Extent Of Sorption Research Articles

Hydrophobic conjugated microporous polymers for sorption of human serum albumin

This paper investigated the sorption of human serum albumin (HSA) from water by three kinds of conjugated microporous polymers (CMPs) with surface hydrophobicity and intrinsic porosity. It was found that the three CMPs captured HSA with fast sorption kinetics and good working capacity. Equilibrium was obtained at 80min for all the tests, and the maximum sorption quantity (qm) ranged from 0.07 to 0.14mg/mg. With the increase in the particle external surface area of the CMPs, a greater extent of HSA sorption was achieved. Moreover, promoting the dispersion of CMPs in HSA aqueous solution was also beneficial to the extraction. Attenuated Total Reflection Fourier Transform Infrared spectroscopy verified the interactions between the CMPs and the NH, CO, and CN groups of HSA. This paper might provide fundamental guidance for the practical application of CMPs to proteins separation and recovery.

Sorption of silver nanoparticles to laboratory plastic during (eco)toxicological testing

Here, we evaluate the extent of sorption of silver nanoparticles (AgNPs) with different primary sizes (30 and 70 nm) and surface properties (branched polyethylene imine, “bPEI” and citrate coating) to laboratory plastic during (eco)toxicological testing. Under conditions of algal growth inhibition assay, up to 97% of the added AgNPs were sorbed onto the test vessels whereas under conditions of in vitro toxicological assay with mammalian cells, the maximum loss of AgNPs was 15%. We propose that the high concentration of proteins and biomolecules in the in vitro toxicological assay originating from serum-containing cell culture medium prevented NP sorption due to steric stabilisation. The sorption of AgNPs to test vessels was clearly concentration dependent. In the conditions of algal growth inhibition assay at 10 ng AgNPs/mL, up to 97% of AgNPs were lost from the test while at higher concentrations (1000 ng AgNPs/mL), the loss of AgNPs was remarkably smaller, up to 64%. Sorption of positively charged bPEI-coated AgNPs was more extensive than the sorption of negatively charged citrate-coated AgNPs and, when calculated on a mass basis, more 70 nm-sized Ag than 30 nm Ag sorbed to plastic surfaces. In summary, this study demonstrates that the loss of AgNPs during (eco)toxicological tests due to sorption on test vessel surfaces is significant, especially in diluted media (e.g. in algal growth medium) and at low NP concentrations. Thus, to ensure the accurate interpretation of (eco)toxicological results, the loss of AgNPs due to adsorption to test vessels should not be overlooked and considered for each specific case.

Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry.

The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM(+) (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

Evaluating the degradation, sorption, and negative mass balances of pharmaceuticals and personal care products during wastewater treatment

Conventional activated sludge (CAS) wastewater treatment processes are insufficient at removing many pharmaceutical and personal care products (PPCPs) from wastewater. In addition, negative mass balances, where the effluent concentration is greater than the influent concentration, have been observed in wastewater treatment studies and a further understanding of these results is needed. In this study, the fate and occurrence of 57 PPCPs and hormones were evaluated in an activated sludge process and the mass balances were determined. The goal of the project was to understand the PPCPs biological degradation and the extent of sorption to solids. The samples containing in situ PPCPs (i.e. samples were not spiked with additional PPCPs) were evaluated. Forty-eight of the PPCPs were detected in the soluble form and 29 were detected sorbed to solids. Two notable results were found. First, the results of this study indicate a subset of the highly biodegradable PPCPs stop being degraded at low, yet notable, concentrations. Second, the results revealed that negative mass balances were present for a subset of the PPCPs when evaluating both the soluble and sorbed concentration, for example carbamazepine and ofloxacin. Desorption from solids was not found to attribute to negative mass balances. Overall, the results from this study provide new insights into the fate of PPCPs during CAS wastewater treatment by evaluating the degradation kinetics and sorption and the results may explain the consistent levels of highly degradable PPCPs being emitted from WWTPs worldwide.

Sorption of heavy metals in organic horizons of acid forest soils at low added concentrations

Vytopilova M., Tejnecký V., Borůvka L., Drabek O. (2015): Sorption of heavy metals in organic horizons of acid forest soils at low added concentrations. Soil & Water Res., 10: 1–9. The individual adsorption/desorption of Cu, Pb, and Zn in six soil samples taken from organic horizons of acid forest soils is studied in batch experiments. These three metals were chosen because of the varying extent of their sorption to the soil organic matter. The initial concentration range for all metals is 0–200 mg/l. 0.01 mol/l Ca(NO3)2 was used as the background electrolyte. Soil samples were taken at random locations throughout a relatively small area and are characterized by small differences in mineralogical composition. Organic matter content and pH of soils are considered as the key factors causing differences in sorption/desorption behaviour of selected metals. In general, the sorption of all the three metals increased with a combination of higher pH value and increasing organic matter content. Anyway, the extent of the influence of these two characteristics on sorption behaviour of metals is different, for desorption significant differences were not determined. Copper sorption seems to reflect mainly the differences in organic matter content in addition to the differences in pH. The average amount of sorbed Pb was approximately 90%, Cu sorption averaged 60%, and that of Zn 30%. Desorption of Pb into 0.01 mol/l Ca(NO3)2 remained at approximately 4%, for Zn at 30%, and desorption of Cu reached up to 13% of the amount adsorbed. All the studied soils proved effective at immobilizing lead and copper, but zinc was relatively highly released from these soils, even when the sorbed amount was minimal. Different vegetational background of these samples (either beech or spruce forests) does not significantly influence the sorption extent of these metals as the lower pH of samples taken under spruce stands is probably compensated by higher organic matter content in these samples. The experimental data are fitted by the Freundlich equation and the parameters of this equation together with the adsorption and desorption efficiency are used for comparison of the behaviour of all the three metals among the six soils.

Sorption and plant uptake of pharmaceuticals from an artificially contaminated soil amended with biochars

Plant uptake of active pharmaceutical ingredients (APIs) is increasingly leading to concerns about their potential exposure to humans and wildlife via dietary intake. Due to the extraordinary ability of biochars to bind organic compounds, plant uptake experiments were conducted to assess the effect of soil-amendment of three different biochars on the uptake of APIs from spiked soil. Pot experiments were undertaken to assess the extent of sorption and corresponding bioaccessibility of two APIs (carbamazepine - CBZ and propranolol -PRL) to ryegrass (Lolium perenne) grown in an API-spiked loamy sand, with and without biochar amendment (5 t/ha equivalent). The soil was amended with three different biochars produced from eucalyptus wood and wheat residues. Both APIs were taken up by ryegrass, with CBZ preferentially accumulated (14.3 mg/kg CBZ, 3.8 mg/kg PRL in unamended soil) due to its comparatively high concentration in porewater. Soil amendment with biochars increased partitioning of the two APIs by up to three- fold, with corresponding decreases in porewater (34–72 % of unamended soil) and plant tissue (17–64 %) concentrations. Biochars were effective in reducing the uptake of APIs into plant tissues from a contaminated soil and may be effective in the management of API residues in contaminated soils.

Sorption of enantiomers and alcohols into Nafion® and the role of air humidity in the experimental data evaluation

Two enantiomers may exhibit completely different biological or pharmacological activities; therefore, the resolution of the enantiomers from a racemic mixture is an important task. The results of the total sorption measurements for the individual (+) and (−) liquid enantiomers from the enantiomeric pair revealed that there is a difference between extents of their sorption in Nafion®. The difference between liquid sorption of the (+) and (−) enantiomers of small molecules, such as the methyl lactates or 2-butanols, is higher than in the case of larger molecules, such as phenylethanols and methylbenzyl amines. This result could be explained by the hypothesis that the size of the chiral molecule must fit like a puzzle piece into the Nafion® helical polymer network. This hypothesis was supported by the 19F MAS NMR analysis, which confirmed the helical structure of Nafion®. Further, the branching of the molecules significantly influences the extent of sorption of the liquid in Nafion®, as shown for the butanols. The trend of this dependence is in agreement with the trend of heat of vaporisation and the normal boiling temperature data of the butanols. Because Nafion® easily absorbs water vapour from the air, the influence of the humidity on the sorption values was studied and discussed.

Test on the Reliability of Gastight Syringes as Transfer/Storage Media for Gaseous VOC Analysis: The Extent of VOC Sorption between the Inner Needle and a Glass Wall Surface

A gastight syringe (GTS) is commonly used as a medium for transfer or storage of gaseous standards (or samples) in the analysis of volatile organic compounds (VOCs). In this study, the sorptive loss patterns of 21 VOCs were examined, using GTS as the transfer medium. The results of the test were evaluated with respect to a number of key variables including concentration, sampling volume, and physicochemical properties (molecular weight and boiling point). The VOCs with relatively high volatility (Group 1: aldehyde, ketone, ester, alcohol, and aromatic hydrocarbons (n = 12)) showed low sorptive losses with a mean (±SD) of 2.56 ± 2.87%, regardless of differences in the aforementioned key variables (p-value by t-test before and after using GTS = mean 0.15 ± 0.13). Conversely, the sorptive losses of seven semi-VOCs (Group 2: carboxyl and cresol (n = 9)) were significantly high, ranging from 18.0 ± 4.10% (propionic acid) to 65.4 ± 10.9% (n-heptanonic acid). In addition, we also measured the sorptive losses on the syringe needle (mean sorptive loss of Group 2 = 5.94 ± 5.63%). A linear regression analysis showed that the sorptive losses for Group 2 increased as molecular weight (or boiling point) increased, exhibiting a highly significant correlation (R(2) value (0.804 ± 0.084) and mean p-value (0.002 ± 0.003).

Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite.

The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu-FA-mineral complexes could enhance colloid-facilitated Pu transport. However, more representative natural conditions need to be investigated to quantify the relevance of these findings.

The power of power: Electrokinetic control of PAH interactions with exfoliated graphite

Exfoliated graphite (EG) exhibits exceptional sorption capacity for petroleum and dissolved hydrocarbons owing to its highly hydrophobic surface and wide pore size distribution. The high price of preparing EG, however, restricts its application. Methods which increase the rate or extent of sorption to EG even further are thus longed for. Here, we assess the effects of weak direct current (DC) fields on the sorption of the polycyclic aromatic hydrocarbon phenanthrene (PHE) to EG. DC applied to an ionic solution in a solid matrix invokes electroosmotic flow (EOF), i.e., the surface charge-induced movement of the solution. EG was exposed to weak DC fields in the presence of dissolved PHE to test if EOF increases transport of PHE to poorly accessible sorption sites. DC fields increased PHE sorption rates in EG sevenfold and reduced the desorption rate of sorbed PHE by >99%. EOF thus appeared to be highly effective in translocating PHE into pores, which contribute most of the sorption sites, but are difficult to access in the absence of EOF by molecular diffusion only. The observed ‘power of power’ may be used to kinetically regulate the interaction of sorbates with EG or other porous sorbents in environmental (bio-) technology.

Attenuation of trace organic compounds (TOrCs) in bioelectrochemical systems

Microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are two types of microbial bioelectrochemical systems (BESs) that use microorganisms to convert chemical energy in wastewaters into useful energy products such as (bio)electricity (MFC) or hydrogen gas (MEC). These two systems were evaluated for their capacity to attenuate trace organic compounds (TOrCs), commonly found in municipal wastewater, under closed circuit (current generation) and open circuit (no current generation) conditions, using acetate as the carbon source. A biocide was used to evaluate attenuation in terms of biotransformation versus sorption. The difference in attenuation observed before and after addition of the biocide represented biotransformation, while attenuation after addition of a biocide primarily indicated sorption. Attenuation of TOrCs was similar in MFCs and MECs for eight different TOrCs, except for caffeine and trimethoprim where slightly higher attenuation was observed in MECs. Electric current generation did not enhance attenuation of the TOrCs except for caffeine, which showed slightly higher attenuation under closed circuit conditions in both MFCs and MECs. Substantial sorption of the TOrCs occurred to the biofilm-covered electrodes, but no consistent trend could be identified regarding the physico-chemical properties of the TOrCs tested and the extent of sorption. The octanol–water distribution coefficient at pH 7.4 (log DpH 7.4) appeared to be a reasonable predictor for sorption of some of the compounds (carbamazepine, atrazine, tris(2-chloroethyl) phosphate and diphenhydramine) but not for others (N,N-Diethyl-meta-toluamide). Atenolol also showed high levels of sorption despite being the most hydrophilic in the suite of compounds studied (log DpH 7.4 = −1.99). Though BESs do not show any inherent advantages over conventional wastewater treatment, with respect to TOrC removal, overall removals in BESs are similar to that reported for conventional wastewater systems, implying the possibility of using BESs for energy production in wastewater treatment without adversely impacting TOrC attenuations.

Plutonium sorption and desorption behavior on bentonite

Understanding plutonium (Pu) sorption to, and desorption from, mineral phases is key to understanding its subsurface transport. In this work we study Pu(IV) sorption to industrial grade FEBEX bentonite over the concentration range 10−7–10−16 M to determine if sorption at typical environmental concentrations (≤10−12 M) is the same as sorption at Pu concentrations used in most laboratory experiments (10−7–10−11 M). Pu(IV) sorption was broadly linear over the 10−7–10−16 M concentration range during the 120 d experimental period; however, it took up to 100 d to reach sorption equilibrium. At concentrations ≥10−8 M, sorption was likely affected by additional Pu(IV) precipitation/polymerization reactions. The extent of sorption was similar to that previously reported for Pu(IV) sorption to SWy-1 Na-montmorillonite over a narrower range of Pu concentrations (10−11–10−7 M). Sorption experiments with FEBEX bentonite and Pu(V) were also performed across a concentration range of 10−11–10−7 M and over a 10 month period which allowed us to estimate the slow apparent rates of Pu(V) reduction on a smectite-rich clay. Finally, a flow cell experiment with Pu(IV) loaded on FEBEX bentonite demonstrated continued desorption of Pu over a 12 day flow period. Comparison with a desorption experiment performed with SWy-1 montmorillonite showed a strong similarity and suggested the importance of montorillonite phases in controlling Pu sorption/desorption reactions on FEBEX bentonite.

Gas permeation in thin films of “high free-volume” glassy perfluoropolymers: Part II. CO2 plasticization and sorption

Carbon dioxide (CO2) plasticization and sorption effects in both thick and thin films of “high free-volume” glassy perfluoropolymers were studied by monitoring CO2 permeability and by observing changes in the film thickness and refractive index with ellipsometry measurements. The film thickness, aging time, thermal history and CO2 exposure protocols have significant effect on the absolute CO2 permeability and plasticization behavior of both thick and thin films. The extent of CO2 plasticization increases as film thickness decreases and as the aging time is increased. The as-cast films showed higher plasticization compared to films which were annealed above Tg; however, the CO2 permeability of both the as-cast and annealed films continuously decreased during the depressurization step unlike other glassy polymers. In general, the various CO2 exposure protocols revealed lower CO2 plasticization for perfluoropolymers compared to other reported glassy polymers. The extent of CO2 sorption obtained from the ellipsometry measurements was found to decrease with the decrease in the excess volume and increase in the aging time for perfluoropolymers; in addition, the structural differences among the various glassy polymers resulting in different polymer–gas interactions also affects the overall sorption characteristics. The lower plasticization in perfluoropolymers compared to Matrimid was also confirmed from the smaller percent increase observed for the experimental diffusion coefficient compared to the theoretically predicted diffusion coefficient from the dual sorption-mobility model. The Langmuir sorption parameter, CH′, and solubility at infinite dilution, S0, obtained from fitting dual sorption-mobility model to sorption data, showed an excellent linear correlation with (Tg-35) °C. The CO2 diffusivity and permeability data obtained for thin films of various glassy polymers also showed a strong correlation with free volume. The somewhat unusual behavior of thin films of AF 2400 in comparison to other glassy polymers studied to date is believed to be related to the low cohesive energy density expected of perfluorinated structures and its high free volume resulting from the bulky dioxole comonomer.

Sorption and Mineral-Promoted Transformation of Synthetic Hormone Growth Promoters in Soil Systems

This work examines the fate of synthetic growth promoters (trenbolone acetate, melengestrol acetate, and zeranol) in sterilized soil systems, focusing on their sorption to organic matter and propensity for mineral-promoted reactions. In organic-rich soil matrices (e.g., Pahokee Peat), the extent and reversibility of sorption did not generally correlate with compound hydrophobicity (e.g., K(ow) values), suggesting that specific binding interactions (e.g., potentially hydrogen bonding through C17 hydroxyl groups for the trenbolone and melengestrol families) can also contribute to uptake. In soils with lower organic carbon contents (1-5.9% OC), evidence supports sorption occurring in parallel with surface reaction on inorganic mineral phases. Subsequent experiments with pure mineral phases representative of those naturally abundant in soil (e.g., iron, silica, and manganese oxides) suggest that growth promoters are prone to mineral-promoted oxidation, hydrolysis, and/or nucleophilic (e.g., H2O or OH(-)) addition reactions. Although reaction products remain unidentified, this study shows that synthetic growth promoters can undergo abiotic transformation in soil systems, a previously unidentified fate pathway with implications for their persistence and ecosystem effects in the subsurface.

Sorption and transport of five sulfonamide antibiotics in agricultural soil and soil–manure systems

Animal manure application is a main spreading route of veterinary antibiotics in soil and groundwater. The sorption and leaching behavior of five commonly used sulfonamides in five typical soil and soil/manure mixtures from China were investigated in this study. Results showed that the empirical Freundlich equation fits well the sorption behavior of selected sulfonamides (r2 was between 0.803 and 0.999, 1/n was between 0.68 and 1.44), and pH and soil organic carbon (OC) were the key impact factors to sorption and leaching. Addition of manure was found to increase the Kd values of sulfonamides in five different soils, following the rules that the more polar substances, the more increased extent of sorption after manure amendment (5.87 times for sulfadiazine with Log Kow = −0.09, and 2.49 times for sulfamethoxazole with Log Kow = 0.89). When the simulated rainfall amount reached 300 mL (180 mm), sulfonamides have high migration potential to the groundwater, especially in the soil with low OC and high pH. However, manure amendment increased the sorption capacity of sulfonamides in the top layer, thus it might play a role in decreasing the mobility of sulfonamides in soils. The systematic study would be more significant to assess the ecological risks and suggest considering the influence of manure amendment for the environmental fate of antibiotics.

Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength.

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO2) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400mg/L TiO2 NPs). Additionally, sorption of NOM to TiO2 NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer-Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO2 NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM's fractional preferential sorption to NPs in the aquatic environment.

The role of polarizability in determining metal ion affinities in polymer-supported reagents: Phosphorylated ethylene glycol

This is the first of a series of reports that probes the polarizabilities of different immobilized ligands in order to build toward a rational design of ion-selective polymer-supported reagents. In this report, the polarizabilities of four ligands on a polystyrene backbone (phosphorylated ethylene glycol (pEG1), ethylene glycol (EG1), sulfonic acid, and dimethylamine (DMA)) are evaluated with Au(III) and Eu(III) as representative of soft and hard ions, respectively. Interactions are followed by the extent of sorption, the effect of acid concentration, band shifts in FTIR spectra, and Langmuir plots. The phosphoryl oxygen, hydroxyl OH, and amine show an affinity of Au(III)>Eu(III) while Eu(III)>Au(III) is evident with the sulfonic acid. The PO stretching frequency shifts from 1263 to 1249cm−1 upon Au(III) binding. The affinities indicate that oxygen can be considered soft and hard, depending on its microenvironment: neutral oxygen is soft while anionic oxygen may be classified as hard. Though Eu(III) prefers ionic binding with a strong acid ligand, it is also capable of weak binding with a neutral oxygen donor at pH 3 and 4. Sorption is affected by solution acidity despite the absence of ion exchange. Three routes to enhancing ion–interactions thus emerge: preparing single-site ligands whose polarizability matches the targeted metal ion, preparing ligands with multiple binding sites each of which bind weakly on their own, and preparing single-site ligands with dual ion exchange/coordination character.

Soil sorption and leaching of active ingredients of Lumax® under mineral or organic fertilization

The study describes the soil sorption of the herbicide Lumax®, composed of S-metolachlor (MTC), terbuthylazine (TBZ), and mesotrione (MST), as influenced by mineral and organic fertilizers. The investigation was performed on a sandy soil of an agricultural area designated as a Nitrate Vulnerable Zone, where mineral and organic fertilizers were applied for many years. Two organic fertilizers, cattle manure and slurry, respectively, and a mineral fertilizer with a nitrification inhibitor, Entec®, were compared. According to the experiments, performed with a batch method, the sorption conformed to Freundlich model. The extent of sorption of Lumax® ingredients was closely related to their octanol–water partition coefficient Kow. The respective desorption was hysteretic. Leaching trials were carried out by using water or solutions of DOM or Entec® as the eluants. Only the elution with the mineral fertilizer promoted the leaching of Lumax® active ingredients.

Sorption of Hydrophobic Organic Compounds on Natural Sorbents and Organoclays from Aqueous and Non-Aqueous Solutions: A Mini-Review

Renewed focus on the sorption of hydrophobic organic chemicals (HOCs) onto mineral surfaces and soil components is required due to the increased and wider range of organic pollutants being released into the environment. This mini-review examines the possibility of the contribution and mechanism of HOC sorption onto clay mineral sorbents such as kaolinite, and soil organic matter and the possible role of both in the prevention of environmental contamination by HOCs. Literature data indicates that certain siloxane surfaces can be hydrophobic. Therefore soils can retain HOCs even at low soil organic levels and the extent will depend on the structure of the pollutant and the type and concentration of clay minerals in the sorbent. Clay minerals are wettable by nonpolar solvents and so sorption of HOCs onto them from aqueous and non-aqueous solutions is possible. This is important for two reasons: firstly, the movement and remediation of soil environments will be a function of the concentration and type of clay minerals in the soil. Secondly, low-cost sorbents such as kaolinite and expandable clays can be added to soils or contaminated environments as temporary retention barriers for HOCs. Inorganic cations sorbed onto the kaolinite have a strong influence on the rate and extent of sorption of hydrophobic organic pollutants onto kaolinite. Structural sorbate classes that can be retained by the kaolinite matrix are limited by hydrogen bonding between hydroxyl groups of the octahedral alumosilicate sheet and the tetrahedral sheet with silicon. Soil organic carbon plays a key role in the sorption of HOCs onto soils, but the extent will be strongly affected by the structure of the organic soil matter and the presence of soot. Structural characterisation of soil organic matter in a particular soil should be conducted during a particular contamination event. Contamination by mining extractants and antibiotics will require renewed focus on the use of the QSAR approaches in the context of the sorption of HOCs onto clay minerals from aqueous and non-aqueous solutions.

Synthesis of polyacrylamide-bound hydroquinone via a homolytic pathway: Application to the removal of heavy metals

Abstract Polyacrylamide (PAAm) was chemically modified with hydroquinone (HQ) via a homolytic route. A degree of modification of approximately 58% was obtained under optimal reaction conditions: time of 6 h, and [modifier]/[acrylamide] molar ratio of 5. PAAm and its modified form HQ–PAAm were characterized by UV–visible spectroscopy, FT–IR spectroscopy, 13C NMR spectroscopy, DSC, TGA, XRD, and SEM. A relatively lower molecular weight of the corresponding hydroquinone-functionalized form was measured. The glass transition temperature of the modified polymeric material was lower than that of the pristine one: 78.82 °C for HQ–PAAm versus 161.19 °C for PAAm. A study of Cu(II) adsorption by the cross-linked PAAm and HQ–PAAm resins was conducted by varying the following parameters: pH, time, temperature, ionic strength, sorbent mass, and initial Cu(II) concentration. The adsorption capacity of Pb(II) and Cd(II) by the different resins and their corresponding extents of desorption were estimated. The optimal conditions for metal ion uptake by polyacrylamide and its modified resin were: pH = 5.4, time = 120 min, temperature = 45 °C. The sorption extent by the modified resin was in the order Pb(II) > Cu(II) > Cd(II). The desorption of the experimented metallic ions from the resins exceeded 97%. A new way of cross-linking PAAm and its modified form is described herein.