical structure) between virgin and aged microplastics were linked to the increased sorption capacity of certain OMPs, allowing to better understand the different affinities observed. Additionally, phytotoxicity tests were performed to evaluate the mobility of the OMPs sorbed on the microplastics and the potential effects (on germination and early growth) of the combo on two species of plants (Lepidium sativum and Sinapis alba). These tests suggest low or no phytotoxicity effect under the conditions tested but indicate a need for further research on the behavior of microplastics on soil-plant systems.

Internal topology and water transport in tetrafunctional epoxy resins

AbstractWater sorption into epoxy resins limits the performance lifetime of many composites, adhesives, and coatings. One hypothesis for the well‐known hygroscopicity of epoxies is that the well‐known internal nodular topology of epoxy networks enhances permeability. This theory has however remained untested to date, since previous attempts to manipulate the internal topology have been accompanied by changes in the hydrogen bonding capability of resins, which dominates water uptake. Here, the nanostructure of highly cross‐linked network polymers based on tetra glycidyl diaminodiphenyl methane is varied in the absence of significant polarity effects by careful optimization of the cure schedule. The internal morphology of resins cured at 100, 150, and 200°C are characterized using Peakforce tapping mode atomic force microscopy, whilst the cure progression at each temperature is analyzed using in‐situ transmission mode infrared spectroscopy. Distinct nodular morphologies are found to form at high cure temperatures (150 and 200°C), where spectroscopic analysis demonstrates that excess epoxy consumption occurs prior to the gel point, as a result of intra‐cluster cross‐linking and reduced reaction selectivity. Surprisingly, the establishment of an internal nanostructure is, however, found to have negligible effect on the extent and kinetics of moisture sorption.

Trace organic contaminants within solid matrices along an anthropized watercourse: Organo-mineral controls on their spatial distribution

Although numerous studies have determined significant contamination in terms of trace organic contaminant (TrOC) diversity and concentration, the occurrence of TrOCs within solid matrices as suspended solids and sediments flies under the radar. In this study, the occurrence of 35 TrOCs of various classes (i.e. pharmaceutical products and pesticides) was investigated in three compartments, namely dissolved phase, suspended particulate matter (SPM) and sediments, within an anthropized river in France. The sampling was performed to assess the spatial contamination dynamics and the impact of a major wastewater treatment plant (WWTP), under two contrasted hydrological conditions, i.e. base level and flood conditions. Solid samples were finely characterized (XRD, grainsize, TOC) in order to assess the impact of organic and mineral composition on the sorption extent of TrOCs. The study reveals that the clear spatial pattern of contamination in water samples, mostly generated by the effluent discharge of WWTPs, is less clear in solid matrices as the variability of the organo-mineral composition of such samples strongly impacts their favourability for sorption. Moreover, the flood event strongly impacted the sedimentary compartment, remobilizing fine and TrOC contaminated particles that were further found in suspended particulate matter. Lastly, the representativeness of contaminant diversity and concentration within the solid matrices displayed more favourable insights for SPM.

Evaluation of Drug Sorption on Laboratory Materials with Abraham Solvation Parameters of Drugs and its Prevention.

Undesired drug sorption on laboratory material surfaces reduces the performance of analytical methods and results in the generation of unreliable data. Hence, we characterized the sorption of drugs and evaluated the sorption extent using a linear free energy relationship (LFER) model with Abraham solvation parameters of drugs. Furthermore, to prevent sorption, the effects of additives, such as organic solvents and salts, were evaluated. The sorption of fifteen model drugs (concentration: 2μM), with various physicochemical properties, on materials in 0.2% dimethyl sulfoxide aqueous solutions was evaluated. Drug sorption extent on the materials was determined using high-performance liquid chromatography. The obtained results were analyzed using an LFER model with Abraham solvation parameters of the drugs. The effect of additives on the sorption of itraconazole, one of the most hydrophobic drugs among those tested in this study, was investigated. Sorption was dependent on the physicochemical properties of drugs, rather than the type of materials used, and additives altered the rate of drug sorption. Equations were developed to evaluate the sorption extent (nmol) of drugs to glass and polypropylene using the Abraham solvation parameters of the drugs. LFER modeling with Abraham solvation parameters of drugs enabled us to evaluate drug sorption on materials. All the additives altered the rate of drug sorption, and some organic solvents effectively prevented sorption. The developed LFER model would be useful for assessment of the sorption properties of compounds in in vitro evaluations in drug discovery research and various other biochemical fields.

Comparative study on polychlorinated biphenyl sorption to activated carbon and biochar and the influence of natural organic matter

The sorption isotherms of polychlorinated biphenyls (PCBs) on carbons (coal based activated carbon named AC and hardwood derived biochar named BC) and natural organic matter (NOM) loaded carbons were examined and carbon-water partition coefficients (KC-W-PCB) were calculated. The purpose was to accurately predict the effectiveness of in-situ carbon treatments on the sediment impacted with hydrophobic organic chemicals (HOCs). For 1 month sorption, AC KC-W-PCB values were significantly higher than BC, corresponding to the much larger surface area (particularly in mesopores) for AC. BC KC-W-PCB values were correlated with PCB total surface area (TSA) and octanol-water partition coefficient (logKow). After loading with NOM, AC adsorption to PCBs strongly reduced and the fitted Freundlich exponents (n) decreased with increasing NOM level. However, NOM loading slightly impacted BC sorption and exhibited an opposite effect on BC n values. It is illustrated that the sorption mechanisms are different between AC and BC thereby the influences of NOM on sorption characteristics differ vastly. As the sorption time increased from 1 month to 6 months, an increase is observed in BC sorption extent but simultaneously NOM reduction effect on BC sorption increases, implying that more accurately evaluating BC application as an in-situ sorbent amendment for HOC impacted sediment need further investigation. On the contrary, AC adsorption attenuation caused by NOM coating greatly decreases over time, encouraging AC application as a sediment amendment.

Water Purification by Potassium Humate–C.I. Basic Blue 3 Adsorption-Based Interactions

Interactions of C.I. Basic Blue 3 with potassium humate in aqueous systems were investigated. Both the humic content and dye removal are of crucial significance in relation to water of a desired quality. Dye retention experiments demonstrated that potassium humate is an exceptionally efficient adsorbent. The effect of both the pH and temperature on the adsorption process was investigated. The temperature proved to only slightly influence the extent of dye sorption; contrarily, under mildly acidic conditions (pH = 4.0), the quantity of dye adsorbed was doubled on standing. At this pH value, interactions between the positively charged dye and the dissociated carboxyl groups of humic substances are encountered. This was also supported by the obedience of the experimental data to the pseudo-second-order kinetic model. Three adsorption models, i.e., Langmuir, Freundlich and BET, were fitted to the experimental data; the equilibrium adsorption conformed to the Langmuir and BET isotherm equations on the basis of electrostatic dye–humics interactions, while the fitting of the Freundlich model referred to the heterogeneities of humic substances attributed to their colloidal behavior. Thermodynamic quantities, i.e., enthalpy, entropy and free energy change in the adsorption, were calculated. The low ΔHadsθ values verify the negligible effect of the temperature on the adsorption; ΔSadsθ denotes a thermodynamically favorable reaction, and ΔGadsθ denotes a spontaneous process.

Microplastics as a Trojan horse for trace metals

Due to an assumed lack of anionic binding sites (most plastics are non-polar), scientists long considered virgin particulate plastics inert towards metal ions. However, we proved significant metal sorption to microplastics at neutral pH and release in a solution mimicking gastrointestinal chemistry serving as a proof-of-principle for environmental and human bioavailability. Competitive ion-exchange incubation experiments comprised 55 metals and metalloids. Fast kinetics were observed with 45 %–75 % of As, Be, Bi, Cr, Fe, In, Pb, Th, Sn and the rare-earth element ions being sorbed after 1 h. The investigated metal and metalloid cations showed significant differences in the extent of sorption, based upon which a distinct categorization was possible. Microplastics are not only a potential danger for aquatic and human life, but - as demonstrated in this paper - also serve as a Trojan Horse for dissolved metal cations. The corresponding effects on aquatic and human health will gain higher importance in the near future due to the predicted increases of marine plastic litter and microplastic sorbents.

Potential of live Spirogyra sp. in the bioaccumulation of copper and nickel ions: A study on suitability and sustainability.

Various industrial and municipal wastes are the major sources of heavy metal contamination in water causing significant environmental issues. Bioremediation is an effective and affordable solution for the removal of metals and metal pollutants from industrial wastewater. This study aimed to assess the efficacy of live and dead Spirogyra sp. for sorption of metals like of Cu2+ and Ni2+ . The live Spirogyra sp. was used for the uptake of Cu2+ and Ni2+ from their aqueous solutions. The equilibrium data were fitted using a Langmuir and Freundlich isotherm model; the maximum uptakes for Cu2+ and Ni2+ were 29 and 521mgg-1 , respectively. Scanning electron microscopic (SEM) and infrared (IR) spectroscopic studies of Spirogyra sp. and treated Spirogyra sp. with specific metal ions were used to assess the bonding site and extent of sorption mechanism. The initial study showed that this biomass takes up a significant amount of metal ions. Compared to the Langmuir model, the Freundlich model showed better sorption process. The pseudo-second-order rate model represented an enhanced kinetics of metal ion adsorption using live Spirogyra sp. As bioaccumulation technology is environmental friendly and potentially cost-effective, live Spirogyra sp. is expected to be a good candidate for managing industrial wastewater.

Sorption of arsenate(Ⅴ) to naturally occurring secondary iron minerals formed at different conditions: The relationship between sorption behavior and surface structure

Arsenic (As) is a problematic pollutant that can cause cancer and other chronic diseases due to its potential toxicity. Iron (oxyhydr)oxides can readily sorb As and play important roles in the geochemical cycle of As. Attention has mainly been given to the affinity and mechanism of As sorption by synthetic pure iron (oxyhydr)oxides, and little is known about the relationship between As behavior and multicomponent secondary iron minerals (SIMs) naturally formed in acid mine drainage (AMD). To investigate this relationship, we performed sorption kinetics, isotherm and competitive sorption experiments to investigate As(V) sorption behaviors on naturally formed SIMs harvested from different runoff zones of an abandoned coal mine. Several spectroscopic analyses were used to evaluate the structural and component changes and phase transformation. Three environmental SIMs formed at nascent (n-SIM), transient (t-SIM) and mature (m-SIM) stages were determined to be similar in the element components of Fe, S and O but different in structure. As(V) sorption behaviors on these environmental SIMs followed a pseudo-second-order kinetic model, and the sorption extent followed the sequence of n-SIM > t-SIM > m-SIM. As(V) sorption is not significantly influenced by Na+/Ca2+ concentration or ionic strength except for that of PO43−, and it slightly decreases as the Cr(Ⅲ) concentration increases but increases with increasing Sb(Ⅲ)/(V) concentration. The results of spectral analyses indicate that As(V) immobilization mainly depends on exchange with SO42− and surface complexation, along with the phase transformation of schwertmannite/jarosite to goethite and other phases. These findings are helpful for better understanding the geochemical behaviors of As(V) associated with environmental SIMs.

Study of Sorption Kinetics and Sorption-Desorption Models to Assess the Transport Mechanisms of 2,4-Dichlorophenoxyacetic Acid on Volcanic Soils.

The sorption behavior of 2,4-dichlorophenoxyacetic acid (2,4-D) in the abundant agricultural volcanic ash-derived soils (VADS) is not well understood despite being widely used throughout the world, causing effects to the environment and human health. The environmental behavior and risk assessment of groundwater pollution by pesticides can be evaluated through kinetic models. This study evaluated the sorption kinetics and 2,4-D sorption–desorption in ten VADS through batch sorption experiments. Differences in the sorption extent for the fast and slow phases was observed through the model where 2,4-D sorption kinetics was controlled by external mass transfer and intra organic matter diffusion in Andisols ( ≠ 0). We confirmed from the spectroscopic analysis that the carboxylate group directly drives the interaction of 2,4-D on Andisol soil. The MLR model showed that , , and are important soil descriptors in the 2,4-D sorption in VADS. The Freundlich model accurately represented sorption equilibrium data in all cases ( values between 1.1 and 24.1 µg1−1/n mL1/ng−1) with comparatively higher sorption capacity on Andisols, where the highest hysteresis was observed in soils that presented the highest and lowest content ( close to 0).

Determination of methane sorption capacity using microstructural analysis in coal of Jharia Coalfield, India

Micrometer-scale pore and fracture structures of coal seams are the crucial parameters for the adsorption of coalbed methane (CBM) and recovery. This paper deals with the microstructure’s influence on coal methane sorption behavior obtained from the Jharia Coalfield, India. Coal samples were collected from different seams to study the variability and heterogeneity of the reservoir parameters. Proximate and ultimate analysis of coal samples were determined to predict the rank of the coal. Microstructural parameters like pore size distribution, surface morphology, and infrared spectroscopy (FT-IR) were studied to predict the extent of gas sorption in the coal. The excess amount of methane sorption was determined using a volumetric method at 47 °C temperature and variable pressure. The identified pore volume varied from 0.2 to 3.07 m3/g. The surface morphology indicated inter- and intraparticle pores with spongy surfaces. The pore volume and surface morphology confirmed the favorable sorption of methane in coal samples. The FT-IR study showed the formation of hydrogen bond and methane sorption in coal. The maximum sorption capacity varied from 5.08 to 9.01 cc/g at 400 to 580 m depth. A strong, positive, and nonlinear correlation was observed with pore volume. The results showed that the presence of meso- and micropores and the spongy surface morphology are vital in defining its methane sorption capacity. As a whole, these coals have a higher porosity from 4.9 to 5.64% and meso- and micropores and are suitable for methane sorption.