Linear Sorption Research Articles

Effects of accumulated straw residues on sorption of pesticides and antibiotics in soils with maize straw return

Outspread straw return practice leads to accumulation of structurally diverse organic materials in soils, including raw straw and straw residues. This practice provides a supplementary source of organic sorbents for compounds released into soils. However, effects of accumulated straw materials on sorption of compounds in soils remain poorly understood. Here we report that straw materials accumulated in soils display changing chemical structure and properties during decomposition, the majority of which distribute in exponential growth or decay manners with decomposition extents of materials. Sorption of straw materials toward 40 commonly used pesticides and antibiotics takes a compromise of decreasing crystalline index and increasing water absorption capacity of the sorbent materials during decomposition. This tradeoff in sorption leads to case-specific sorption trends of organic compounds in soils with straw return practice, following a composite linear sorption model of mixed soils and straw materials. The predictive model shows that relatively hydrophobic, hydrogen bond acceptor-rich chemicals (about 22.5% of the 40 compounds) display decreasing sorption capacity in organic matter-rich and/or relatively acidic soils with straw return. This finding may contradict the notion that crop straw return usually increases sorption and decreases leaching of compounds in soils.

The role of crystallinity and particle morphology on the sorption of dibutyl phthalate on polyethylene microplastics: Implications for the behavior of phthalate plastic additives

The sorption behavior of phthalate additives in plastic and microplastic litter is an important process controlling the exposure, net health risk and ecotoxicity of these co-occurring pollutants. Plastic crystallinity and particle morphology are hypothesized to be important variables for microplastics sorption behavior, but to date there have been few direct studies to explicitly test for the influence of these parameters. To address this, in this study we explored the sorption of dibutyl phthalate (DBP) as a probe molecule to diverse polyethylene microplastics including irregularly-shaped pure polyethylene microplastics (IPPM), black plastic film microplastics (BPFM), white plastic film microplastics (WPFM), and commercial microspheres (CM), which had crystallinities ranging from 17 to 99%. Sorption kinetics for all materials could be well represented with both a pseudo-first-order (R2 = 0.87–0.93) and pseudo-second-order model (R2 = 0.87–0.93). Further, sorption was highly linear in the concentration range of 0.5–10 mg L−1, with no greater performance from a linear sorption model (R2 = 0.96–0.99) than the non-linear Freundlich or Temkin sorption models. The partition coefficient (Kd) of DBP sorption onto IPPM, BPFM, WPFM and CMs were 1974.55 L kg−1, 1483.85 L kg−1, 1477.45 L kg−1 and 509.37 L kg−1, respectively, showing a significant decrease with increasing crystallinity (r2 = 0.98). The particle size of microplastics (27–1000 μm) is, however, an indecisive factor affecting their sorption behavior for DBP in this study. This study provides new insight that crystallinity plays a governing role on the sorption of phthalate from microplastic. This should be considered in future exposure studies and assessments of phthalates from plastics and microplastics.

Toxicity assessment of typical polycyclic aromatic hydrocarbons to Daphnia magna and Hyalella azteca in water-only and sediment–water exposure systems

While the equilibrium partitioning (EqP) method has been demonstrated to effectively predict the adverse effects of nonionic organic chemicals in sediment on benthic organisms by sediment toxicity tests, only a limited number of studies have been performed both in water-only and whole-sediment toxicity tests using the same species and verified the validity of EqP-based toxicity assessment. To further examine the validity of the EqP method for application in a wide range of hydrophobicity, we conducted sorption/desorption experiments and both water-only and sediment toxicity tests using a popular aquatic crustacean species, Daphnia magna (48 h), and benthic species Hyalella azteca (96 h) for six typical polycyclic aromatic hydrocarbons (PAHs) with three to five rings and an amine derivative: anthracene, phenanthrene, fluoranthene, pyrene, benzo[a]pyrene, dibenzo[a,h]anthracene, and 1-aminopyrene. The linear sorption coefficient was determined and ranged from 2.7 × 102 (phenanthrene) and 1.2 × 104 L/kg (benzo[a]pyrene) highly depending on the hydrophobicity while the aqueous concentrations were stable after 24 h in the desorption test. As result of acute toxicity tests in the water-only exposure system, anthracene and dibenz[a,h]anthracene were found to be nontoxic to both species, while median effect/lethal concentrations (EC50/LC50) were determined as ranging from 0.66 (benzo[a]pyrene) to 330 μg/L (phenanthrene), and from 11 (1-aminopyrene) to 180 μg/L (phenanthrene) for D. magna and H. azteca, respectively. Among these compounds, three PAHs with three, four, and five rings each, and 1-aminopyrene were subjected to sediment-water toxicity tests. In the sediment-water tests, the LC50 of phenanthrene and pyrene was three to six times higher than that of the water-only tests for H. azteca while the EC50 was 1.1 to 2.0 times higher for D. magna. In contrast, the EC50/LC50 of benzo[a]pyrene (BaP) in the sediment-water toxicity test was more than 5 times higher than that in the water-only test for both H. azteca and D. magna. The EC50/LC50 values of 1-aminopyrene were similar in both the sediment-water and the water-only toxicity tests, ranging narrowly from 21 to 28 μg/L and 8.8 to 11 μg/L for D. magna and H. azteca, respectively. The EC50/LC50 based on the body residue (ER50/LR50) was investigated for two of the representative PAHs, pyrene, and BaP. The ER50/LR50 of pyrene in both species was 2.3 and 11 times higher in the water-only toxicity test for D. magna and H. azteca, respectively, while those of BaP in the sediment-water toxicity test were not calculated for the sediment-water toxicity tests, and the highest body concentration in the sediment-water tests was lower than the ER50/LR50 in the water-only toxicity test. Although the experimental results were comparable with the predicted sediment toxicity values based on the EqP method for the selected PAHs in this study, there is a risk of phenanthrene and pyrene being slightly underestimated (1.4–1.9 fold for phenanthrene and 3.7–6.1 fold for pyrene) by the EqP method for H. azteca. These results reaffirm that the bioavailability of poorly water-soluble chemicals is important for sediment toxicity and that the exposure pathway should be further investigated to avoid under- and overestimation via the EqP method.

Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.

Sorption of anthracene (C14H10) and 9-anthroic acid (C15H10O2) onto biochar-amended soils as affected by field aging treatments

There is a lack of information on how aging affects the sorption of ionizable organic compounds on biochar-amended soils. To that end, this study investigates the sorption of two hydrophobic solutes (anthracene (ANT) and 9-anthroic acid (9-ANCA)) onto biochar-amended (5%, w/w) soils as a function of aging period (0, 6, and 12 months), electrolyte (5 mM CaCl2 and 10 mM KCl), and aqueous pH. The isotherm plot of both solutes was fairly linear (r2 > 0.998) and the linear sorption coefficient (Kd, L kg−1) was obtained from this. In CaCl2 solution at pH 5, the log Kd of ANT tended to decrease (from 3.90 to 3.72) with an increasing aging period, which was attributed to clogged pore surface, whereas the differences in 9-ANCA sorption (from 2.56 to 2.51) were not significant (α = 0.05). The increased ANT sorption at acidic pH (<4) could be attributed to π-π interaction. Aqueous Ca2+ ions played an important role in 9-ANCA sorption by forming a Ca-bridge between anionic solute and negatively charged adsorbent surface, thus accounting for up to 35% of its sorption at alkaline pH (>8). The spectroscopic data and isoelectric point measurement results indicated that the number of oxygen-containing functional groups and the content of elemental oxygen were both higher in aged samples, resulting in a more polar (negatively charged) surface. The formation of surface polar groups and the associated deformation altered the adsorbent nature of the tested biochar, thereby fortifying the hydrophilic retention propensity for ionizable organic solutes.

Study of 2D contaminant transport with depth varying input source in a groundwater reservoir

Abstract This study deals with a two-dimensional (2D) contaminant transport problem subject to depth varying input source in a finite homogeneous groundwater reservoir. A depth varying input source at the upstream boundary is assumed as the location of disposal site of the pollutant from where the contaminant enters the soil medium and ultimately to the groundwater reservoir. At the extreme boundary of the flow site, the concentration gradient of the contaminant is assumed to be zero. Contaminant dispersion is considered along the horizontal and vertical directions of the groundwater flow. The governing transport equation is the advection–dispersion equation (ADE) associated with linear sorption and first-order biological degradation. The ADE is solved analytically by adopting Laplace transform method. Crank–Nicolson scheme is also adopted for the numerical simulation of the modelled problem. In the graphical comparison of the analytical and numerical solutions, the numerical solution follows very closely with the analytical solution. Also, Root Mean Square (RMS) error and CPU run time are obtained to account for the performance of the numerical solution.

Utilization of factorial design methodology to optimize Pr Red Hegxl dye uptake and prediction of removal efficiency via artificial neural network: comparison of linear vs non-linear sorption isotherm and kinetic parameters

Utilization of factorial design methodology to optimize Pr Red Hegxl dye uptake and prediction of removal efficiency via artificial neural network: comparison of linear vs non-linear sorption isotherm and kinetic parameters

Fe(II) interaction with cement phases: Method development, wet chemical studies and X-ray absorption spectroscopy

Fe(II) interaction with cement phases was studied by means of co-precipitation and sorption experiments in combination with X-ray absorption fine structure (XAFS) spectroscopy. Oxidation of Fe(II) was fast in alkaline conditions and therefore, a methodology was developed which allowed Fe(II) to be stabilised in the sorption experiments and to prepare samples for spectroscopy. X-ray diffraction (XRD) of the co-precipitation samples showed uptake of a small portion of Fe(II) by calcium-silicate-hydrates (C-S-H) in the interlayer indicated by an increase in the interlayer spacing. Fe(II) incorporation by AFm phases was not indicated. Wet chemical experiments using 55Fe radiotracer revealed linear sorption of Fe(II) irrespective of the Ca/Si ratio of C-S-H and equilibrium pH. The Kd values for Fe(II) sorption on C-S-H are more than three orders of magnitude lower as compared to Fe(III), while they are comparable to those of other bivalent metal cations. XAFS spectroscopy showed Fe(II) binding by C-S-H in an octahedral coordination environment. The large number of neighbouring atoms rules out the formation of a single surface-bound Fe(II) species. Instead the data suggest presence of Fe(II) in a structurally bound entity. The data from XRD and XAFS spectroscopy suggests the presence of both surface- and interlayer-bound Fe(II) species.

Influence of metal cation and surface iron oxide on the transport of sulfadiazine in saturated porous media

Sulfadiazine (SDZ) is an antibiotic frequently detected in soil and groundwater. The transport of SDZ in subsurface environment is a critical process affecting its retention in soil. To date, the effects of iron oxide and metal cation on the transport of SDZ remain largely unknown, so we investigated the transport properties of SDZ in cleaned and iron oxides coated quartz sand, as affected by the presence of conventional cations (Ca2+, Mg2+, K+, and Na+) and Cd2+ through column experiments and simulation. We found that iron oxide coating on sand surface inhibited the transport of SDZ, mainly due to hydrophobic effect, complexation, and electrostatic attraction. The inhibitory effect became more marked with increasing concentration of Cd2+. It favors the transport of Cd2+ due to the electrostatic repulsion between positively charged iron oxide and Cd2+. Ca2+ promoted the transport of SDZ in coated sand, while all the conventional cations had no effect on the transport of SDZ in cleaned sand. The increase in the concentration of Cd2+ favors the transport of SDZ in cleaned sand. However, in iron oxide coated sand, the influence of Cd2+ on the transport of SDZ was dependent on the concentration of Cd2+. At lower concentration of Cd2+ and by competition, the transport is favored. At high concentration, the transport is inhibited mainly due to the formation of ternary surface complexes. A convective–dispersive transport model was applied to simulate and interpret experimental data. Breakthrough curves fitted well with a one-site model (OSM), indicating that SDZ adsorption on the sand experiences reversible kinetic. A low level of KF values with nearly linear sorption isotherm shows high mobility of SDZ and a high potential risk of surface and groundwater contamination. However, such high mobility can be reduced by increasing the content of iron oxides in porous media.

Modelling of Transportation Process in Plane Flows with Stagnation Points

We study transport of passive tracers by plane laminar flows with stagnation points. This setup serves as a simple model of transport in porous media. Close to stagnation points, the flow velocity is much lower than on the average. Many experimental data disclose that transport through porous media is slower than predictions of the standard advection-diffusion model. Commonly, in descriptions of flows through porous media the heterogeneity of flow is disregarded, and some average velocity is adopted. To model regular arrays of flow patterns with stagnation points, we employ the construction of special flow: a combination of mapping and a sort of ceiling function with singularity. We show that, depending on the type of stagnation points, many experimentally established effects can be reproduced. This includes the linear sorption, usually described by the standard MIM model, as well as subdiffusion, described by the fractional MIM model. We also show that slow molecular diffusion does not eliminate the effects of the transport slowdown.

Large-strain numerical solution for coupled self-weight consolidation and contaminant transport considering nonlinear compressibility and permeability

Based on the one-dimensional (1D) consolidation equation and advection-dispersion transport equation, this paper presents a large-strain numerical solution for coupled self-weight consolidation and contaminant transport in saturated deforming porous media considering nonlinear compressibility and permeability relationships. The finite difference method is used to solve the governing equations for consolidation and transport. The proposed numerical solution for consolidation accounts for vertical strain, soil self-weight, and nonlinearly changing compressibility and hydraulic conductivity during consolidation. The solution for solute transport accounts for advection, diffusion, mechanical dispersion, linear and nonlinear equilibrium sorption, and porosity-dependent effective diffusion coefficient. The proposed numerical solution is verified against a self-weight consolidation field tank test, an analytical solution in the literature, and the CST1 numerical model. Using the verified solution, a series of parametric study is conducted to investigate the effect of several important parameters on the contaminant transport process for confined disposal of dredged contaminated sediments. The results indicate that the consolidation process and contaminant transport process induced by soil self-weight- can be very different from those induced by the more traditional external surcharge loading. Treating the self-weight loading as traditional external surcharge loading can underestimate the rate of contaminant outflow, especially in the early times. The compressibility and permeability relationships of sediment and the type of loading (i.e., self-weight loading versus external surcharge loading) can all significantly affect the contaminant transport process for confined disposal of dredged contaminated sediment.

Modeling carbamazepine transport in wastewater‐irrigated soil under different land uses

The pharmaceutical compound carbamazepine (CBZ) is a contaminant of emerging concern. Wastewater irrigation can be a long-term, frequent source of CBZ; therefore, understanding the fate and transport of CBZ as a result of wastewater reuse practices has important environmental implications. The objective of this study was to estimate long-term soil transport of CBZ originating from treated wastewater irrigation on plots under different land uses. Field data from a previous study comparing CBZ concentrations in soil under different land uses were used in numerical modeling with HYDRUS-2D for the estimation of CBZ soil transport during 20 yr of irrigation with treated wastewater. This study showed high CBZ retention in soil under all investigated land uses. Adequate modeling results were obtained by using soil organic carbon-water partitioning coefficient (Koc ) for the CBZ linear sorption coefficient (Kd ) estimation, yet an underestimation of CBZ concentration in soil was still noted. Thus, results suggest that, although highly important, organic carbon content is probably not the only soil property governing CBZ sorption at this site, indicating the potential research perspective. Modeling results showed wastewater irrigation containing CBZ for 20 yr increased the CBZ concentration in the soil profile and its vertical movement, with the slowest vertical transport rate occurring on the forested plots. Overall results suggest that a beneficial management practice could be to increase soil organic carbon (e.g., compost addition) when using treated wastewater for irrigation in order to retain CBZ in the surface soil and thus limit its leaching through the soil profile.

Sorption and desorption of seven steroidal synthetic progestins in five agricultural soil-water systems.

Manure fertilization and wastewater irrigation can introduce the biologically potent synthetic progestins into agricultural soils, causing endocrine disruption in organisms of nearby surface waters. Therefore, this study investigated the sorption and desorption potential of etonogestrel, medroxyprogesterone, gestodene, norgestrel, cyproterone acetate, levonorgestrel, and dienogest in five agricultural soil-water systems. Sorption data were well-described by the linear sorption model. In most batch systems, cyproterone acetate exhibited the highest affinities for soils, followed by etonogestrel, medroxyprogesterone, levonorgestrel, gestodene, norgestrel, and dienogest. The sorption magnitudes (logKoc or logKd) were significantly correlated with the progestin hydrophobicities (R2=0.72-0.86, p<0.05). The Kd values of the progestins were also significantly correlated with organic carbon content and pore volumes of the soils (R2=0.68-0.98, p<0.05). In addition, 0.5M urea resulted in 3-19% decreases in Kd values of the progestins. Taken together, these data indicated that hydrophobic partitioning interaction, hydrogen bonding interaction, and pore filling were the sorption mechanisms for the progestins in soil-water systems. No significant desorption hysteresis was observed for the progestins, indicating that they can be readily desorbed under rainfall or irrigation events. Based on the sorption and desorption data, we estimated the dynamic transport of the progestins in conventional agricultural management systems, and predicted the concentrations of the progestins as a function of soil-sorbed concentration, water-soil ratio, and dilution factor of receiving waters. This study will improve the understanding of the risks posed by the progestins under field-scale hydrological conditions.

Fate of the nonsteroidal, anti-inflammatory veterinary drug flunixin in agricultural soils and dairy manure.

A large percentage of flunixin, a nonsteroidal anti-inflammatory drug widely used for treating livestock, is excreted in intact form and thus potentially available for environmental transport. As the fate of flunixin in the environment is unknown, our objective was to quantify sorption, desorption, and transformation in five agricultural soils and manure using batch equilibrium methods. Concentrations of flunixin and degradation products were determined by high performance liquid chromatography time of flight mass spectrometry. For all studied soils, sorption of flunixin exhibited linear character, with both linear and Freundlich models providing adequate fit. Linear sorption coefficients varied from 8 to 112Lkg-1. The strongest Pearson correlations with sorption coefficients were for clay content (r = 0.8693), total nitrogen (r = 0.7998), and organic carbon (r = 0.6291). Desorption of the reversibly bound fraction (3-10% of total sorbed flunixin) from all five studied soils exhibited non-hysteretic character suggesting low affinity of this fraction of flunixin to soil. Flunixin degradation in soils was relatively slow, exhibiting half-lives of 39-203days, thus providing time for off-site transport and environmental contamination. The biological impacts of flunixin at environmentally relevant concentrations must be determined given its environmental behavior and extensive use as a nonsteroidal anti-inflammatory drug in livestock. Graphical abstract.

Estimating the transport parameters of propyphenazone, caffeine and carbamazepine by means of a tracer experiment in a coarse-gravel unsaturated zone

Among the emerging contaminants today, pharmaceuticals are some of the most demanding chemical compounds when it comes to understanding their transport within aquifers. The transport of pharmaceuticals in an unsaturated zone is influenced by many factors, including compound sorption and degradation, which is essential in assessing contaminant migration in soil and groundwater. Coarse-gravel aquifers are particularly important for drinking water sources and industrial water supply. Globally, little data on the transport characteristics of coarse-gravel unsaturated zones is available. However, such data is crucial to understanding the transport of pollutants and to implementing the appropriate management strategies to protect the aquifers. In this article, we present tracer experiments employed to determine pharmaceutical transport parameters in the coarse-gravel unsaturated zone. The tracer experiment was performed as a multi-tracer exercise, where deuterated water was infiltrated as a conservative tracer to define the characteristics of the unsaturated zone, together with pharmaceuticals (propyphenazone, caffeine and carbamazepine) as reactive tracers. Based on the breakthrough curves measured at various depths, inverse modelling in combination with analytical and numerical methods (HYDRUS-1D) was performed. Hydraulic parameters for the unsaturated zone were estimated. Linear sorption coefficients (Kd) and degradation half-lives (t1/2) were evaluated for each pharmaceutical. In the unsaturated zone of the coarse-gravel aquifer caffeine has the lowest sorption capacity (mean Kd = 0.027 Lkg-1), while the sorption coefficient of propyphenazone is higher (Kd = 0.07 Lkg-1). Results for the degradation constant of the first order and t1/2 indicate that caffeine has the fastest decay rate (highest t1/2 = 69.3 days), followed by propyphenazone (highest t1/2 = 92.4 days). The parameters for carbamazepine could not be determined using an advection dispersion equation.

Controls of fluorescent tracer retention by soils and sediments

Abstract. Fluorescent dyes like uranine (UR) and sulforhodamine B (SRB) have been used for decades as artificial tracers in hydrological studies. Recently, attempts have been made to trace organic pollutants in soil with such dyes, but the knowledge of the controls of sorption of UR and SRB in soils is still incomplete and poorly standardised. For this reason, we selectively controlled clay, organic matter (OM) and pH within batch experiments and quantified systematically the impact and possible interactions of these controls on the adsorption of UR and SRB. Sorption isotherms were determined using a sandy sediment and a silty loamy subsoil and topsoil (0.6–2.8 % organic carbon (OC)) at pH values of 5.5, 6.5 and 7.5. Additionally, OM was removed from topsoil and subsoil samples by H2O2 treatment and the clay mineral montmorillonite was added to the sandy sediment. We found a negative relationship between the linear sorption coefficient Kd and pH that was stronger for UR than for SRB. Increasing repulsion forces between negative sorption sites and tracer functional groups at higher pH values might explain these results. Adsorption of UR and SRB increased with increasing clay content due to more specific surface area and associated sorption sites. An addition of 4 % of the clay mineral montmorillonite sufficed to adsorb nearly 100 % of both tracers. The influence of OM was more complex: while the adsorption of UR increased with increasing OC concentration, the opposite was observed for SRB. Our study indicates the high relevance of physico-chemical properties of soils and sediments for the fate of applied tracers and for their more conservative or non-conservative behaviour. Overall, the reported results will help to optimise the use of fluorescent tracers in terrestrial ecosystems and to increase their potential as a cheap and fast tool to gain insights into the fate of pollutants in soils and sediments.

Subsurface Based Contaminant Transport Modelling of SDS Nac12h25so4

Subsurface contamination by emerging contaminants from inappropriate effluent discharge is one of the serious issues directly affecting the quality of groundwater. This study is aimed at transport and transformations of anionic surfactant (SDS). Sodium Dodecyl Sulfate [NaC12H25SO4 ] from grey wastewater containing detergents in unsaturated soils and its impacts on groundwater. HYDRUS-1D model to predict the transport mechanisms was developed. In this regard, surfactant concentrations for SDS from the sewage treatment plant of KCET, Virudhunagar was taken for evaluation. This research work reveals that inlet, outlet, sludge with ample quantities of SDS concentrations (13, 9.55 and 15.67 mg/L). Soil irrigated with sewage was taken as primary sample. Soil column experiments were conducted first with tracer to calculate the dispersion at a flow rate of 1 cm/h, estimated to be 3.1cm. A series of transport experiments were started with 10 mg/L of SDS to comprehend the sorption tied biodegradation. It was observed that leaching phenomenon was the dominant process when compared to biodegradation and sorption. An initial concentration of 13.44 mg/L was administered and found 12 mg/L at the outlet. Hence, 1.44 mg/L underwent sorption and biodegradation. The model estimated linear sorption parameter with first order degradation coefficient 0.131cc/g and 0.01/h. The calibrated HYDRUS model was adopted to study the various scenarios with GWT depth of 30 m. The simulated SDS concentration at GWT of 30m is 4.13mg/litre.

Application of analytical solution of advection-dispersion-reaction model to predict the breakthrough curve and mass transfer zone for the biosorption of heavy metal ion in a fixed bed column

This work aims to apply an analytical solution of the contaminant transport model to predict the sorption's breakthrough curve and mass transfer zone of single component heavy metal ions using green macroalga, Caulerpa lentillifera, in a small scale cylindrical fixed-bed columns. The model was represented in a form of differential equation with two model constants which were diffusion coefficient (Deff) and linear sorption coefficient (kp). The linear isotherm could be well described for the sorption at a lower range of sorbate concentration while the Langmuir isotherm was suitable for a wider range of concentration. The reference set of experiments (with a bed depth of 4cm and a flow rate of 6mL/min) were used for calibrating the model to obtain the model constants. The model could be well applied to predict the breakthrough curve of varying bed depth from the reference set of experiments for the sorption of Pb2+ and Cd2+. However, the model predicts slower breakthrough time than that in the experimental results when the flow rate is changed from the reference set of experiments. Three-dimensional plots and contour plots were generated to analyze the sorption behavior of metal ion in the column. The relationship between bed depth and service time (BDST) obtained from the model in this work is not linear, as often seen in the general BDST model. Both advection and dispersion processes govern the sorbate transport in the column. The mass transfer zone (MTZ) is continuously expanding along with the column length in this study. The relationship between MTZs and bed depth is also not linear.

Predicting Solute Transport Parameters in Saturated Porous Media Using Hybrid Algorithm

This study aims to estimate the solute transport parameters in saturated porous media using a hybrid algorithm. In this study, the Physical Non-Equilibrium (PNE) model was used to describe the transport of solutes in porous media. A numerical solution for the PNE model is obtained using the Finite Volume Method (FVM) based on the Ttri-Diagonal Matrix Algorithm (TDMA). The developed program, written in Matlab, is capable to solve the advection-dispersion (ADE) and the PNE equations for the mobile -immobile (MIM)model with linear sorption isotherm. The Solute transport parameters, (immobile water content, mass transfer coefficient, and dispersion coefficient), are estimated using different algorithms such as the Levenberg-Marquardt algorithm (LM), genetic algorithm (GA), simulated annealing algorithm (SA). To overcome the limitations of deterministic optimization models which are rather unstable and divergent around a local minimum, a hybrid algorithm (GA+LM, SA+LM) permits to estimate of the solute transport parameters. Numerical solutions are verified using the experiments conducted by Semra (2003) which are about the transport of toluene through a column composed of impregnated Chromosorb grains at ambient temperature (20 °C) for three flow rates (1, 2 and 5ml/min). The results show that the hybrid algorithm (GA+LM, SA+LM) is more accurate than others (GA, SA, and LM). Comparing to the ADE model, The PNE with linear isotherm model gives a better description to the BeakThrough Curves (BTCs) with higher values of determination coefficient (R2) and lower values of Root Mean Square Error (RMSE). Also, the solute transport parameters tended to vary with the flow rate.

Sorption of oxytetracycline in particulate organic matter in soils and sediments: Roles of pH, ionic strength and temperature

Particulate organic matter (POM) is a fraction of organic matter with dissimilar properties in different soils. POM isolated from soils and sediments (wetland, oil waste field, farmlands and aquaculture pond sediment) was used to study its sorption behavior on the antibiotic oxytetracycline (OTC). Impacts of solution pH, ionic strength and temperature on the OTC sorption were studied. The sorption rates of OTC in POM from wetland (POM-w) and farmland (POM-f1, POM-f2) were rapid during the first 3 h and gradually decreased with reaction time until reaching the equilibrium. Linear sorption occurred from 3 to 12 h in POM from oil waste field land (POM-o) and aquaculture pond sediment (POM-a). The organic carbon normalized partition coefficient (koc) varied from 215.0 to 4493.6 L kg−1, and it was nearly 10× higher for the POM-w, POM-f1 and POM-f2 than in the POM-o and POM-a. Sorption of OTC by POM exhibited strong pH dependence. Ionic factors affected OTC sorption in POM-f1, POM-f2 and POM-a. The sorption capacity declined >50% in a solution with Ca2+ compared to other ions with similar ionic strength. Sorption thermodynamics showed an entropy increasing and endothermic progress during the OTC sorption in POM, implying a spontaneous sorption process. Several mechanisms were involved in OTC sorption in POM, including hydrogen bonding, cation exchange, hydrophobic partitioning and surface complexation.