Batch and Column Experiments to Support Heavy Metals (Cu,Zn, and Mn) Transport Modeling in Alluvial Sediments Between the Mogan Lake and the Eymir Lake,Gölbaşı, Ankara

This article describes laboratory batch sorption and column transport experiments that were conducted using heterogeneous alluvial sediments with a wide physical characteristic from wells, located between Lake Mogan and Lake Eymir, Gölbaşı, Ankara. The batch sorption experiment was conducted in two separate systems, that is, single and multicomponents. Single batch experiment was performed to determine equilibrium condition between the heavy metal ions and the soil adsorption sites. The sorption isotherms data from multibatch experiments were used to calculate the sorption parameters. Single batch experiment indicated that equilibrium was attained within 9 days from the start of the sorption test. As a result of multicomponents batch experiments, for Zn and Mn, the sorption process was well described by the Freundlich or Langmuir isotherm model, whereas sorption of Cu was better described by the linear isotherm model. The K_d of Cu were found to be highest in soil 1 (32550.350 L kg⁻¹) and lowest in soil 5 (18170.76 L kg⁻¹). The maximum and minimum sorption capacity values for Zn were found to be in soil 1 (10985.148 mg kg⁻¹) and in soil 2 (8597.14 mg kg⁻¹) units, respectively. [Correction added after online publication 15 July, 2010: In the preceding sentence, the words “minimum” and “maximum” were initially switched.] Similarly, soil 1 (7587.391 mg kg⁻¹) and soil 5 (4908.695 mg kg⁻¹) units provided the maximum and minimum values for Mn. In the column experiments, flow and tracer transport was studied under saturated conditions using conservative tracer to determine the transport parameters. Transport parameter values were obtained by curve-fitting using the nonlinear least-squares optimization code CXTFIT. Results of the column experiments indicated that the dispersivity values obtained for soil samples were in the range of 0.024 to 1.13 cm.     

Sensitivity of soil parameters in unsaturated zone modelling and the relation between effective,laboratory and in situ estimates

Simulation of soil moisture content requires effective soil hydraulic parameters that are valid at the modelling scale. This study investigates how these parameters can be estimated by inverse modelling using soil moisture measurements at 25 locations at three different depths (at the surface, at 30 and 60 cm depth) on an 80 by 20 m hillslope. The study presents two global sensitivity analyses to investigate the sensitivity in simulated soil moisture content of the different hydraulic parameters used in a one‐dimensional unsaturated zone model based on Richards' equation. For estimation of the effective parameters the shuffled complex evolution algorithm is applied. These estimated parameters are compared to their measured laboratory and in situ equivalents. Soil hydraulic functions were estimated in the laboratory on 100 cm³ undisturbed soil cores collected at 115 locations situated in two horizons in three profile pits along the hillslope. Furthermore, in situ field saturated hydraulic conductivity was estimated at 120 locations using single‐ring pressure infiltrometer measurements. The sensitivity analysis of 13 soil physical parameters (saturated hydraulic conductivity (K_s), saturated moisture content (θ_s), residual moisture content (θ_r), inverse of the air‐entry value (α), van Genuchten shape parameter (n), Averjanov shape parameter (N) for both horizons, and depth (d) from surface to B horizon) in a two‐layer single column model showed that the parameter N is the least sensitive parameter. K_s of both horizons, θ_s of the A horizon and d were found to be the most sensitive parameters. Distributions over all locations of the effective parameters and the distributions of the estimated soil physical parameters from the undisturbed soil samples and the single‐ring pressure infiltrometer estimates were found significantly different at a 5% level for all parameters except for α of the A horizon and K_s and θ_s of the B horizon. Different reasons are discussed to explain these large differences. Copyright © 2004 John Wiley & Sons, Ltd.     

Determining hydraulic properties of a loam soil by alternative infiltrometer techniques

Testing infiltrometer techniques to determine soil hydraulic properties is necessary for specific soils. For a loam soil, the water retention and hydraulic conductivity predicted by the BEST (Beerkan Estimation of Soil Transfer parameters) procedure of soil hydraulic characterization was compared with data collected by more standard laboratory and field techniques. Six infiltrometer techniques were also compared in terms of saturated soil hydraulic conductivity, K_s. BEST yielded water retention values statistically similar to those obtained in the laboratory and K_s values practically coinciding with those determined in the field with the pressure infiltrometer (PI). The unsaturated soil hydraulic conductivity measured with the tension infiltrometer (TI) was reproduced satisfactorily by BEST only close to saturation. BEST, the PI, one‐potential experiments with both the TI and the mini disk infiltrometer (MDI), the simplified falling head (SFH) technique and the bottomless bucket (BB) method yielded statistically similar estimates of K_s, differing at the most by a factor of three. Smaller values were obtained with longer and more soil‐disturbing infiltration runs. Any of the tested infiltration techniques appears usable to obtain the order of magnitude of K_s at the field site, but the BEST, BB and PI data appear more appropriate to characterize the soil at some stage during a rainfall event. Additional investigations on both similar and different soils would allow development of more general procedures to apply infiltrometer techniques for soil hydraulic characterization. Copyright © 2015 John Wiley & Sons, Ltd.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

In situ measurements of soil saturated hydraulic conductivity: Assessment of reliability through rainfall–runoff experiments

The saturated hydraulic conductivity, K_s, is a soil property that has a key role in the partitioning of rainfall into surface runoff and infiltration. The commonly used instruments and methods for in situ measurements of K_s have frequently provided conflicting results. Comparison of K_s estimates obtained by three classical devices—namely, the double ring infiltrometer (DRI), the Guelph version of the constant‐head well permeameter (GUELPH‐CHP) and the CSIRO version of the tension permeameter (CSIRO‐TP) is presented. A distinguishing feature in this study is the use of steady deep flow rates, obtained from controlled rainfall–runoff experiments, as benchmark values of K_s at local and field‐plot scales, thereby enabling an assessment of these methods in reliably reproducing repeatable values and in their capability of determining plot‐scale variation of K_s. We find that the DRI grossly overestimates K_s, the GUELPH‐CHP gives conflicting estimates of K_s with substantial overestimation in laboratory experiments and underestimation at the plot scale, whereas the CSIRO‐TP yields average K_s values with significant errors of 24% in the plot scale experiment and 66% in laboratory experiments. Although the DRI would likely yield a better estimate of the nature of variability than the GUELPH‐CHP and CSIRO‐TP, a separate calibration may be warranted to correct for the overestimation of K_s values. The reasons for such discrepancies within and between the measurement methods are not yet fully understood and serve as motivation for future work to better characterize the uncertainty associated with individual measurements of K_s using these methods and the characterization of field scale variability from multiple local measurements.     

Sorption behavior of nonylphenol on marine sediments: effect of temperature, medium, sediment organic carbon and surfactant

The sorption behavior of nonylphenol (NP, a toxic endocrine disruptor) on marine sediments was studied in detail through a series of kinetic and thermodynamic sorption experiments. The results showed that the sorption reaction of NP on marine sediments reached equilibrium in 1.5 h and that it accorded well with the non-linear Ho-McKay pseudo-second-order model. The sorption isotherms of NP on H₂O-treated sediments could be well described by the Linear isotherm model, while the sorption isotherm on H₂O₂-treated sediments could be well fitted with the Freundlich isotherm model. A positive correlation was found between the distribution coefficient (K_d) and the sediment organic carbon contents. The medium salinity showed a positive relation with the K_d and a negative relation with the dissolved organic carbon (DOC). Hexadecyl trimethyl ammonium bromide (CTAB) enhanced the sorption amount of NP the most, while sodium dodecylbenzenesulfonate (SDBS) enhanced it the least. The sorption reaction of NP on marine sediments was a spontaneous, physical, exothermic and entropy-decreasing process.     

Sorption Behaviour of Phenols on Natural Sandy Aquifer Material during Flow‐through Column Experiments: The Effect of pH

Flow‐through column experiments were carried out to investigate the influence of pH on the sorption of three phenols (2‐methyl‐4, 6‐dinitrophenol, 2, 4, 6‐trichlorophenol, pentachlorophenol) onto a natural sandy aquifer material collected from a bank filtration site of River Elbe, Germany. For the phenols investigated, an increase in sorption (retardation) with decreasing pH is observed indicating a stronger sorption of the neutral species in comparison to that of the anions formed by dissociation. The anions of 2‐methyl‐4, 6‐dinitrophenol and 2, 4, 6‐trichlorophenol do not show significant sorption. On the contrary, pentachlorophenol showed sorption not only in neutral form but also in ionic form significantly which should be taken into account while assessing the fate and transport of such compound. A linear model based on the degree of protonation (calculated from pH and pK_a) can be used to resolve the apparent (observed) sorption coefficient (K_{d, app}) into its neutral (K_{d, n}) and ionised (K_{d, i}) components. Knowing pK_a, K_{d, n}, and K_{d, i} the apparent sorption coefficient for pH values other than experimentally investigated can be predicted.     

Determination of Partition Coefficients of Metals in Natural Tropical Water

The values for the partition coefficient (K_d) were calculated for Ca, Mg, Cd, Cr, Cu, Fe, Mn, Pb, Ni, and Zn at 19 sites in the Capivara hydroelectric reservoir in Brazil. It was found that the relative values of K_d follow the order: Cr > Mn > Fe > Cu > Zn > Ni > Pb > Ca > Cd, differing from the values reported for K_d in aquatic systems in the northern hemisphere. A hierarchical cluster analysis and linear correlations showed that Cr is strongly associated with Fe and Cu, and that Cd is the only metal found in complexation with organic matter, explaining its higher solubility.     

Relationships between physical‐geochemical soil properties and erodibility of streambanks among different physiographic provinces of Tennessee,USA

Erosion of cohesive soils in fluvial environments is dependent on physical, geochemical and biological properties, which govern inter‐particle attraction forces and control detachment rates from stream beds and banks. Most erosion rate models are based on the excess shear stress equation where the soil erodibility coefficient (k_d) is multiplied by the difference between the boundary hydraulic shear stress (τ_b) and the soil critical shear stress (τ_c). Both k_d and τ_c are a function of soil properties and must be obtained through in situ field or laboratory testing. Many studies have generated predictive relationships for k_d and τ_c derived from various soil properties. These studies typically were conducted in watersheds within a single physiographic region with a common surficial geology and/or investigated a limited number of soil properties, particularly geochemical properties. With widely reported differences in relationships between τ_c and soil properties, this study investigated differences in predictive relationships for τ_c among different physiographic provinces in Tennessee, USA. Erodibility parameters were determined in the field using a mini‐jet test device. Among these provinces, statistically four unique clusters were identified from a dataset of 128 observations and these data clusters were used to develop predictive models for τ_c to identify dominant properties governing erosion. In these clusters, 16 significant physical and geochemical soil properties were identified for τ_c prediction. Among these soil properties, water content and passing #200 sieve (percentage soil less than 75 μm) were the dominant controlling parameters to predict τ_c in addition to clay percentage (< 2 μm), bulk density, and soil pore water chemistry. This study suggests that unique relationships exist for physiographic provinces that are likely due to soil physical‐geochemical processes associated with surficial geology that determine minerology of the cohesive soil. Copyright © 2017 John Wiley & Sons, Ltd.     

Partitioning of Fluoroquinolones on Wastewater Sludge

Laboratory‐scale batch experiments were conducted to investigate the adsorption behavior of eight fluoroquinolones (FQs) on aerobic, anoxic, and anaerobic sludge, under different adsorpiton time, pH, and temperature conditions. Results indicated that adsorption of FQs onto all sludge was a physical sorption process. The relationship of the partitioning coefficient (K_d) and the octanol/water partition coefficient (K_ow) for each FQ was established. The adsorbed fraction of FQs on sludge could then be predicted with the K_d. It was calculated that about 50–72% of the FQs were adsorbed on the sludge. Therefore, the adsorption effect must be considered when studying the fate and occurrence of FQs in wastewater treatment systems.     

Predicting physical equations of soil detachment by simulated concentrated flow in Ultisols (subtropical China)

Soil detachment in concentrated flow is due to the dislodging of soil particles from the soil matrix by surface runoff. Both aggregate stability and shear strength of the topsoil reflect the erosion resistance of soil to concentrated runoff, and are important input parameters in predicting soil detachment models. This study was conducted to develop a formula to predict soil detachment rate in concentrated flow by using the aggregate stability index (As), root density (R_d) and saturated soil strength (σ_s) in the subtropical Ultisols region of China. The detachment rates of undisturbed topsoil samples collected from eight cultivated soil plots were measured in a 3.8 m long, 0.2 m wide hydraulic flume under five different flow shear stresses (τ = 4.54, 9.38, 15.01, 17.49 and 22.54 Pa). The results indicated that the stability index (As) was well related with soil detachment rate, particularly for results obtained with high flow shear stress (22.54 Pa), and the stability index (As) has a good linear relationship with concentrated flow erodibility factors (K_c). There was a positive linear relationship between saturated soil strength (σ_s) and critical flow shear stress (τ_c) for different soils. A significant negative exponential relationship between erodibility factors (K_c) and root density (R_d) was detected. This study yielded two prediction equations that allowed comparison of their efficiency in assessing soil detachment rate in concentrated flow. The equation including the root density (R_d) may have a better correlation coefficient (R² = 0.95). It was concluded that the formula based on the stability index (As), saturated soil strength (σ_s) and root density (R_d) has the potential to improve methodology for assessing soil detachment rate in concentrated flow for the subtropical Chinese Ultisols. Copyright © 2012 John Wiley & Sons, Ltd.     

Behavior and Fate of PFOA and PFOS in Sandy Aquifer Sediment

Microcosms were constructed with sediment from beneath a landfill that received waste containing PFOA (perfluorooctanoic acid) and PFOS (perfluorooctane sulfonate). The microcosms were amended with PFOA and PFOS, and sampled after 91, 210, 343, 463, 574, and 740 d of incubation. After 740 d, selected microcosms were extracted to determine the mass of PFOA and PFOS remaining. There was no evidence for degradation of PFOA or PFOS. Over time, the aqueous concentrations of PFOA and PFOS increased in the microcosms, indicating that PFOA and PFOS that had originally sorbed to the sediment was desorbing. At the beginning of the experiment, the adsorption coefficient, K_d, averaged 0.27 L/kg for PFOA and 1.2 L/kg for PFOS. After 740 d of incubation, sorption of PFOA was not detectable and the K_d of PFOS was undetectable in two microcosms and was 0.08 L/kg in a third microcosm. During incubation, the pH of the pore water in the microcosms increased from pH 7.2 to pH ranging from 8.1 to 8.8. The zeta potential of the sediment decreased with increasing pH. These observations suggest that the sorption of PFOA and PFOS at near neutral pH was controlled by the electrostatic sorption on ferric oxide minerals, and not by the sorption to organic carbon. Accurate predictions of PFOA and PFOS mobility in ground water should be based on empirical estimates of sorption using affected aquifer sediment.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Inter-laboratory calibration of low-field magnetic and anhysteretic susceptibility measurements

Inter-laboratory and absolute calibrations of rock magnetic parameters are fundamental for grounding a rock magnetic database and for semi-quantitative estimates about the magnetic mineral assemblage of a natural sample. Even a dimensionless ratio, such as anhysteretic susceptibility normalized by magnetic susceptibility (K_a/K) may be biased by improper calibration of one or both of the two instruments used to measure K_a and K. In addition, the intensity of the anhysteretic remanent magnetization (ARM) of a given sample depends on the experimental process by which the remanence is imparted. We report an inter-laboratory calibration of these two key parameters, using two sets of artificial reference samples: a paramagnetic rare earth salt, Gd₂O₃ and a commercial “pozzolanico” cement containing oxidized magnetite with grain size of less than 0.1 μm according to hysteresis properties. Using Gd₂O₃ the 10 Kappabridges magnetic susceptibility meters (AGICO KLY-2 or KLY-3 models) tested prove to be cross-calibrated to within 1%. On the other hand, Kappabridges provide a low-field susceptibility value that is ca. 6% lower than the tabulated value for Gd₂O₃, while average high-field susceptibility values measured on a range of instruments are indistinguishable from the tabulated value. Therefore, we suggest that Kappabridge values should be multiplied by 1.06 to achieve absolute calibration. Bartington Instruments magnetic susceptibility meters with MS2B sensors produce values that are 2-13% lower than Kappabridge values, with a strong dependence on sample centering within the sensor. The K_a/K ratio of ca. 11, originally obtained on discrete cement samples with a 2G Enterprises superconducting rock magnetometer and a KLY-2, is consistent with reference parameters for magnetites of grain size <0.1 μm. On the other hand, K_a values from a 2G Enterprises magnetometer and K values from a Bartington Instruments MS2C loop sensor for u-channel and discrete cement samples, will produce average K_a/K values that are unrealistically high if not properly corrected for the nominal volume detected by the sensors for these instruments. Inter-laboratory measurements of K and K_a for standard paleomagnetic plastic cubes filled with cement indicate remarkable differences in the intensity of the newly produced ARMs (with a standard deviation of ca. 21%), that are significantly larger than the differences observed from the calibration of the different magnetometers employed in each laboratory. Differences in the alternating field decay rate are likely the major source of these variations, but cannot account for all the observed variability. With such large variations in experimental conditions, classical interpretation of a “King plot” of K_a versus K would imply significant differences in the determination of grain size of magnetite particles on the same material.     

Optimum characteristic properties of isolators with bilinear force–displacement hysteresis for seismic protection of bridges built on various site soils

In this study, closed form equations as functions of the isolator, bridge and ground motion properties are formulated to calculate the optimum characteristic strength, Q_d and post-elastic stiffness, k_d, of the isolator to minimize the maximum isolator displacement (MID) and force (MIF) for seismic isolated bridges (SIBs). For this purpose, first, sensitivity analyses are conducted to identify the bridge, isolator and ground motion parameters that affect the optimum values of Q_d and k_d. Next, for the identified parameters, nonlinear time history analyses of typical SIBs are conducted to determine the optimum values of Q_d and k_d for a wide range of values of the parameters. Next, nonlinear regression analyses of the available data are conducted to obtain closed form equations for the optimum values of Q_d and k_d, to minimize the MID and MIF. The equations are then simplified for various site soil conditions. It is observed that the optimum Q_d and k_d are highly dependent on the site soil condition. Furthermore, the optimum Q_d is found to be a linear function of the peak ground acceleration.     

A Practical Measurement Strategy to Estimate Nonlinear Chlorinated Solvent Sorption in Low foc Sediments

In this study, we tested a practical strategy useful for accurate chlorinated volatile organic compound (cVOC) sorption prediction. Corresponding to the feature of the superposition of adsorption due to thermally altered carbonaceous matter (TACM) with organic carbon‐water partitioning, a nonlinear Freundlich sorption isotherm covering a wide range of aqueous concentrations was defined by equilibrium sorption measurement at one or a few low concentration points with extrapolation to the empirical organic carbon‐water partition coefficient (K_oc,e) near compound solubility. We applied this approach to obtain perchloroethene equilibrium sorption isotherm parameters for TACM‐containing glacial sand and gravel subsoil samples from a field site in New York. Sorption and associated K_oc,c applicable to low (5–500 µg/L) and high (>100,000 µg/L) aqueous concentrations were determined in batch experiments. (The K_oc,c is the organic carbon‐normalized sorption partition coefficient corresponding to aqueous concentration C_w.) The K_oc,c measurements at low concentration (~5 µg/L) were 6 to 34 times greater than the K_oc,e. The importance of this type of data is illustrated through presentation of its substantial impact on the site remedy. In so doing, we provide an approach that is broadly applicable to cVOC field sites with similar circumstances (low carbon content glacial sand and gravel with TACM).     

Laboratory Testing of Sulfamethoxazole and its Metabolite Acetyl‐Sulfamethoxazole in Soil

The fate of ¹⁴C‐labeled sulfamethoxazole and acetyl‐sulfamethoxazole in soil has been investigated with special respect to possible entry routes of human and veterinary pharmaceuticals into soil environments. Therefore, the stability of the test substances was monitored first in sewage sludge and bovine manure. Within the incubation period of 72 d, 1% at maximum of the initially applied radiotracers was released as ¹⁴C‐carbon dioxide while ?75% was transferred to non‐extractable residues that were operationally defined by the ethyl acetate extraction. Test‐sludge and test‐manure samples with defined aged residues were prepared and, supplementary to standard solutions, applied to silty‐clay soil samples. After standard and test‐sludge application, soil/water distribution coefficients of K_d < 5 L kg^–1 were determined revealing both test substances as potential leachers. In contrast, the sorption of sulfamethoxazole increased after test‐manure application (K_d > 10 L kg^–1). In the long‐term degradability tests, the metabolic fate of both test substances was characterized by the continuous decrease of extractable residues, resulting in disappearance times of DT₉₀ ? 33 d, and the increase of non‐extractable residues. Mineralization reached 11% at maximum. Thereby, the dynamics of these processes differed whether the test substances were applied via standard, test‐sludge or test‐manure application. This fact emphasized the relevance of entry route specific matrix effects on the fate of both test substances in soil.     

Accounting for the influence of runoff on event soil erodibilities associated with the EI30 index in RUSLE2

Soil erodibilities (K) associated with the EI₃₀ index vary not only with soil properties but also with soil moisture as it varies in time and space. In Revised Universal Soil Loss Equation Version 2 (RUSLE2), temporal variations in soil erodibility in the USA are calculated using monthly precipitation and temperature as independent variables. K_UM, the soil erodibility factor associated with the Q_REI₃₀ index, varies independently of runoff and the product of K_UM and the runoff ratio for the unit plot (Q_R1) provides an alternative to the temporally varying Ks currently used in predicting storm soil loss in RUSLE2. Comparisons were made between the product of Q_R1 and K_UM and RUSLE2 Ks for representative storms at four locations representing the north to south variation in climate in the USA. Peak erosion associated with the current approach used in RUSLE2 was slightly higher at two locations and slightly lower at the other two locations. One other location, Morris, MN, provided an exception with the peak loss predicted by using the product of Q_R1 and K_UM being 1.7 times that obtained using RUSLE2 Ks. In theory, average annual K_UM values should be better related to soil properties than the average annual values of K frequently used when the average annual values of EI₃₀ are used to predict soil loss. However, work has yet to be performed to determine how K_UM varies directly with soil properties and in space and time. Copyright © 2014 John Wiley & Sons, Ltd.