Transport of pharmaceutically active compounds in saturated laboratory columns

Occurrences of pharmaceutically active compounds in surface water and sewage water have been widely reported. Investigations show the presence of several classes of pharmaceuticals such as antirheumatics (e.g., diclofenac), analgesics (e.g., propyphenazone), and blood lipid regulators (clofibric acid), even in ground water. Compared to their occurrences in surface water, however, the reported incidences of drugs in ground water are much rarer. This may be due to the input, but also to transport processes and degradation in the aquifer. In field studies investigating ground water sampled at a bank infiltration site at Lake Tegel, Berlin, Germany, clofibric acid was found at concentrations up to 290 ng/L, and propyphenazone up to 250 ng/L, whereas concentrations of diclofenac were around the detection limit. The aim of this study was to investigate the ground water transport behavior of the pharmaceuticals clofibric acid, propyphenazone, and diclofenac with a laboratory soil column experiment. Results show that clofibric acid exhibits no degradation and almost no retardation (Rf = 1.1). Diclofenac (Rf = 2.0) and propyphenazone (Rf = 1.6) are retarded, whereas significant degradation was not observed for both pharmaceuticals under the prevailing conditions in the soil column. We conclude that the concentration distribution of the pharmaceuticals at the bank filtration site at Lake Tegel is controlled by sorption, desorption, and input variation, rather than by degradation.     

Verhalten ausgewählter Arzneimittel bei der künstlichen Grundwasseranreicherung – Eliminierung und Effekte auf die mikrobielle Besiedlung

Behaviour of Some Pharmaceuticals during Artificial Groundwater Recharge – Elimination and Effects on Microbiology The behaviour of bezafibrate, carbamazepine, clofibric acid, diclofenac, ibuprofen, and gemfibrozil during artificial groundwater recharge was investigated with different test systems simulating field conditions. The given concentrations of the pharmaceuticals were 100 μg/L in the influent of the systems. Concentrations in the influent as well as in the effluent were measured by GC‐MS. These column experiments indicated a significant elimination of bezafibrate, diclofenac, and ibuprofen (60 to 80%) during slow sand filtration. The results showed a moderate elimination of clofibric acid and gemfibrozil (40 to 60%) but a rather low elimination of carbamazepine (<40%). The adaptation times until the elimination processes started were about 5 days. Only the elimination of carbamazepine needed a lag phase up to 17 days. Additional column experiments with groundwater model systems indicated a high persistence of pharmaceuticals under aerobic and anaerobic groundwater conditions. The elimination was less than 20%. Only diclofenac was eliminated with rates between 60% and 80% in aerobic systems and between 40% and 60% in anaerobic systems. Analysis of eubacterial 16S‐rDNA by PCR and DGGE demonstrated changes in the microbial community structure in slow sand filters after application of pharmaceuticals. Adaptation processes may cause these changes, e.g. the appearance or disappearance of single species. Also differences between the populations of water and of the solid phase in slow sand filters could be demonstrated by DGGE pattern.     

Ground Water Remediation Using an Extraction, Treatment, and Recharge System

Ground water remediation of volatile organic compound (VOC) contamination at a site in Michigan was initiated as a result of a consent agreement between the Michigan Department of Natural Resources (MDNR) and the responsible party. Under the direction of the MDNR, the responsible party conducted a remedial investigation/feasibility study using federal guidelines to define the extent of contamination at the site and to select a response action for site remediation. The selected alternative included a combination of ground water extraction, treatment, and recharge, and soil flushing. The extraction system withdraws ground water from various depths in heavily contaminated areas. The ground water is treated using an air stripper. A spray distribution system spreads effluent from the stripper over a recharge basin constructed over the most contaminated areas. Additional contaminant removal is achieved by volatilization from the spray and percolation through the gravel bed. Recharge water moves downward through the contaminated soils, thus flushing residual soil contaminants. The initial operating data demonstrated that the system can effectively remove trichloroethylene (TCE) from ground water (approximately 95 percent overall removal efficiency). The annualized capital and operation and maintenance (O & M) costs of the remedial action were estimated for several operating periods (15, 20, and 30 years).     

Analysis of Endocrine Disrupting Steroids: Investigation of Their Release into the Environment and Their Behavior During Bank Filtration

A reliable and sensitive analytical method for the determination of estrone (E1), 17β-estradiol (E2), and the synthetic hormone 17α-ethinylestradiol (EE2) has been established. Samples are concentrated using automated solid-phase extraction and analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Recoveries of all analytes were between 93% and 107%, and limits of quantification (LOQs) between 0.1 and 0.4 ng/L for purified sewage, and surface, ground, and drinking water, and between 1 and 2 ng/L in case of raw sewage. For the investigation of estrogen release into the environment and its behavior during sewage and surface water treatment, and during ground water recharge, samples from municipal waste water treatment plants (WWTPs), a surface water treatment plant, a bank filtration site, and a ground water enrichment (GWE) pond were analyzed. El was found in the raw waste water with an average concentration of 157 ng/L, whereas E2 and EE2 were found with mean concentrations of only 18 and 9 ng/L, respectively. Sewage treatment by municipal WWTPs affected a removal of EE2 (76%), El (92%), and E2 (94%). In the investigated surface water of Berlin, only E1 could be detected at concentrations around or below 1 ng/L. E2 and EE2 were not present in the Berlin surface water above the LOQ of 0.2 ng/L, respectively. Surface water treatment also leads to a significant removal of E1 (> 80%). In the ground water samples from the GWE site near Lake Tegel, only a few samples contained detectable concentrations of E1. These samples were collected from a shallow monitoring well located very close to the bank of the pond. Even a short distance between the bank and observation wells led to concentrations of El below the LOQ showing the potential of ground water recharge systems for the retention of estrogenic steroids depending on the environmental setting.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.     

Investigation of groundwater residence times during bank filtration in Berlin: a multi‐tracer approach

Berlin relies on induced bank filtration from a broad‐scale, lake‐type surface water system. Because the surface water contains treated sewage, wastewater residues are present in surface water and groundwater. Multiple environmental tracers, including tritium and helium isotopes (³H, ³He, ⁴He), stable isotopes (δ¹⁸O and δ²H) and a number of persistent sewage indicators, such as chloride, boron and a selection of pharmaceutical residues (phenazone‐type analgesics and their metabolites, carbamazepine and anthropogenic gadolinium, Gd_excess), were used to estimate travel times from the surface water to individual production and observation wells at two sites. The study revealed a strong vertical age stratification throughout the upper aquifer, with travel times varying from a few months to several decades in greater depth. Whereas the shallow bank filtrate is characterized by the reflection of the time‐variant tracer input concentrations and young ³H/³He ages, the deeper, older bank filtrate displays no tracer seasonality, ³H/³He ages of a few years to decades and strongly deviating concentrations of several pharmaceutical residues, reflecting concentrations of the source surface water over time. The phenazone‐type pharmaceuticals persist in the aquatic environments for decades. Bank filtration in Berlin is only possible at the sandy lakeshores. In greater water depth, impermeable lacustrine sapropels inhibit infiltration. The young bank filtrate originates from the nearest shore, whereas the older bank filtrate infiltrates at more distant shores. This paper illustrates the importance of using multiple tracer methods, capable of resolving a broad range of residence times, to gain a comprehensive understanding of time‐scales and infiltration characteristics in a bank filtration system. Copyright © 2007 John Wiley & Sons, Ltd.     

Production of Drinking Water from Highly Contaminated Surface Waters: Removal of Organic,Inorganic, and Microbial Contaminants Applying Mobile Membrane Filtration Units

In military out of area missions of the Bundeswehr, it can be necessary to produce drinking water even from highly polluted surface waters containing a variety of organic, inorganic, and microbiological contaminants. Thus, mobile drinking water purification systems must be able to remove such contaminants as far as possible to meet the requirements of the German and European drinking water regulation/directive. Presently, two novel drinking water purification units applying membrane filtration undergo intensive long‐term trials carried out by the Bundeswehr. If these trials positively proof the functionality of these units and their ability to remove all possible contaminants they shall substitute so far available devices which use large amounts of chemicals and charcoal filtration for water purification.In the course of a research project, the functionality of the new devices and their efficacy to remove high amounts of algae, microbes, and organic and inorganic pollutants are additionally tested in “worst‐case” field studies. In September 2000, the first mobile drinking water purification unit was tested at the Teltowkanal in Berlin, Germany.This canal was chosen because it carries high burdens of municipal sewage effluents. The results from the fatigue test confirmed the ability of the water purification unit to reduce the concentrations of all contaminants meeting the maximum tolerance levels set by the German/European drinking water regulation.The pre‐filtration device was very effective in removing algae and solid particles to protect the membranes from clogging and to enable an almost maintenance‐free operation. Residues of pharmaceuticals and some other organic contaminants have almost totally been removed from the surface water where they were detected at individual concentrations up to the μg/L‐level.     

Untersuchungen zum Abbau von Pharmaka in kommunalen Kläranlagen mit HPLC-Electrospray-Massenspektrometrie

Examination of the Degradation of Drugs in Municipal Sewage Plants Using Liquid Chromatography-Electrospray Mass Spectrometry Numerous drugs can be identified in the secondary effluent of municipal sewage plants. In order to obtain information about the degree of elimination (adsorption, aerobic degradation) of these compounds, a batch reactor containing different drugs in environmentally relevant concentrations and a suspension of activated sludge was coupled to a HPLC-MS-MS system. During a testing period of three days concentration-time-curves were recorded. For most of the examined drugs (acetamidoantipyrine, crotamiton, diclofenac, primidone, propyphenazone) solely a strong decrease of the initial concentration within the first 15 minutes was observed, which was interpreted primarily as adsorption to the activated sludge. For acetaminophenol and pentoxifyllin an additional slower decrease in concentration within several hours was observed. This slower elimination was interpreted to be caused mainly by primary degradation. It could be shown that dihydrocodeine is oxidized to hydrocodone in the batch reactor. The conjugate acetaminophen glucuronide was cleaved.     

Multicomponent simulations of contrasting redox environments at an LNAPL site

A two-dimensional multicomponent reactive transport modeling approach was used to simulate contaminant transport and the evolution of redox processes at a large-scale kerosene-contaminated site near Berlin, Germany. In contrast to previous site-scale modeling studies that focused either on one or two contaminants or on steady-state redox conditions, multiple contaminants and electron acceptors, including mineral phase Iron (III), were considered with an evolving redox zonation. Inhibition terms were used to switch between the different electron acceptor processes in the reaction scheme. The transient evolution of redox zones and contaminant plumes was simulated for two separate transects of the site, which have different geology and ground water recharge distributions and where quite different downstream contaminant and terminal electron–accepting process (TEAP) distributions are observed. The same reaction system, calibrated to measured concentrations along one of the transects, was used in both cases, achieving a reasonable match with observed concentrations. The differences between the two transects could thus to some extent be attributed to the different hydrological and hydrogeological conditions, in particular ground water recharge distributions. Long-term simulations showed that the distribution of TEAPs evolves as Fe(III) becomes depleted, with conditions becoming increasingly methanogenic, leading to changes in contaminant plume lengths. The models were applied to assess the potential effects of planned changes in land use at the site that may affect the ground water recharge distribution. The simulated redox zonation responded strongly to changes in recharge, which in turn led to changes in the contaminant plume lengths.     

Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

Delineating and quantifying ground water discharge zones using streambed temperatures

Streambed temperature mapping, hydraulic testing using minipiezometers, and geochemical analyses of interstitial water of the streambed were used to delineate the pattern of ground water discharge in a sandy streambed and to develop a flux-based conceptual model for ground water/surface water interactions. A new and simple empirical method was used to relate fluxes obtained from minipiezometer data to streambed temperatures. The relationship allowed flux to be calculated at locations where only streambed temperature measurements were made. Slug testing and potentiomanometer measurements at 34 piezometers indicated ground water discharge ranged from 0.03 to 446 L/m2/day (and possibly as high as 7060 L/m2/day) along a 60 m long by 11 to 14 m wide reach of river. Complex but similar plan-view patterns of flux were calculated for both summer and winter using hundreds of streambed temperatures measured on a 1 by 2 m grid. The reach was dominated by ground water discharge and 5% to 7% of the area accounted for approximately 20% to 24% of the total discharge. < 12% of the total area consisted of recharge zones or no-discharge zones. A conceptual model for ground water/surface water interactions consisting of five different behaviors was developed based on the magnitude and direction of flux across the surface of the streambed. The behaviors include short-circuit discharge (e.g., high-flow springs), high discharge (e.g., preferential flowpaths), low to moderate discharge, no discharge (e.g., horizontal hyporheic or ground water flow), and recharge. Geological variations at depth played a key role in determining which type of flow behavior occurred in the streambed.     

Estimating Persistent Mass Flux of Volatile Contaminants from the Vadose Zone to Ground Water

Contaminants may persist for long time periods within low permeability portions of the vadose zone where they cannot be effectively treated and are a potential continuing source of contamination to ground water. Setting appropriate vadose zone remediation goals typically requires evaluating these persistent sources in terms of their impact on meeting ground water remediation goals. Estimating the impact on ground water can be challenging at sites with low aqueous recharge rates where vapor-phase movement is the dominant transport process in the vadose zone. Existing one-dimensional approaches for simulating transport of volatile contaminants in the vadose zone are considered and compared to a new flux-continuity-based assessment of vapor-phase contaminant movement from the vadose zone to the ground water. The flux-continuity-based assessment demonstrates that the ability of the ground water to move contaminant away from the water table controls the vapor-phase mass flux from the vadose zone across the water table. Limitations of these approaches are then discussed with respect to the required assumptions and the need to incorporate three-dimensional processes when evaluating vapor-phase transport from the vadose zone to the ground water. The carbon tetrachloride plume at the U.S. Department of Energy Hanford Site is used as the example site where persistent vadose zone contamination needs to be considered in the context of ground water remediation.     

Removal of Two Pharmaceutically Active Compounds from Aqueous Phase Using an Engineered Floodplain Filtration System

This study investigated the removal of two model pharmaceutically active compounds (PhAcs), viz., ibuprofen and triclosan, in lab‐scale engineered floodplain filtration (EFF) system. Biodegradation experiments were performed to acquire knowledge about the degradation of the targeted PhAcs, at an initial concentration of 350 µg/L. Biodegradation results showed that the two compounds were bio‐transformed to >70% after 15 days of incubation. Column tests were performed in a statistically significant manner to determine the adsorptive potential of the suggested filler layer in the EFF (C/C₀), by varying the flow rate and initial concentration of the compound. It was observed based on the F and p‐values that the main effects (F = 3163, p < 0.005) were more significant than the interactive effects (F = 9561, p < 0.05) for both ibuprofen and triclosan removal. Besides, by performing the Student's “t” test, it was concluded that the flow rate plays a major role in determining the rapidness of achieving complete breakthrough than the initial concentration of both the compounds. The data obtained from column studies under biotic conditions indicated that the removal mechanism for PhAcs is mainly biotransformation based, and that an EFF system may be effectively used to remove these emerging compounds during ground water recharge for water recycling.     

Impact of Recharge Through Residual Oil Upon Sampling of Underlying Ground Water

At an aviation gasoline spill site in Traverse City, Michigan, historical records indicate a positive correlation between significant rainfall events and increased concentrations of slightly soluble organic compounds in the monitoring wells of the site. To investigate the recharge effect on ground water quality due to infiltrating, water percolating past residual oil and into the saturated zone, an in situ infiltration experiment was performed at the site. Sampling cones were set at various depths below a circular test area, 13 feet (4 meters) in diameter. Rainfall was simulated by sprinkling the test area at a rate sufficiently low to prevent runoff. The sampling cones for soil-gas and ground water quality were installed in the unsaturated and saturated zones to observe the effects of the recharge process. At the time of the test, the water table was below the residual oil layer. The responses of the soil-gas and ground water quality were monitored during the recharge and drainage periods, which resulted from the sprinkling.
Infiltrated water was determined to have transported organic constituents of the residual oil, specifically benzene, toluene, ethylbenzene, and ortho-xylene (BTEX), into the ground water beneath the water table, elevating the aqueous concentrations of these constituents in the saturated zone. Soil-gas concentrations of the organic compounds in the unsaturated zone increased with depth and time after the commencement of infiltration. Reaeration of the unconfined aquifer via the infiltrated water was observed. It is concluded that water quality measurements are directly coupled to recharge events for the sandy type of aquifer with an overlying oil phase, which was studied in this work. Ground water sampling strategies and data analysis need to reflect the effect of recharge from precipitation on shallow, unconfined aquifers where an oil phase may be present.     

Temporal Changes in VOC Discharge to Surface Water from a Fractured Rock Aquifer During Well Installation and Operation, Greenville, South Carolina

Analysis of the vapor in passive vapor samplers retrieved from a streambed in fractured rock terrain implied that volatile organic carbon (VOC) discharge from ground water to surface water substantially increased following installation of a contaminant recovery well using air rotary drilling. The air rotary technique forced air into the aquifer near the stream. The injection produced an upward hydraulic gradient that appears to have transported water and contaminants from deeper parts of the aquifer through fractures into shallow parts of the aquifer. Once in the shallow flow regime, the contamination was transported to the stream, where it discharged during the next several weeks following well installation. After the recovery well was activated and began continuously pumping contaminated ground water to a treatment facility, the VOC concentrations in the stream bottom passive vapor samplers decreased to below detectable concentrations, suggesting that the withdrawal had captured the contaminated ground water that previously had discharged to the stream.     

Estrogenic Activity and Volume Fraction of Waste Water Origin in Monitoring Wells Along the Santa Cruz River, Arizona

The fate of estrogenic activity in waste water effluent was examined during surface transport and incidental recharge along the Santa Cruz River in Pima County, Arizona. Based on measurement of boron isotopes, the fractional contribution of reclaimed water in surface waters and ground water wells proximate to the river was determined for a contemporary sample set. Estrogenic activity decreased by −60% over the 25 mi length of the river below effluent discharge points in Tucson. In ground water samples obtained from monitoring wells that are proximate to the Santa Cruz River, both dissolved organic carbon ( p = 0.0003) and estrogenic activity ( p = 3 × 10⁻⁶) were highly correlated to fractional waste water content. Results indicate that proximate ground water quality is sensitive to incidental recharge of reclaimed water in the Santa Cruz River bed. In a few locations, little attenuation of estrogenic activity was apparent during percolation of effluent in the river channel to well withdrawal points.     

Eolian Transport of Geogenic Hexavalent Chromium to Ground Water

A conceptual model of eolian transport is proposed to address the widely distributed, high concentrations of hexavalent chromium (Cr⁺⁶) observed in ground water in the Emirate of Abu Dhabi, United Arab Emirates. Concentrations (30 to more than 1000 μg/L Cr⁺⁶) extend over thousands of square kilometers of ground water systems. It is hypothesized that the Cr is derived from weathering of chromium-rich pyroxenes and olivines present in ophiolite sequence of the adjacent Oman (Hajar) Mountains. Cr⁺³ in the minerals is oxidized to Cr⁺⁶ by reduction of manganese and is subsequently sorbed on iron and manganese oxide coatings of particles. When the surfaces of these particles are abraded in this arid environment, they release fine, micrometer-sized, coated particles that are easily transported over large distances by wind and subsequently deposited on the surface. During ground water recharge events, the readily soluble Cr⁺⁶ is mobilized by rain water and transported by advective flow into the underlying aquifer. Chromium analyses of ground water, rain, dust, and surface (soil) deposits are consistent with this model, as are electron probe analyses of clasts derived from the eroding Oman ophiolite sequence. Ground water recharge flux is proposed to exercise some control over Cr⁺⁶ concentration in the aquifer.     

Nitrate transport in the unsaturated zone: a case study of the riverbank filtration system Karany,Czech Republic

Nitrate transport in the unsaturated zone of a riverbank filtration (RBF) system in Karany, Czech Republic, was studied. Previous study of the system estimated RBF recharge as 60% riverbank filtrate and 40% local groundwater contaminated by nitrates. Nitrate concentrations observed in RBF recently cannot be explained by simple groundwater contamination and a new conception of groundwater recharge is suggested. A two‐component model based on water ¹⁸O data modelled recharge of local groundwater. One component of groundwater recharge is rainfall and irrigation water moving through the unsaturated zone of the Quaternary sediments in piston flow. The second component is groundwater from the Cretaceous deposits with a free water table. Both the components of groundwater recharge have different nitrate concentrations, and resulting contamination of groundwater depends on the participation of water from Quaternary and Cretaceous deposits. Nitrates' origins and their mixing in the subsurface were traced by ¹⁵N data. Nitrate transport from the unsaturated zone is important and time variable source of groundwater contamination. Copyright © 2011 John Wiley & Sons, Ltd.     

Anthropogenic organic contaminants in water, sediments and benthic organisms of the mangrove-fringed Segara Anakan Lagoon, Java, Indonesia

Segara Anakan, a mangrove-fringed coastal lagoon in Indonesia, has a high diversity of macrobenthic invertebrates and is increasingly affected by human activities. We found >50 organic contaminants in water, sediment and macrobenthic invertebrates from the lagoon most of which were polycyclic aromatic compounds (PACs). Composition of PACs pointed to petrogenic contamination in the eastern lagoon. PACs mainly consisted of alkylated PAHs, which are more abundant in crude oil than parent PAHs. Highest total PAC concentration in sediment was above reported toxicity thresholds for aquatic invertebrates. Other identified compounds derived from municipal sewage and also included novel contaminants like triphenylphosphine oxide. Numbers of stored contaminants varied between species which is probably related to differences in microhabitat and feeding mode. Most contaminants were detected in Telescopium telescopium and Polymesoda erosa. Our findings suggest that more attention should be paid to the risk potential of alkylated PAHs, which has hardly been addressed previously.