Determination of sorption coefficients of pharmaceutically active substances carbamazepine, diclofenac, and ibuprofen, in sandy sediments

Laboratory batch studies were conducted to characterize the sorption behavior of three pharmaceutically active substances (carbamazepine, diclofenac, and ibuprofen) in different sediment types. The sediments were natural sandy sediments from the water saturated zone and the unsaturated zone in the Berlin (Germany) area. They are characterized as medium and fine-grained sands, both with low organic carbon content. The results of the experiments show that sorption coefficients were generally quite low. Distribution coefficients (K(d) values) determined by the batch experiments varied from 0.21 to 5.32 for carbamazepine, 0.55 to 4.66 for diclofenac, and 0.18 to 1.69 for ibuprofen. Comparison of the organic carbon normalized sorption coefficient K(OC) values based on correlation equations with actual experimental data revealed that the calculated data for carbamazepine is of the same order as the experimental data. For diclofenac and ibuprofen the calculated values are much higher than the experimental data, showing a much higher mobility of diclofenac and ibuprofen in natural aquifer sediments than indicated by correlation equations based on octanol water distribution coefficients.     

Transport of Escherichia coli through variably saturated sand columns and modeling approaches

A sand column leaching system with well-controlled suction and flow rate was built to investigate the effects on bacterial transport of air-water interface effects (AWI) correlated to water content, particle size, and column length. Adsorption of Escherichia coli strain D to silica sands was measured in batch tests. The average % adsorption for coarse and fine sands was 45.9+/-7.8% and 96.9+/-3.2%, respectively. However, results from static batch adsorption experiments have limited applicability to dynamic bacterial transport in columns. The early breakthrough of E. coli relative to bromide was clear for all columns, namely c. 0.15 to 0.3 pore volume earlier. Column length had no significant effects on the E. coli peak concentration or on total recovery in leachate, indicating retention in the top layer of sands. Tailing of breakthrough curves was more prominent for all fine sand columns than their coarse sand counterparts. Bacterial recovery in leachate from coarse and saturated sand columns was significantly higher than from fine and unsaturated columns. Observed data were fitted by the convection-dispersion model, amended for one-site and two-site adsorption to particles, and for air-water interface (AWI) adsorption. Among all models, the two-site+AWI model achieved consistently high model efficiency for all experiments. Thus it is evident from experimental and modeling results that AWI adsorption plays an important role in E. coli transport in sand columns.     

Sorption and mobility of pharmaceutical compounds in soil irrigated with reclaimed wastewater

Use of reclaimed wastewater for irrigation is an important route for the introduction of pharmaceutical compounds (PCs) into the environment. In this study, the mobility and sorption-desorption behavior of carbamazepine, naproxen and diclofenac were studied in soil layers sampled from a plot irrigated with secondary-treated wastewater (STWW). Carbamazepine and diclofenac were significantly retarded in the 0-5 cm soil sample rich in soil organic matter (SOM): carbamazepine was not affected by the water quality (freshwater versus STWW), whereas diclofenac exhibited a higher retardation factor (RF) in the freshwater system. Naproxen exhibited significantly lower RFs than diclofenac but with a similar trend - higher retardation in the freshwater versus STWW system. In the 5-15 cm soil sample containing low SOM, naproxen was highly mobile while carbamazepine and diclofenac were still retarded. In the 15-25 cm sample, all compounds exhibited their lowest RFs. Sorption data suggested that SOM governs the studied PCs' interactions with the soil samples. However, higher carbon-normalized sorption coefficients were measured for the PCs in the 15-25 cm sample, suggesting that both quantity and the physicochemical nature of SOM affect sorption interactions. While both naproxen and carbamazepine exhibited reversible sorption isotherms, diclofenac exhibited pronounced sorption-desorption hysteresis. This study suggests that carbamazepine and diclofenac can be classified as slow-mobile compounds in SOM-rich soil layers. When these compounds pass this layer and/or introduced into SOM-poor soils, their mobility increases significantly. This emphasizes the potential transport of PCs to groundwater in semiarid zones due to intensive irrigation with reclaimed wastewater in SOM-poor soils.     

Determination of bromacil transport as a function of water and carbon content in soils

This study was conducted to determine the significance of bromacil transport as a function of water and carbon content in soils and to explore the implications of neglecting sorption when making assessments of travel time of bromacil through the vadose zone. Equilibrium batch sorption tests were performed for loamy sand and sandy soil added with four different levels of powdered activated carbon (PAC) content (0, 0.01, 0.05, and 0.1%). Column experiments were also conducted at various water and carbon contents under steady-state flow conditions. The first set of column experiments was conducted in loamy sand containing 1.5% organic carbon under three different water contents (0.23, 0.32, and 0.41) to measure breakthrough curves (BTCs) of bromide and bromacil injected as a square pulse. In the second set of column experiments, BTCs of bromide and bromacil injected as a front were measured in saturated sandy columns at the four different PAC levels given above. Column breakthrough data were analyzed with both equilibrium and nonequilibrium (two-site) convection-dispersion equation (CDE) models to determine transport and sorption parameters under various water and carbon contents. Analysis with batch data indicated that neglect of the partition-related term in the calculation of solute velocity may lead to erroneous estimation of travel time of bromacil, i.e. an overestimation of the solute velocity by a factor of R. The column experiments showed that arrival time of the bromacil peak was larger than that of the bromide peak in soils, indicating that transport of bromacil was retarded relative to bromide in the observed conditions. Extent of bromacil retardation (R) increased with decreasing water content and increasing PAC content, supporting the importance of retardation in the estimation of travel time of bromacil even at small amounts of organic carbon for soils with lower water content.     

Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment

The presence of pharmaceutical compounds in surface waters is an emerging environmental issue. Sewage treatment plants (STPs) are recognized as being the main point discharge sources of these substances to the environment. A monitoring campaign of STP effluents was carried out in four European countries (Italy, France, Greece and Sweden). More than 20 individual pharmaceuticals belonging to different therapeutic classes were found. For six selected pharmaceuticals (carbamazepine, diclofenac, clofibric acid, ofloxacin, sulfamethoxazole and propranolol) present in the STP effluents, the persistence towards abiotic photodegradation was evaluated submitting them to solar experiments at 40° N latitude during spring and summer. Based on experimentally measured quantum yields for the direct photolysis in bi-distilled water, half-life times (t_1/2) at varying seasons and latitude were predicted for each substance. In salt- and organic-free (bi-distilled) water carbamazepine and clofibric acid are characterized by calculated half-life times of the order of 100 days at the highest latitudes (50° N) in winter, whereas under the same conditions sulphamethoxazole, diclofenac, ofloxacin and propranolol undergo fast degradation with t_1/2 respectively of 2.4, 5.0, 10.6 and 16.8 days. For almost all studied compounds, except propranolol the presence of nitrate ions in aqueous solutions results in a reduction of t_1/2. When present, humic acids act as inner filters towards carbamazepine and diclofenac, and as photosensitizers towards sulphamethoxazole, clofibric acid, oflaxocin and propranolol.     

Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.     

Effects of water content on reactive transport of 85Sr in Chernobyl sand columns

It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.     

Bacterial deposition in unsaturated porous media as related to surface properties

Transport of Escherichia coli, Pseudomonas fluorescens and Bacillus subtilis in silica sand under water-unsaturated conditions was investigated using column experiments. It was hypothesised that bacterial deposition was due to their interactions within the pore environment, which was a function of their surface physicochemical properties as well as pore water chemistry. Surface thermodynamic properties of these bacterial strains were measured independently by means of contact angle measurements under different water saturation conditions using variable lawn moisture contents. Bacterial interactions with the liquid-gas interface and the porous media were calculated based on their surface properties and were related to their transport observations.     

Comparison of the solution behaviour of a pyrite-calcite mixture in batch and unsaturated sand column

A successful application of reaction transport algorithms to calculate the chemical evolution of natural systems requires accurate methods to compute the rates of mineral/fluid surface reactions. Regarding the transport of radio-nuclides in mining dumps the dissolution of minerals is of special importance. Using a kinetic rate law of the mineral dissolution verified for unsaturated conditions will allow a realistic modelling of the mineral weathering in the environment. Dissolution rates of minerals in an aqueous solution are determined by several characteristics. These are surface reaction rates, morphology of the mineral's surface and, in case it is the unsaturated zone, the degree of the water saturation. For this process, the quantity of the particle surfaces which are in contact with percolating water is most decisive. In order to study the differences of mineral dissolution under saturated and unsaturated conditions batch and column experiments were carried out with a pyrite-calcite mixture. The experimental results were verified by calculations. Comparing the dissolution in batch with those in the column experiment, which was performed with a water flow velocity of 0.64 cm/day and was analyzed in the region of a water saturation of 0.11, one can conclude that only a small portion of about 5% of the grain surface is chemically reactive in this unsaturated flow.     

Evaluation of aquatic plants for removing polar microcontaminants: a microcosm experiment

Microcosm wetland systems (5 L containers) planted with Salvinia molesta, Lemna minor, Ceratophyllum demersum, and Elodea canadensis were investigated for the removal of diclofenac, triclosan, naproxen, ibuprofen, caffeine, clofibric acid and MCPA. After 38 days of incubation, 40-99% of triclosan, diclofenac, and naproxen were removed from the planted and unplanted reactors. In covered control reactors no removal was observed. Caffeine and ibuprofen were removed from 40% to 80% in planted reactors whereas removals in control reactors were much lower (2-30%). Removal of clofibric acid and MCPA were negligible in both planted and unplanted reactors. The findings suggested that triclosan, diclofenac, and naproxen were removed predominantly by photodegradation, whereas caffeine and naproxen were removed by biodegradation and/or plant uptake. Pseudo-first-order removal rate constants estimated from nonlinear regressions of time series concentration data were used to describe the contaminant removals. Removal rate constants ranged from 0.003 to 0.299 d(-1), with half-lives from 2 to 248 days. The formation of two major degradation products from ibuprofen, carboxy-ibuprofen and hydroxy-ibuprofen, and a photodegradation product from diclofenac, 1-(8-Chlorocarbazolyl)acetic acid, were followed as a function of time. This study emphasizes that plants contribute to the elimination capacity of microcontaminants in wetlands systems through biodegradation and uptake processes.     

Biodegradation of hydrocarbons vapors: Comparison of laboratory studies and field investigations in the vadose zone at the emplaced fuel source experiment, Airbase Vaerløse, Denmark

The natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone can only be predicted when information about microbial biodegradation rates and kinetics are known. This study aimed at determining first-order rate coefficients for the aerobic biodegradation of 13 volatile petroleum hydrocarbons which were artificially emplaced as a liquid mixture during a field experiment in an unsaturated sandy soil. Apparent first-order biodegradation rate coefficients were estimated by comparing the spatial evolution of the resulting vapor plumes to an analytical reactive transport model. Two independent reactive numerical model approaches have been used to simulate the diffusive migration of VOC vapors and to estimate degradation rate coefficients. Supplementary laboratory column and microcosm experiments were performed with the sandy soil at room temperature under aerobic conditions. First-order kinetics adequately matched the lab column profiles for most of the compounds. Consistent compound-specific apparent first-order rate coefficients were obtained by the three models and the lab column experiment, except for benzene. Laboratory microcosm experiments lacked of sensitivity for slowly degrading compounds and underestimated degradation rates by up to a factor of 5. Addition of NH3 vapor was shown to increase the degradation rates for some VOCs in the laboratory microcosms. All field models suggested a significantly higher degradation rate for benzene than the rates measured in the lab, suggesting that the field microbial community was superior in developing benzene degrading activity.     

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

Behaviour and fate of nine recycled water trace organics during managed aquifer recharge in an aerobic aquifer

The fate of nine trace organic compounds was evaluated during a 12month large-scale laboratory column experiment. The columns were packed with aquifer sediment and evaluated under natural aerobic and artificial anaerobic geochemical conditions, to assess the potential for natural attenuation of these compounds during aquifer passage associated with managed aquifer recharge (MAR). The nine trace organic compounds were bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR), carbamazepine, oxazepam, iohexol and iodipamide. In the low organic carbon content Spearwood sediment, all trace organics were non-retarded with retardation coefficients between 1.0 and 1.2, indicating that these compounds would travel at near groundwater velocities within the aquifer. The natural aerobic geochemical conditions provided a suitable environment for the rapid degradation for BPA, E2, iohexol (half life <1day). Lag-times for the start of degradation of these compounds ranged from <15 to 30days. While iodipamide was persistent under aerobic conditions, artificial reductive geochemical conditions promoted via the addition of ethanol, resulted in rapid degradation (half life <1days). Pharmaceuticals (carbamazepine and oxazepam) and disinfection by-products (NDMA and NMOR) did not degrade under either aerobic or anaerobic aquifer geochemical conditions (half life >50days). Field-based validation experiments with carbamazepine and oxazepam also showed no degradation. If persistent trace organics are present in recycled waters at concentrations in excess of their intended use, natural attenuation during aquifer passage alone may not result in extracted water meeting regulatory requirements. Additional pre treatment of the recycled water would therefore be required.     

Reactive transport of 85Sr in a chernobyl sand column: static and dynamic experiments and modeling

The effects of nonlinear sorption and competition with major cations present in the soil solution on radioactive strontium transport in an eolian sand were examined. Three laboratory techniques were used to identify and quantify the chemical and hydrodynamic processes involved in strontium transport: batch experiments, stirred flow-through reactor experiments and saturated laboratory columns. The major goal was to compare the results obtained under static and dynamic conditions and to describe in a deterministic manner the predominant processes involved in radioactive strontium transport in such systems. Experiments under dynamic conditions, namely flow-through reactor and column experiments, were in very good agreement even though the solid/liquid ratio was very different. The experimental data obtained from the flow-through reactor study pointed to a nonlinear, instantaneous and reversible sorption process. Miscible displacement experiments were conducted to demonstrate the competition between stable and radioactive strontium and to quantify its effect on the 85Sr retardation factor. The results were modeled using the PHREEQC computer code. A suitable cation-exchange model was used to describe the solute/soil reaction. The model successfully described the results of the entire set of miscible displacement experiments using the same set of parameter values for the reaction calculations. The column study revealed that the stable Sr aqueous concentration was the most sensitive variable of the model, and that the initial state of the sand/solution system had also to be controlled to explain and describe the measured retardation factor of radioactive strontium. From these observations, propositions can be made to explain the discrepancies observed between some data obtained from static (batches) and dynamic (reactor and column) experiments. Desorbed antecedent species (stable Sr) are removed from the column or reactor in the flow system but continue to compete for sorption sites in the batch system. Batch experiments are simple and fast, and provide a very useful means of multiplying data. However, interpretation becomes difficult when different species compete for sorption sites in the soil/solution system. A combination of batches, flow-through reactor and column experiments, coupled with hydrogeochemical modeling, would seem to offer a very powerful tool for identifying and quantifying the predominant processes on a cubic decimeter scale (dm3) and for providing a range of radioactive strontium retardation factor as a function of the geochemistry of the soil/solution system.     

Investigation of the behavior and metabolism of pharmaceutical residues during purification of contaminated ground water used for drinking water supply

Residues of phenazone-type pharmaceuticals originating from spills of a former pharmaceutical production plant have recently been detected in ground water in Berlin, Germany. The degradation pathways of phenazone, propyphenazone, and dimethylaminophenazone (DMAA) during water purification were enlightened in batch experiments with groundwater and filter material obtained from operating waterworks. For phenazone and propyphenazone a complete biological transformation into their respective metabolites 1,5-dimethyl-1,2-dehydro-3-pyrazolone (DP) and 4-(2-methylethyl)-1,5-dimethyl-1,2-dehydro-3-pyrazolone (PDP) was observed. Generally, removal of phenazone-type pharmaceutical residues during rapid sand filtration was almost exclusively caused by microorganisms only present in polluted raw water. DMAA applied to fresh filter materials was rapidly degraded into its metabolites 1-acetyl-1-methyl-2-phenylhydrazide (AMPH), acetoaminoantipyrine (AAA), formylaminoantipyrine (FAA), and 1-acetyl-1-methyl-2-dimethyloxamoyl-2-phenylhydrazide (AMDOPH). DMAA, AAA, and FAA were, however, only detected at low levels in a few samples of purified water from an operating water works. Whereas, the metabolites AMDOPH and DP were detected up to 1 microg l(-1). Propyphenazone was rapidly removed and AMPH, phenazone, and PDP were only measured with concentrations in the low ng l(-1) range. The concentrations of the metabolites DP and PDP are even higher in the purified water than in the raw water caused by their formation during degradation of phenazone and propyphenazone. Reduction of filtration velocity on an experimental filter from 5 m h(-1) down to 2 m h(-1) resulted in improved removal of phenazone, propyphenazone and their metabolites DP and PDP, respectively. AMDOPH, however, was highly persistent in all experiments independent from filtration velocities and contact times.     

Behaviour and redox sensitivity of pharmaceutical residues during bank filtration - Investigation of residues of phenazone-type analgesics

The behaviour of residues of phenazone-type pharmaceuticals during bank filtration was investigated at a field site in Berlin, Germany, where bank-filtered water is used for drinking water production. The concentrations of the pharmaceutical residues in the shallow, young bank filtrate (travel times相似文献   

Infiltration and redistribution of perchloroethylene in partially saturated, stratified porous media

Contamination of the subsurface by nonaqueous phase liquids (NAPLs) is a widespread problem. To investigate the behavior of a nonspreading, dense NAPL (DNAPL) in the vadose zone, we conducted perchloroethylene (PCE) infiltration experiments in nominally 1- and 2-dimensional (D), stratified porous media. In addition, the usefulness and limitations of a multifluid flow simulator to describe PCE infiltration and redistribution under the experimental conditions were tested. The physical simulations were conducted in a column (1-D) and a flow container (2-D) which were packed with two distinct layers of coarse-grained sand and a fine-grained sand layer in between. Volumetric water and PCE contents were determined with a fully automated dual-energy gamma radiation system. While migrating through the drier parts of the coarse-grained sand layers, PCE appeared to wet the water–air interface rather than displacing any water. In the wetter parts of the porous medium, PCE displaced water and behaved as a true nonwetting fluid. PCE showed a limited response to gradients in capillary pressure and rather high values for the volumetric PCE content were measured in the fine-grained sand layers. This was attributed to the nonspreading nature of PCE. The multifluid flow simulator appeared to predict the initial PCE movement in the vadose zone reasonably well. However, the model was not capable of predicting the final amounts of PCE retained in either the unsaturated or saturated part of the flow domain, mainly because the simulator does not consider the nonspreading flow behavior of NAPLs.     

Effects of pH and ionic strength on sulfamethoxazole and ciprofloxacin transport in saturated porous media

Many antibiotics regarded as emerging contaminants have been frequently detected in soils and groundwater; however, their transport behaviors in soils remain largely unknown. This study examined the transport of two antibiotics, sulfamethoxazole (SMZ) and ciprofloxacin (CIP), in saturated porous media. Laboratory columns packed with quartz sand was used to test the effects of solution pH and ionic strength (IS) on their retention and transport. The results showed that these two antibiotics behaved differently in the saturated sand columns. In general, SMZ manifested a much higher mobility than CIP for all experimental conditions tested. Almost all SMZ transported through the columns within one pore volume in deionized water (i.e., pH=5.6, IS=0), but no CIP was detected in the effluents under the same condition after extended column flushing. Perturbations in solution pH (5.6 and 9.5) and IS (0 and 0.1M) showed no effect on SMZ transport in the saturated columns. When pH increased to 9.5, however, ~93% of CIP was eluted from the sand columns. Increase of IS from 0 to 0.1M also slightly changed the distribution of adsorbed CIP within the sand column at pH 5.6, but still no CIP was detected in the effluents. A mathematical model based on advection-dispersion equation coupled with equilibrium and kinetic reactions successfully simulated the transport of the antibiotics in water-saturated porous media with R(2)=0.99.