Janek Greskowiak

Modeling the fate of organic micropollutants during river bank filtration (Berlin, Germany).

Emerging organic contaminants (EOCs) are frequently detected in urban surface water and the adjacent groundwater and are therefore an increasing problem for potable water quality. River bank filtration (RBF) is a beneficial pretreatment step to improve surface water quality for potable use. Removal is mainly caused by microbial degradation of micropollutants, while sorption retards the transport. The quantification of biodegradation and adsorption parameters for EOCs at field scale is still scarce. In this study, the fate and behavior of a range of organic compounds during RBF were investigated using a two dimensional numerical flow- and transport model. The data base used emanated from a project conducted in Berlin, Germany (NASRI: Natural and Artificial Systems for Recharge and Infiltration). Oxygen isotope signatures and hydraulic head data were used for model calibration. Afterwards, twelve organic micropollutants were simulated with a reactive transport model. Three compounds (primidone, EDTA, and AMDOPH) showed conservative behavior (no biodegradation or sorption). For the nine remaining compounds (1.5 NDSA, AOX, AOI, MTBE, carbamazepine, clindamycin, phenazone, diclofenac and sulfamethoxazole), degradation and/or sorption was observed. 1.5 NDSA and AOX were not sorbed, but slightly degraded with model results for λ=2.25e(-3) 1/d and 2.4e(-3) 1/d. For AOI a λ=0.0106 1/d and R=1 were identified. MTBE could be characterized well assuming R=1 and a low 1st order degradation rate constant (λ=0.0085 1/d). Carbamazepine degraded with a half life time of about 66 days after a threshold value of 0.2-0.3 μg/L was exceeded and retarded slightly (R=1.7). Breakthrough curves of clindamycin, phenazone, diclofenac and sulfamethoxazole could be fitted less well, probably due to the dependency of degradation on temperature and redox conditions, which are highly transient at the RBF site. Conditions range from oxic to anoxic (up to iron-reducing), with the oxic and denitrifying zones moving spatially back and forth over time.

Temperature dependent redox zonation and attenuation of wastewater-derived organic micropollutants in the hyporheic zone

The hyporheic zone - a spatially fluctuating ecotone connecting surface water and groundwater - is considered to be highly reactive with regard to the attenuation of organic micropollutants. In the course of the presented study an undisturbed sediment core was taken from the infiltration zone of a bank filtration site in Berlin and operated under controlled laboratory conditions with wastewater-influenced surface water at two different temperatures, simulating winter and summer conditions. The aim was to evaluate the fate of site-relevant micropollutants, namely metoprolol, iopromide, diclofenac, carbamazepine, acesulfame, tolyltriazole, benzotriazole, phenazone and two phenazone type metabolites, within the first meter of infiltration dependent on the prevailing temperature. A change in temperature resulted in a development of significantly distinct redox conditions. Both temperature dependencies and related redox dependencies were identified for all micropollutants except for benzotriazole and carbamazepine, which behaved persistent under all conditions. For the remaining compounds degradation rate constants generally decreased from warm and oxic/penoxic/suboxic over cold and oxic/penoxic to warm and manganese reducing (transition zone). Individual degradation rate constants ranged from 0 (e.g. diclofenac, acesulfame and tolyltriazole in the transition zone) to 1.4×10(-4)s(-1) for metoprolol under warm conditions within the oxic to suboxic zone.

Sorption behavior of 20 wastewater originated micropollutants in groundwater — Column experiments with pharmaceutical residues and industrial agents

Since sorption is an essential process with regard to attenuation of organic pollutants during subsurface flow, information on the sorption properties of each pollutant are essential for assessing their environmental fate and transport behavior. In the present study, the sorption behavior of 20 wastewater originated organic micropollutants was assessed by means of sediment column experiments, since experimentally determined data for these compounds are not or sparsely represented in the literature. Compounds investigated include various psychoactive drugs, phenazone-type pharmaceuticals and β-blockers, as well as phenacetine, N-methylphenacetine, tolyltriazole and para-toluenesulfonamide. While for most of the compounds no or only a low sorption affinity was observed, an elevated tendency to sorb onto aquifer sand was obtained for the β-blockers atenolol, propranolol and metoprolol. A comparison between experimental data and data estimated based on the octanol/water partition coefficient following the QSAR approach demonstrated the limitations of the latter to predict the adsorption behavior in natural systems for the studied compounds.

Redox-dependent removal of 27 organic trace pollutants: compilation of results from tank aeration experiments

The biodegradation of various wastewater-derived organic trace pollutants occurring in different aquatic compartments of the environment was previously reported to be influenced by the prevailing redox conditions. However, comparative studies on the redox-dependent degradation behavior of organic trace pollutants are scarce. The objective of the study presented herein, was to compile and evaluate data from several comparable previous tank experiments, thus, providing an overview on the redox-dependent removal of a total of 27 wastewater-derived trace compounds, including phenazone type compounds, antimicrobials, ß-blockers, psychoactive drugs and sulfonamides. Removal rate constants were fitted assuming first-order degradation kinetics. Six compounds were identified to be removed solely under oxic, three compounds solely under anoxic conditions. Others persisted under all experimental conditions, while some were removed under both oxic and anoxic conditions.

The fate of organic micropollutants during long-term/long-distance river bank filtration

The fate of organic micropollutants during long-term/long-distance river bank filtration (RBF) at a temporal scale of several years was investigated along a row of monitoring wells perpendicular to the Lek River (the Netherlands). Out of 247 compounds, which were irregularly analyzed in the period 1999-2013, only 15 were detected in both the river and river bank observation wells. Out of these, 10 compounds (1,4-dioxan, 1,5-naphthalene disulfonate (1,5-NDS), 2-amino-1,5-NDS, 3-amino-1,5-NDS, AOX, carbamazepine, EDTA, MTBE, toluene and triphenylphosphine oxide) showed fully persistent behavior (showing no concentration decrease at all), even after 3.6 years transit time. The remaining 5 compounds (1,3,5-naphthalene trisulfonate (1,3,5-NTS), 1,3,6-NTS, diglyme, iopamidol, triglyme) were partially removed. Their reactive transport parameters (removal rate constants/half-lives, retardation coefficients) were inferred from numerical modeling. In addition, maximum half-lives for 14 of the fully removed compounds, for which the data availability was sufficient to deduce 100% removal during sub-surface passage, were approximated based on travel times to the nearest well. The study is one of very few reporting on the long-term field-scale behavior of organic micropollutants. It highlights the efficiency of RBF for water quality improvement as a pre-treatment step for drinking water production. However, it also shows the very persistent behavior of various compounds in groundwater.

Tide‐induced salt‐fingering flow during submarine groundwater discharge

This study investigated the stability of the upper saline plume (USP) within shallow tide-affected submarine groundwater discharge (SGD) zones. In contrast to earlier studies, numerical modeling revealed a number of realistic hydrological and hydrogeological conditions where the USP becomes unstable and salt-fingering flow occurs. These conditions were reasonably well identified in a stability diagram based on two dimensionless numbers that characterize the system. If fingering flow occurs, the SGD pattern is distinctly different from that of stable flow conditions: (i) freshwater discharge zones along the beach face are manifold and change their location with time, (ii) undulating freshwater/seawater interface that is extended along the groundwater flow path, and (iii) the total tide-averaged fresh SGD rate varies considerably in an irregular pattern. This has presumably important implications on reactive transport processes in the subterranean estuary, as well as on the interpretation of field data on water and solute fluxes during SGD.

Kinetic reaction modeling framework for identifying and quantifying reductant reactivity in heterogeneous aquifer sediments.

Water-sediment interactions triggered by the injection of oxidized aqueous solutions into anoxic groundwater systems usually modify both the aquifer matrix and control the final aqueous composition. The identification and quantification of these reactions in complex heterogeneous systems remains a challenge for the analysis and prediction of water quality changes. Driven by the proposed injection of large quantities of oxic water into a deep anoxic heterogeneous pyritic aquifer; this study was undertaken to quantify the reactivity of aquifer sediments with respect to oxidant consumption and to characterize the variability of the reaction rates across different lithological units. A total of 53 samples were incubated for periods of 14, 37, and 50 days, during which the gas-phase was continuously monitored and the aqueous composition analyzed. A geochemical modeling framework was developed that incorporated a mixed set of equilibrium and kinetic reactions and supported the interpretation and quantification of the geochemical controls. The good agreement between simulated and experimental results of O2 consumption, CO2 production, pH, major ions, and trace metals suggests that the framework was able to successfully quantify reaction rates of competing redox and buffering reactions for the different lithological aquifer material.

Influence of calcite on uranium(VI) reactive transport in the groundwater-river mixing zone

Calcite is an important, relatively soluble mineral phase that can affect uranium reactive transport in subsurface sediments. This study was conducted to investigate the distribution of calcite and its influence on uranium adsorption and reactive transport in the groundwater-river mixing zone of the Hanford 300A site, Washington State. Simulations using a two-dimensional (2D) reactive transport model under field-relevant hydrological and hydrogeochemical conditions revealed the development of a calcite reaction front through the mixing zone as a result of dynamic groundwater-river interactions. The calcite concentration distribution, in turn, affected the concentrations of aqueous carbonate and calcium, and pH through dissolution, as river waters intruded and receded from the site at different velocities in response to stage changes. The composition variations in groundwater subsequently influenced uranium mobility and discharge rates into the river in a complex fashion. The results implied that calcite distribution and concentration are important variables that need to be quantified for accurate reactive transport predictions of uranium, especially in dynamic groundwater-river mixing zones.

Modeling the transport behavior of 16 emerging organic contaminants during soil aquifer treatment.

In this study, four one-dimensional flow and transport models based on the data of a field scale experiment in Greece were constructed to investigate the transport behavior of sixteen organic trace pollutants during soil aquifer treatment. At the site, tap water and treated wastewater were intermittently infiltrated into a porous aquifer via a small pilot pond. Electrical conductivity data was used to calibrate the non-reactive transport models. Transport and attenuation of the organic trace pollutants were simulated assuming 1st order degradation and linear adsorption. Sorption was found to be largely insignificant at this site for the compounds under investigation. In contrast, flow path averaged first order degradation rate constants were mostly higher compared to the literature and lay between 0.036 d(-1) for clofibric acid and 0.9 d(-1) for ibuprofen, presumably owing to the high temperatures and a well adapted microbial community originating from the wastewater treatment process. The study highlights the necessity to obtain intrinsic attenuation parameters at each site, as findings cannot easily be transferred from one site to another.

Detecting Small Groundwater Discharge Springs Using Handheld Thermal Infrared Imagery

Ground-based handheld thermal infrared imagery was used for the detection of small-scale groundwater springs at the northwestern beach of Spiekeroog Island (northwest Germany). The surveys and in situ measurements of electric conductivity were carried out from shortly before to shortly after low tide along the low water line. Several brackish groundwater discharge springs with a diameter of 1-2 cm were observed along the beach at a distance of 2-3 m above the low water line. The high fresh water portion in the discharging water derives from the fresh water lens in the center of the island. During cold weather, the springs were identified by a significantly increased temperature (3-5 °C higher) and a lower electric conductivity (<10 mS/cm) in contrast to the surrounding sea water (1-2 °C, >30 mS/cm). During warmer weather conditions, an inverse temperature contrast was observed. The measurements confirm the applicability of thermal imagery for the detection of small-scale groundwater discharge locations as an extension to the established method of aerial thermal scans and prove the existence of submarine groundwater seeps in porous systems. A ground-based handheld thermal infrared imagery survey enables a precise installation of sampling devices as, for example, seepage meters.