Preparation of Magnetic Hydroxyapatite and Their Use as Recyclable Adsorbent for Phenol in Wastewater

Magnetic hydroxyapatite (HAP), which combined superparamagnetic Fe₃O₄ nanoparticles and HAP, composite materials were prepared by ultrasound method in this paper. It has also been found that these materials have the ability to adsorb phenol in wastewater. The magnetic materials were investigated by scanning electron microscope, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, thermal gravimetric analysis, vibrating sample magnetometer, and N₂ adsorption in order to elucidate the morphology, structure, and other properties. When the prepared magnetic materials were calcined at 200°C, the prepared Fe₃O₄ was oxidized to Fe₂O₃, possessing loose‐shaped holes with a high specific area of 325.2 m²/g, a magnetization intensity of 12.5 emu/g, and the N₂ adsorption isotherm belongs to porous adsorption type I. Moreover, the magnetic HAP can adsorb 90% phenol in wastewater. This means that it is an excellent recyclable phenol sorbent for sewage treatment. Experiments confirmed that the Freundlich adsorption isotherms model applies to lower phenol concentrations (0–50 mg/L), while for high phenol concentrations (50–500 mg/L) the Langmuir adsorption isotherms model fits. The magnetic sorbents have the capacity to regenerate after reaching adsorption saturation using ethanol as eluant and external magnetic field as separation unit. The efficiency of adsorption was reduced only by 10% over a six time use period.     

Lapse time and frequency-dependent attenuation characteristics of coda waves in the Northwestern Himalayas

We analyzed the local earthquakes waveform recorded on a broadband seismic network in the northwestern Himalayan Region to compute lapse time and frequency dependence of coda Q (Q _c). The observed Q _c values increase with increasing lapse time at all frequency bands. The increase in Q _c values with lapse time is attributed to an increase in Q _c with depth. This implies that attenuation decreases with increasing depth. The approximate radius of medium contributing to coda generation varies from 55 to 130 km. By comparing the Q _c values with those from other regions of the world, we find that they are similar to those obtained from tectonically active regions. The estimated Q _c values show a frequency-dependent relationship, Q _c = Q ₀ f ⁿ , where Q ₀ is Q _c at 1 Hz and n represents degree of frequency dependence. They represent the level of heterogeneity and tectonic activity in an area. Our results show that northwest Himalayas are highly heterogeneous and tectonically very active. Q ₀ increases from 113 ± 7 to 243 ± 10 and n decreases from 1.01 ± 0.05 to 0.85 ± 0.03 when lapse time increases from 30 to 70 s. As larger time window sees the effect of deeper part of the Earth, it is concluded that Q ₀ increases and n decreases with increasing depth; i.e., heterogeneity decreases with depth in the study area.     

Solute movement through intact columns of cryoturbated Upper Chalk

Cryoturbated Upper Chalk is a dichotomous porous medium wherein the intra‐fragment porosity provides water storage and the inter‐fragment porosity provides potential pathways for relatively rapid flow near saturation. Chloride tracer movement through 43 cm long and 45 cm diameter undisturbed chalk columns was studied at water application rates of 0·3, 1·0, and 1·5 cm h^?1. Microscale heterogeneity in effluent was recorded using a grid collection system consisting of 98 funnel‐shaped cells each 3·5 cm in diameter. The total porosity of the columns was 0·47 ± 0·02 m³ m^?3, approximately 13% of pores were ≥ 15 µm diameter, and the saturated hydraulic conductivity was 12·66 ± 1·31 m day^?1. Although the column remained unsaturated during the leaching even at all application rates, proportionate flow through macropores increased as the application rate decreased. The number of dry cells (with 0 ml of effluent) increased as application rate decreased. Half of the leachate was collected from 15, 19 and 22 cells at 0·3, 1·0, 1·5 cm h^?1 application rates respectively. Similar breakthrough curves (BTCs) were obtained at all three application rates when plotted as a function of cumulative drainage, but they were distinctly different when plotted as a function of time. The BTCs indicate that the columns have similar drainage requirement irrespective of application rates, as the rise to the maxima (C/C_o) is almost similar. However, the time required to achieve that leaching requirement varies with application rates, and residence time was less in the case of a higher application rate. A two‐region convection–dispersion model was used to describe the BTCs and fitted well (r² = 0·97–0·99). There was a linear relationship between dispersion coefficient and pore water velocity (correlation coefficient r = 0·95). The results demonstrate the microscale heterogeneity of hydrodynamic properties in the Upper Chalk. Copyright © 2007 John Wiley & Sons, Ltd.     

Transect study on solute transport in a macroporous soil

Solute transport experiments using a non-reactive tracer were conducted on short, undisturbed, saturated columns of a sandy loam soil. All columns, 20 cm in diameter and 20 cm long, were collected along a transect of 35 m. Most of the soil columns had pre-existing macropores. The columns were leached at a steady flow-rate under ponding conditions. The resulting breakthrough curves (BTCs) showed a large heterogeneity. Several of the BTCs displayed early breakthrough and long tailing. All the data were interpreted in terms of dimensional time moments, the classical convection-dispersion equation (CDE) and the mobile-immobile transport model (MIM). Experimental time moments were found to vary significantly among the different BTCs. Analysis of the time moments also revealed that the variance of the field-scale BTC was several times larger than the average of the local-scale variance. The pore water velocity v and dispersion coefficient D were obtained by fitting the CDE to the local-scale BTCs, resulting in an average dispersivity of 7·4 cm. Frequency distributions for the CDE parameters v and D were equally well described by a normal or log-normal probability density function (pdf). When a log-normal pdf for D is considered, the variance of the log_e transformed D values (σ_{ln D}²) was found to be 2·1. For the MIM model, two additional parameters were fitted: the fraction of mobile water, θ_m/θ, and the first-order mass transfer coefficient, α. The MIM was more successful in describing the data than the CDE transport model. For the MIM model, the average dispersivity was about 2 cm. The MIM parameters v, D and θ_m/θ were best described by a log-normal pdf rather than a normal pdf. Only the parameter α was better described by a normal pdf. Mobile water fractions, θ_m/θ ranged from 0·01 to 0·98, with a mean of 0·43 (based on a log-normal pdf). When the CDE and MIM were applied to the data, the fitted pore water velocities, v, compared favourably with the effective pore water velocities, v_eff, obtained from moment analysis.     

Inhibition Concentration of Phenolic Substances under Different Cultivation Conditions. Part I: Phenol Oxidation by Mixed Microbial Population in a Model System

The effects of oxygen supply rate and the presence or absence of nutrients on the kinetics of phenol degradation and oxygen consumption by a mixed microbial population were tested in a model system. The values for the maximum specific rate of phenol degradation (q_Smax), the saturation constant (K_S), and the inhibition concentration (S_CR) were determined for unlimited growth (K_La = 340 h^?1, growth medium) with 1.7 mmol g^?1 h^?1, 65 mg L^?1, and 190 mg L^?1. Under limitation conditions, alterations occur depending on the type of limitation. Nutrient limitations lead to values of 0.8 mmol g^?1 h^?1, 45 mg L^?1, and 160 mg L^?1, and oxygen limitations lead to 1.2 mmol g^?1 h^?1. 30 mg L^?1, and 120 mg L^?1, respectively. The results suggest that with excess oxygen, the rate of phenol degradation was higher and the inhibition effect of phenol was suppressed to some extent. Under the same high oxygen supply rate, the presence of nutrients in the model water significantly supported the phenol degradation rate.     

The Adsorption Behavior of Functional Particles Modified by Polyvinylimidazole for Cu(II) Ion

In this paper, a novel composite material the silica grafted by poly(N‐vinyl imidazole) (PVI), i.e., PVI/SiO₂, was prepared using 3‐methacryloxypropyl trimethoxysilane (MPS) as intermedia through the “grafting from” method. The adsorption behavior of metal ions by PVI/SiO₂ was researched by both static and dynamic methods. Experimental results showed that PVI/SiO₂ possessed very strong adsorption ability for metal ions. For different metal ions, PVI/SiO₂ exhibited different adsorption abilities with the following order of adsorption capacity: Cu²⁺ > Cd²⁺ > Zn²⁺. The adsorption material PVI/SiO₂ was especially good at adsorbing Cu(II) ion and the saturated adsorption capacity could reach up to 49.2 mg/g. The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. Higher temperatures facilitated the adsorption process and thus increased the adsorption capacity. The pH and grafting amount of PVI had great influence on the adsorption amount. In addition, PVI/SiO₂ particles had excellent eluting and regenerating property using diluted hydrochloric acid solution as eluent. The adsorption ability trended to steady during 10 cycles.     

Study of the Contributions of Non‐Specific and Specific Interactions during Fluoxetine Adsorption onto Activated Carbons

The adsorption of fluoxetine onto activated carbons (ACs) prepared from almond tree pruning by steam and CO₂ activation under different temperature conditions (650–950°C), was studied. In both series increasing the temperature caused an increase in the BET apparent surface area, yielding ACs with S_BET up to 870 and 710 m² g^?1 after steam and CO₂ activation, respectively. Also, a slight widening of the porosity was found in both cases. In order to modify the functionality of the ACs, two of them were impregnated with triethylenediamine (TEDA) prior to the adsorption process, which caused a decrease in the AC apparent surface mainly due to micropore blockage. The fluoxetine adsorption isotherms at 25°C showed maximum adsorption capacities between 110 and 224 mg g^?1. The adsorption isotherms were analyzed using Langmuir and Freundlich models. Although the impregnation reduced the pore volume, it did not cause a decrease in the fluoxetine maximum adsorption capacity, but a modification in the adsorption mechanism was observed.     

Bias of Apparent Tracer Ages in Heterogeneous Environments

The interpretation of apparent ages often assumes that a water sample is composed of a single age. In heterogeneous aquifers, apparent ages estimated with environmental tracer methods do not reflect mean water ages because of the mixing of waters from many flow paths with different ages. This is due to nonlinear variations in atmospheric concentrations of the tracer with time resulting in biases of mixed concentrations used to determine apparent ages. The bias of these methods is rarely reported and has not been systematically evaluated in heterogeneous settings. We simulate residence time distributions (RTDs) and environmental tracers CFCs, SF₆, ⁸⁵Kr, and ³⁹Ar in synthetic heterogeneous confined aquifers and compare apparent ages to mean ages. Heterogeneity was simulated as both K‐field variance (σ²) and structure. We demonstrate that an increase in heterogeneity (increase in σ² or structure) results in an increase in the width of the RTD. In low heterogeneity cases, widths were generally on the order of 10 years and biases generally less than 10%. In high heterogeneity cases, widths can reach 100 s of years and biases can reach up to 100%. In cases where the temporal variations of atmospheric concentration of individual tracers vary, different patterns of bias are observed for the same mean age. We show that CFC‐12 and CFC‐113 ages may be used to correct for the mean age if analytical errors are small.     

Exchangeable Characteristics of Potassium in Five Important Soils of Taiwan

The application of potassium fertilizer by farmers is often not appropriate and causing environmental pollution. By understanding the adsorptive characteristics of potassium (K) on different soils, we can prevent excessive application of K‐fertilizer that can cause environmental impact. The Gapon exchange coefficient (K_G), for exchange between K and Ca, was considered as an important factor influencing the adsorption of K. This study was conducted to compare the constant K_G of five important farm soils in Taiwan. The K_G and CEC were then used to predict K buffering capacity (PBC). Finally, the relationship between exchangeable K ratio (E_P) and K adsorption ratio (PAR) was examined. The results show that five soils have same trends, indicating that K_G decreases with increase in K saturation. The CEC and K_G of Liuying (Ly) soil are both high, so that their K buffering capacity is high. The K_G and CEC of Chanjing (Cj) and Sanhua (Sh) soil show moderate values. The CEC of Erling (El) soil is high, but its K_G is low, so that its K buffering capacity is moderate. On the other hand, the K_G of Newniaokang (Nnk) soil is high but its CEC is low, so its K buffering capacity is also moderate. The correlations between E_P and PAR of five soil show linear relationship at three treatments of CaCl₂ concentration. This study may provide an important clue to the fertilization management of K‐fertilizer on the different soil properties in Taiwan.     

Attenuation characteristics of Garwhal–Kumaun Himalayas from analysis of coda of local earthquakes

Coda of local earthquakes that occurred during 2006–2007 are used to study the attenuation characteristics of the Garhwal–Kumaun Himalayas. The coda attenuation characteristics are represented in terms of coda Q or Q _c . It is observed that Q _c increases with frequency. Q _c also varies with increase in lapse time of coda waves. Q _c increases up to an 85-s average lapse time. This is similar to observations around the world reported by many workers who have interpreted this as a manifestation of the fact that heterogeneity decreases with depth. However, around a 90-s average lapse time Q _c is lower than its values for lower and higher average lapse times. This is interpreted as an indication of possible presence of a fluid-filled medium or a medium having partial melts at around a 160-km depth. Q ₀, i.e., Q _c at 1 Hz, increases, and frequency parameter n decreases with increasing lapse time, barring around a 90-s lapse time. This again shows that in general, heterogeneity decreases with increasing depth. The Q ₀ and n values for smaller lapse times are similar to those for tectonically active areas. By comparing Q _c values obtained in this study with those obtained by us using the 1999 Chamoli earthquake aftershocks, it is concluded that the crust is turbid and the mantle is more transparent. However, whether the variation in Q _c values between 1999 and 2006–2007 is temporal or not cannot be definitely established from the available data set.     

Removal of Copper,Nickel and Zinc Ions from Aqueous Solution by Chitosan‐8‐Hydroxyquinoline Beads

In this work, 8‐hydroxyquinoline is used as the active sites in cross‐linked chitosan beads with epichlorohydrin (CT‐8HQ). The CT‐8HQ material was shaped in bead form and used for heavy metal removal from aqueous solution. The study was carried out at pH 5.0 with both batch and column methods and the maximum adsorption capacity of metal ions by the CT‐8HQ was attained in 4 h in the batch experiment. The adsorption capacity order was: Cu²⁺ > Ni²⁺ > Zn²⁺ for both mono‐ and multi‐component systems with batch conditions. From breakthrough curves with column conditions, the adsorption capacity followed the order Cu²⁺ > Zn²⁺ > Ni²⁺ for both mono‐ and multi‐component systems. The CT‐8HQ beads maintained good metal adsorption capacity for all five cycles with absorbent restoration achieved with the use of 1.0 mol L^–1 HCl solution, with 90% regeneration.     

Quantification of longitudinal dispersion by upscaling Brownian motion of tracer displacement in a 3D pore-scale network model

We present a 3D network model with particle tracking to upscale 3D Brownian motion of non-reactive tracer particles subjected to a velocity field in the network bonds, representing both local diffusion and convection. At the intersections of the bonds (nodes) various jump conditions are implemented. Within the bonds, two different velocity profiles are used. At the network scale the longitudinal dispersion of the particles is quantified through the coefficient D_L, for which we evaluate a number of methods already known in the literature. Additionally, we introduce a new method for derivation of D_L based on the first-arrival times distribution (FTD). To validate our particle tracking method, we simulate Taylor’s classical experiments in a single tube. Subsequently, we carry out network simulations for a wide range of the characteristic Péclet number Pe_? to assess the various methods for obtaining D_L. Using the new method, additional simulations have been carried out to evaluate the choice of nodal jump conditions and velocity profile, in combination with varying network heterogeneity. In general, we conclude that the presented network model with particle tracking is a robust tool to obtain the macroscopic longitudinal dispersion coefficient. The new method to determine D_L from the FTD statistics works for the full range of Pe_?, provided that for large Pe_? a sufficiently large number of particles is used. Nodal jump conditions should include molecular diffusion and allow jumps in the upstream direction, and a parabolic velocity profile in the tubes must be implemented. Then, good agreement with experimental evidence is found for the full range of Pe_?, including increased D_L for increased porous medium heterogeneity.     

One-dimensional solute dispersion along unsteady flow through a heterogeneous medium,dispersion being proportional to the square of velocity

Abstract

One-dimensional solute transport, originating from a continuous uniform point source, is studied along unsteady longitudinal flow through a heterogeneous medium of semi-infinite extent. Velocity is considered as directly proportional to the linear spatially-dependent function that defines the heterogeneity. It is also assumed temporally dependent. It is expressed in both the independent variables in degenerate form. The dispersion parameter is considered to be proportional to square of the velocity. Certain new independent variables are introduced through separate transformations to reduce the variable coefficients of the advection–diffusion equation to constant coefficients. The Laplace Transformation Technique (LTT) is used to obtain the desired solution. The effects of heterogeneity and unsteadiness on the solute transport are investigated.

Editor D. Koutsoyiannis; Associate editor F.F. Hattermann

Citation Kumar, A., Jaiswal, D.K., and Kumar, N., 2012. One-dimensional solute dispersion along unsteady flow through a heterogeneous medium, dispersion being proportional to the square of velocity. Hydrological Sciences Journal, 57 (6), 1223–1230.     

Effective dispersion in a chemically heterogeneous medium under temporally fluctuating flow conditions

We investigate effective solute transport in a chemically heterogeneous medium subject to temporal fluctuations of the flow conditions. Focusing on spatial variations in the equilibrium adsorption properties, the corresponding fluctuating retardation factor is modeled as a stationary random space function. The temporal variability of the flow is represented by a stationary temporal random process. Solute spreading is quantified by effective dispersion coefficients, which are derived from the ensemble average of the second centered moments of the normalized solute distribution in a single disorder realization. Using first-order expansions in the variances of the respective random fields, we derive explicit compact expressions for the time behavior of the disorder induced contributions to the effective dispersion coefficients. Focusing on the contributions due to chemical heterogeneity and temporal fluctuations, we find enhanced transverse spreading characterized by a transverse effective dispersion coefficient that, in contrast to transport in steady flow fields, evolves to a disorder-induced macroscopic value (i.e., independent of local dispersion). At the same time, the asymptotic longitudinal dispersion coefficient can decrease. Under certain conditions the contribution to the longitudinal effective dispersion coefficient shows superdiffusive behavior, similar to that observed for transport in s stratified porous medium, before it decreases to its asymptotic value. The presented compact and easy to use expressions for the longitudinal and transverse effective dispersion coefficients can be used for the quantification of effective spreading and mixing in the context of the groundwater remediation based on hydraulic manipulation and for the effective modeling of reactive transport in heterogeneous media in general.     

Effect of pH on Adsorption Equilibria for Dissolved Weak Organic Electrolytes on Activated Carbon

The influence of pH on the adsorption equilibria of a-picolin and phenol from aqueous solution on activated carbon is studied experimentally for the single solutes and their mixtures. For these weak bases and weak acids the effect of pH on adsorption capacity is contrary, thus allowing an efficient separation by adsorption. A model based on the concept of competitive adsorption of ionic and molecular forms of the organic electrolytes represents the experimental data qualitatively. Deviations between theoretical and experimental results are discussed on the basis of possible interactions of the organic solutes and the activated carbon with components of the buffer used in the experiments.     

Modeling Transient Streaming Potentials in Falling‐Head Permeameter Tests

We present transient streaming potential data collected during falling‐head permeameter tests performed on samples of two sands with different physical and chemical properties. The objective of the work is to estimate hydraulic conductivity (K) and the electrokinetic coupling coefficient (C_l) of the sand samples. A semi‐empirical model based on the falling‐head permeameter flow model and electrokinetic coupling is used to analyze the streaming potential data and to estimate K and C_l. The values of K estimated from head data are used to validate the streaming potential method. Estimates of K from streaming potential data closely match those obtained from the associated head data, with less than 10% deviation. The electrokinetic coupling coefficient was estimated from streaming potential vs. (1) time and (2) head data for both sands. The results indicate that, within limits of experimental error, the values of C_l estimated by the two methods are essentially the same. The results of this work demonstrate that a temporal record of the streaming potential response in falling‐head permeameter tests can be used to estimate both K and C_l. They further indicate the potential for using transient streaming potential data as a proxy for hydraulic head in hydrogeology applications.     

The stability of density-driven flows in saturated heterogeneous porous media

This work concludes the investigations into the stability of haline flows in saturated porous media. In the first part [33] a stability criterion for density-driven flow in a saturated homogeneous medium was derived excluding dispersion. In the second part [34], the effects of dispersion were included. The latter criterion made reasonable predictions of the stability regimes (indicated by the number of fingers present) as a function of density and dispersivity variations. We found out that destabilising variables caused an increase in the number of fingers and vice versa. The investigation is extended here for the effects of the medium heterogeneity. The cell problem derived via homogenization theory [20] is solved and its solution used to evaluate the elements of the macrodispersion tensor as functions of time for flow aligned parallel to gravity. The longitudinal coefficient exhibits asymptotic behaviour for favourable and moderately unfavourable density contrasts while it grows indefinitely for higher density contrasts. The range of densities stabilised by medium heterogeneities can thus be estimated from the behaviour of the coefficient. The d³f software program is used for the numerical simulations. The code uses the cell-centred finite volume and the implicit Euler techniques for the spatial and temporal discretisations respectively.     

Field Study of Subsurface Heterogeneity with Steady‐State Hydraulic Tomography

Remediation of subsurface contamination requires an understanding of the contaminant (history, source location, plume extent and concentration, etc.), and, knowledge of the spatial distribution of hydraulic conductivity (K) that governs groundwater flow and solute transport. Many methods exist for characterizing K heterogeneity, but most if not all methods require the collection of a large number of small‐scale data and its interpolation. In this study, we conduct a hydraulic tomography survey at a highly heterogeneous glaciofluvial deposit at the North Campus Research Site (NCRS) located at the University of Waterloo, Waterloo, Ontario, Canada to sequentially interpret four pumping tests using the steady‐state form of the Sequential Successive Linear Estimator (SSLE) ( Yeh and Liu 2000 ). The resulting three‐dimensional (3D) K distribution (or K‐tomogram) is compared against: ( 1 ) K distributions obtained through the inverse modeling of individual pumping tests using SSLE, and ( 2 ) effective hydraulic conductivity (K_eff) estimates obtained by automatically calibrating a groundwater flow model while treating the medium to be homogeneous. Such a K_eff is often used for designing remediation operations, and thus is used as the basis for comparison with the K‐tomogram. Our results clearly show that hydraulic tomography is superior to the inversions of single pumping tests or K_eff estimates. This is particularly significant for contaminated sites where an accurate representation of the flow field is critical for simulating contaminant transport and injection of chemical and biological agents used for active remediation of contaminant source zones and plumes.     

Frequency dependence of long-period t*

Multi-phase long-period t* measurements are among the key evidences for the frequency-dependent mantle attenuation factor, Q. However, similarly to Q, poorly constrained variations of Earth’s structure may cause spurious frequency-dependent effects in the observed t*. By using an attenuation-coefficient approach which incorporates measurements of geometric spreading (GS), such effects can be isolated and removed. The results show that the well-known increase of body P-wave t* from ~0.2 s at short periods to ~1–2 s at long periods may be caused by a small and positive bias in the underlying GS, which is measured by a dimensionless parameter γ*?≈?0.06. Similarly to the nearly constant t* at teleseismic distances, this GS bias is practically range-independent and interpreted as caused by velocity heterogeneity within the crust and uppermost mantle. This bias is accumulated within a relatively thin upper part of the lithosphere and may be closely related to the crustal body-wave GS parameter γ?~?4–60 mHz reported earlier. After a correction for γ, P-wave t _P * becomes equal ~0.18 s at all frequencies. By using conventional dispersion relations, this value also accounts for ~40 % of the dispersion-related delay in long-period travel times. For inner-core attenuation, the attenuation coefficient shows a distinctly different increase with frequency, which is remarkably similar to that of fluid-saturated porous rock. As a general conclusion, after the GS is accounted for, no absorption-band type or frequency-dependent upper-mantle Q is required for explaining the available t* and velocity dispersion observations. The meaning of this Q is also clarified as the frequency-dependent part of the attenuation coefficient. At the same time, physically justified theories of elastic-wave attenuation within the Earth are still needed. These conclusions agree with recent re-interpretations of several surface, body and coda-wave attenuation datasets within a broad range of frequencies.