Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Sorption and desorption of diuron on Typic Argiudoll,Oxic Argiudoll and on their clay fractions: environmental aspects

Abstract

The sorption and desorption of diuron by soil samples from Horizons A and B (HA and HB) and by their different clay fractions were investigated, using two soil samples, classified as Typic Argiudoll and Oxic Argiudoll. The sorption and desorption curves were adjusted to the Freundlich model and evaluated by parameters K_f, K_d and K_oc. Based on the data of groundwater ubiquity score (GUS), leachability index (LIX) and hysteresis index (HI), the risk of groundwater pollution was evaluated. The K_d values obtained for soil samples were between 4.5?mL g^?1 (Oxic Argiudoll – HB) and 15.9?mL g^?1 (Typic Argiudoll – HA) and between 1.13 and 14.0?mL g^?1 for the different mineral fractions, whereas the K_oc values varied between 276 (Oxic Argiudoll – HB) and 462 (Typic Argiudoll – HA). According to the parameter GUS, only Oxic Argiudoll – HB presented leaching potential, and based on the LIX index this same soil presented the highest leaching potential. Some samples presented low LIX and GUS values, indicating no leaching potential, but none presented HI results indicative of hysteresis, suggesting weak bonds between diuron and the soil samples and, hence, the risk of groundwater pollution by diuron.     

Cosolvent effects on sorption isotherm linearity

Sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. In this study, aqueous and mixed solvent systems were used to investigate the effects of a cosolvent, methanol, on sorption isotherm linearity with natural organic matter (NOM), and to evaluate whether these results support, or weaken, the rubbery/glassy polymer conceptualization of NOM. All of the sorption isotherms displayed some nonlinear character. Our data indicates that all of the phenanthrene and atrazine isotherms were nonlinear up to the highest equilibrium solution concentration to solute solubility in water or cosolvent ratios (Ce/Sw,c) used, approximately 0.018 and 0.070, respectively. Isotherm linearity was also observed to increase with volumetric methanol content (fc). This observation is consistent with the NOM rubbery/glassy polymer conceptualization: the presence of methanol in NOM increased isotherm linearity as do solvents in synthetic polymers, and suggests that methanol is interacting with the NOM, enhancing its homogeneity as a sorptive phase so that sorption is less bimodal as fc increases. When the equilibrium solution concentration was normalized for solute solubility in water or methanol-water solutions, greater relative sorption magnitude was observed for the methanol-water treatments. This observation, in conjunction with the faster sorption kinetics observed in the methanol-water sediment column systems, indicates that the increase in relative sorption magnitude with fc may be attributed to the faster sorption kinetics in the methanol-water systems, and hence, greater relative sorptive uptake for the rubbery polymer fraction of NOM at similar time scales.     

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers’ breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils’ hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.     

The impact of contact time on pyrene sorptive behavior by a sandy-loam soil

Batch experiments with pyrene (PYR) were conducted to quantify the effect of contact time on its sorption and desorption behavior by a sandy-loam soil. Twenty-four and 48 h contact times were chosen for the nonequilibrium conditions and 240 h for the pseudoequilibrium study. All times was selected based on the kinetic results. The nonlinear, pseudoequilibrium sorption isotherm was fit to a two-stage Freundlich model: 3-7 mg/l for the first stage and 7-15 mg/l for the second stage. A substantial fraction of the sorbed PYR was not desorbed within the given desorption time. The reason of hysteresis was found to be a sorption enhancement due to soil hydration which provided more sorption sites. A desorption enhancement at 240-h desorption steps was attributed to the increased dissolved organic matter evolution. This study also found that both soil organic matter and clay materials had an equal role in PYR sorption enhancement and desorption resistance.     

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Carbon nanotubes (CNTs), as a type of superior adsorbents for both organic and inorganic contaminants, are increasingly introduced into the environment. Ubiquitous natural organic matter (NOM) would coat on the released CNTs and change their physicochemical properties and sorption of contaminants. The effects of four sequentially extracted humic acids (HAs, as a model NOM) from a peat soil on the physicochemical properties and Cd(II) sorption of three multiwalled CNTs (MWNTs) with different surface areas were investigated. The MWNTs as purchased with very few oxygen-containing functional groups had relatively low sorption capacities (0.93–1.49 mg g⁻¹) for Cd(II) and the sorption capacity increased with increasing surface area of the MWNTs. Surface-coating with the HAs lowered surface areas of the MWNTs but greatly increased their sorption capacities (5.42–18.4 mg g⁻¹). The MWNT-bound HAs introduced oxygen-containing functional groups and negative charges to the MWNT surfaces, which could thus increase the apparent sorption of Cd(II) through chemical complexation and electrostatic attraction, respectively. The later-extracted HAs with lower polarity were more favorable for the surface-coating but increased less Cd(II) sorption by the MWNTs. The results are expected to shed light on understanding the underlying mechanism of the effect of NOM on the sorption of heavy metal ions by CNTs.     

Sorption-desorption behavior of polycyclic aromatic hydrocarbons in upstream and downstream river sediments

Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: a case study with carbamazepine

Natural organic matter (NOM) in soils and sediments is recognized to strongly affect environmental distributions of organic compounds. Water associated with NOM may have a significant impact on NOM-organic compound interactions. The objectives of this research were (1) to determine the effect of hydration of a model NOM sorbent on interactions with a probe organic compound, carbamazepine (CBZ), and (2) based on the comparison with the literature data, to evaluate the effect of organic compound structure on the cooperative participation of water molecules in organic sorbate-NOM interactions. CBZ is one of the most widely reported water pollutants from the pharmaceutical and personal care products family. Therefore, CBZ sorption on Pahokee peat was compared from water and from n-hexadecane, using solubility-normalized solute concentrations. CBZ-NOM interactions were enhanced by one to two orders of magnitudes when NOM became fully hydrated. This enhancement is associated with the distinct ability of CBZ to undergo strong, specific interactions with NOM which was revealed by comparing the transfer of CBZ and another model sorbate, phenanthrene, from solution in n-hexadecane to the hydrated NOM sorbent. The enhancing effect of NOM hydration on CBZ-NOM interactions was also observed when CBZ sorption was examined on partially hydrated NOM. In comparison with a smaller-size organic sorbate such as phenol, CBZ needs more NOM-associated water in order to demonstrate the strengthening of interactions with NOM. Therefore, for penetration of the larger sorbate molecules into the NOM interior, a greater number of water molecules are needed to compensate for the local NOM disintegration thus suggesting the greater extent of the cooperativity in an involvement of water molecules in the CBZ-NOM interactions.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

Phenanthrene sorption/desorption sequences provide new insight to explain high sorption coefficients in field studies

The sorption coefficients obtained in field investigation vary greatly from laboratory sorption experiments. The possible reasons were discussed in literature. Observing the commonly reported desorption hysteresis, this study proposed that the unclear sorption history of the field study could also result in the diverse sorption coefficients. This study conducted a comparative study regarding phenanthrene sorption/desorption behavior in low-concentration multi-time sorption process and the commonly applied high-concentration one-time sorption process. The sorption coefficients determined during the desorption process were much higher than those at sorption process. Thus, the prediction of sorption coefficient should be related with sorption history. Desorption hysteresis was increased with increased equilibration time and decreased solid-phase concentration. In addition, although the apparent contact time between sorbate and sorbent was shorter for low-concentration multi-time sorption, the desorption hysteresis was much stronger, which consequently result in higher sorption coefficients in comparison to high-concentration one-time sorption. Pore swelling or diffusion-controlled sorption kinetics could not explain this phenomenon. This study calls for research attention on sorption history, especially for field investigations.     

Sorption of phenanthrene by nanosized alumina coated with sequentially extracted humic acids

Background, aim, and scope  

Sorption of hydrophobic organic compounds (HOCs) to natural organic matter (NOM) is an important process that affects the transport, transformation, bioavailability, and fate of HOCs in the environment. Manufactured nanoparticles (NPs) such as nano-oxides will inevitably enter the environment in the processes of their production, transfer, and use and could be coated by the ubiquitous NOM. Thus, sorption of HOCs to NOM in the environment could be affected by the NP interactions with NOM. Furthermore, the toxicity of nano-oxides could be increased due to the adsorbed HOCs. Therefore, sorption of phenanthrene by nano-Al₂O₃ coated with humic acid (HA) was examined in this study to explore the possible effect of nanoparticles (NPs) on the environmental behavior of HOCs and the potential environmental and health risks of NPs.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.     

Sorption and desorption of glyphosate,MCPA and tetracycline and their mixtures in soil as influenced by phosphate

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg^?1) and elevated (81 to 99 mg kg^?1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.     

Soil remediation time to achieve clean-up goals II: Influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8-13 h) and decreased the remediation efficiency (RE) (99-90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8-4.9 h) and decreased the RE (99-97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.     

Characterization and Cu sorption properties of humic acid from the decomposition of rice straw

Humic acid (HA) derived from rice straw decomposed for 1 (HA-1), 3 (HA-3), 6 (HA-6) and 12 (HA-12) months was characterized by potentiometric titration and solid-state cross-polarization magic-angle spinning ¹³C nuclear magnetic resonance spectroscopy (CPMAS ¹³C NMR). The sorption of Cu on examined HA was investigated using a combination of batch sorption, isothermal titration calorimetry (ITC) and sequential desorption. Results showed that the functional group content and the humification degree of HA tended to increase with increasing decomposition time especially in the latter stage of examined decomposition period. Cu sorption on HA was a rapid process that occurred within the first 1 h and the sorption capacity increased from 245.4 mmol kg⁻¹ on HA-1 to 294.6 mmol kg⁻¹ on HA-12. The sorption of Cu was endothermic, spontaneous and the randomness was increased during Cu sorption. Sorbed Cu on examined HA can be hardly released by NH₄Ac but nearly fully released by EDTA. Forming inner-sphere complexes was the main mechanism of Cu sorption on examined HA. This study could provide valuable information for a better understanding on the environmental impacts of the decomposition of organic waste.