Effect of fragmentation on the transport of polyvinyl chloride and low-density polyethylene in saturated quartz sand.

Microplastics are an obstinate pollutant in terrestrial environments, posing a risk to the subsurface soil matrix and potentially to groundwater. In this study, the transport and retention behaviour of two major plastic polymers, 125-300 µm Polyvinyl chloride (PVC) plastic fragments and 300 µm Low-density polyethylene (LDPE) spherical particles, were explored in saturated quartz sand (1.6-2.0 mm) columns. The PVC used in this study represented secondary microplastics, while the LDPE represented primary microplastics. Retention profiles at different ultrapure water flow rates (2.0-3.5 ml/min) were compared and analysed. At the beginning and end of each column test, the microplastic particles were scrutinized, identified, and quantified by light microscopy. The results showed that the transport distance of microplastic particles increased with their decreasing diameter. Small-sized PVC microplastic particles, whose morphology was more 1-dimensional, were more susceptible to fragmentation within the column, promoting migration. Spherical LDPE remained at their initial position without fragmenting. Microplastic degradation into fragments appeared to play an important role in improving the movement of particles. This study offers initial indications of infiltration depths and shape-dependent fragmentation of secondary microplastics in coarse sand based on the lab experiments.

Transport-based source tracking of contaminants in a karst aquifer: Model implementation, proof of concept, and application to event-based field data.

Identification and location of contamination sources is crucial for water resource protection - especially in karst aquifers which provide 25% of the world´s population with water but are highly vulnerable to contamination. Transport-based source tracking is proposed and verified here as a complementary approach to microbial and chemical source tracking in karst aquifers for identifying and locating such sources of contamination and for avoiding ambiguities that might arise from using one method alone. The transport distance is inversely modelled from contaminant breakthrough curves (BTC), based on analytical solutions of the 1D two-region non-equilibrium advection dispersion equation using GNU Octave. Besides the BTC, the model requires reliable estimates of transport velocity and input time. The model is shown to be robust, allows scripted based, automated 2D sensitivity analyses (interplay of two parameters), and can be favourable when distributed numerical models are inappropriate due to insufficient data. Sensitivity analyses illustrate that the model is highly sensitive to the input time, the flow velocity, and the fraction of the mobile fluid region. A conclusive verification approach was performed by applying the method to synthetic data, tracer tests, and event-based field data. Transport distances were correctly modelled for a set of artificial tracer tests using a discharge-velocity relationship that could be established for the respective karst catchment. For the first time such an approach was shown to be applicable to estimate the maximum distance to the contamination source for coliform bacteria in karst spring water combined with microbial source tracking. However, prediction intervals for the transport distance can be large even in well-studied karst catchments mainly related to uncertainties in the flow velocity and the input time. Using a maximum transport distance is proposed to account for less permeable, "slower" pathways. In general, transport-based source tracking might be used wherever transport can be described by the 1D two-region non-equilibrium model, e.g. rivers and fractured or porous aquifers.

Transport behavior of the pharmaceutical compounds carbamazepine, sulfamethoxazole, gemfibrozil, ibuprofen, and naproxen, and the lifestyle drug caffeine, in saturated laboratory columns.

Despite the large number of pharmaceutically active compounds found in natural environments little is known about their transport behavior in groundwater, which is complicated by their wide range of physical and chemical properties. The transport behavior of five widely used and often detected pharmaceutical compounds and one lifestyle drug has therefore been investigated, using a set of three column experiments. The investigated compounds were the anticonvulsant carbamazepine, the lifestyle drug caffeine, the antibiotic sulfamethoxazole, the lipid regulator gemfibrozil, and the nonsteroidal anti-inflammatories ibuprofen and naproxen. The columns were filled with three different types of sand. The substrates consisted of artificially prepared iron-coated sand, artificially prepared organic carbon sand (with 5% leaf compost), and natural aquifer sand from Long Point, Ontario (Canada). The experiments were conducted simultaneously under the same hydraulic conditions and with the same input solution of about 1µg·L-1 of each compound. The transport behavior of the organic compounds differed significantly between both the different columns and the different compounds. A strong correlation was observed between the retardation factors for carbamazepine, gemfibrozil, and ibuprofen and the organic carbon content of the substrate. While the retardation increased with increasing organic carbon content, no direct relationship was observed between the organic carbon content and the removal of these compounds. In contrast, the retardation factors for sulfamethoxazole and naproxen showed no correlation with the organic carbon content but these compounds were significantly removed in the presence of organic matter. The influence of the Fe3+ surfaces in the iron-coated sand was less significant than expected, with all compounds except for sulfamethoxazole having retardation factors <1.8. Caffeine was so strongly removed during transport through those substrates containing organic carbon that no reliable retardation factor could be determined.

Transport and Attenuation of Particles of Different Density and Surface Charge: A Karst Aquifer Field Study.

Although karst aquifers are far more susceptible to contamination than porous aquifers, with the transport of particulate matter being an important factor, little is known about the attenuation of solutes within karst aquifers and even less about the attenuation of particulate matter. These in situ investigations have therefore aimed to systematically identify the processes that influence the transport and attenuation of particles within a karst aquifer through multitracer testing, using four different types of 1 µm fluorescent particles and the fluorescent dye uranine. Each of the types of particles used were detected at the observed spring, which drains the investigated aquifer. However, the transport behavior varied significantly between the various particles and the uranine dye, with the breakthrough of particles occurring slightly earlier than that of uranine. Attenuation was determined from the tracer recovery and attributed to filtration processes. These processes were affected by the hydrophobicity and surface charge of the particles. Carboxylated polystyrene particles with a density and surface charge comparable to pathogenic microorganisms were found to be mobile in groundwater over a distance of about 3 km. No attenuation was observed for plain silica particles. Particles with these characteristics thus pose a major threat to karst spring water as they might occur as contaminants themselves or facilitate the transport of other contaminants.

Use of two artificial sweeteners, cyclamate and acesulfame, to identify and quantify wastewater contributions in a karst spring.

The identification and differentiation of different sources of contamination are crucial aspects of risk assessment in water resource protection. This is especially challenging in karst environments due to their highly heterogeneous flow fields. We have investigated the use of two artificial sweeteners, cyclamate and acesulfame, as an indicator set for contamination by wastewater within the rural catchment of a karst spring. The catchment was investigated in detail to identify the sources of artificial sweeteners and quantify their impact. Spring water was analysed following two different but typical recharge events: (1) a rain-on-snow event in winter, when no wastewater overflow from the sewer system was observed, and (2) an intense rainfall event in summer triggering an overflow from a stormwater detention basin. Acesulfame, which is known to be persistent, was quantified in all spring water samples. Its concentrations decreased after the winter event with no associated wastewater spillage but increased during the summer event following a recent input of untreated wastewater. Cyclamate, which is known to be degradable, was only detected following the wastewater inflow incident. The cyclamate signal matched very well the breakthrough of faecal indicator bacteria, indicating a common origin. Knowing the input function, cyclamate was used quantitatively as a tracer in transport modelling and the impact of 'combined sewer overflow' on spring water quality was quantified. Signals from artificial sweeteners were compared to those from bulk parameters (discharge, electrical conductivity and turbidity) and also to those from the herbicides atrazine and isoproturon, which indicate 'old' and 'fresh' flow components, respectively, both originating from croplands. High concentration levels of the artificial sweeteners in untreated wastewater (cyclamate and acesulfame) and in treated wastewater (acesulfame only) make them powerful indicators, especially in rural settings where wastewater input is relatively low, and in karst systems where dilution is often high.

Relationship between organic micropollutants and hydro-sedimentary processes at a karst spring in south-west Germany.

Karst aquifers are known to be highly vulnerable to contamination due to their particular hydraulic characteristics. A number of parameters (such as turbidity, dissolved organic matter concentration, particle size distribution) have been proposed as proxies that can be used to detect changes in water quality or contamination of karst springs. However, most of these are not very specific concerning the source of any contamination. Organic micropollutants (OMPs) such as artificial sweeteners or herbicides are possible source-specific indicators that can be used in karst catchment areas, but real time monitoring is not as yet possible for these compounds. We have investigated the possibility of combining the source-specific features of OMPs with real-time measurements of electrical conductivity (EC) and turbidity by means of ECturbidity hysteresis plots. These plots allow for identifying different hydro-sedimentary processes. Our investigations were carried out at the Gallusquelle karst spring in south-west Germany, during high flow conditions that occurred in 2013 after heavy precipitation. The herbicide atrazine, which derives from the aquifer matrix, was detectable in the spring water until resuspended particles appeared at the spring. The herbicide metazachlor, which is present in recharge from cropland, was found to be associated with periods of direct transfer of particles originating from the land surface. The artificial sweetener cyclamate was used as a wastewater indicator, but neither hysteresis plots of EC and turbidity nor any other real-time parameters were able to detect the presence of cyclamate following a wastewater spill. Since EC and turbidity are easily measurable parameters, the systematic relationships of ECturbidity hysteresis behavior to OMPs might assist in the sustainable management of raw water within karst catchments.

Impact of materials used in lab and field experiments on the recovery of organic micropollutants.

Organic micropollutants are frequently detected in the aquatic environment. Therefore, a large number of field and laboratory studies have been conducted in order to study their fate in the environment. Due to the diversity of chemical properties among these compounds some of them may interact with materials commonly used in field and laboratory studies like tubes, filters, or sample bottles. The aim of our experiment was to study the interaction between those materials and an aqueous solution of 43 widely detected basic, neutral, and acidic organic micropollutants hereby covering a broad range of polarities. Experiments with materials were conducted as a batch study using spiked tap water and for different syringe filters by filtration with subsequent fraction collection. The best recoveries over a wide range of organic compounds were observed for batches in contact with the following materials (in descending order) acryl glass, PTFE, HDPE, and PP. The use of Pharmed©, silicone, NBR70, Tygon©, and LDPE should be avoided. Flexible tubing materials especially influence many of the investigated compounds here. Filtration with most of the tested filter types leads to no significant loss of almost all of the investigated micropollutants. Nonetheless, significant mass losses of some compounds (loratadine, fluoxetine, sertraline, and diuron) were observed during the first mL of the filtration process. No systematic correlation between compound properties, tested materials, and observed mass losses could be identified in this study. The behavior of each compound is specific and thus, not predictable. It is therefore suggested to study the interaction of compounds with filters and material prior to the actual experiment or include blank studies.

Potential of zerovalent iron nanoparticles for remediation of environmental organic contaminants in water: a review.

Zerovalent iron (ZVI) has the potential to degrade different organic contaminants. Nanoscale zerovalent iron (NZVI) can reduce the contaminants even more rapidly due to its small size and large specific surface area (SSA), compared to granular ZVI. The main objective of this paper is to assess and compare the potential of NZVI for degradation of different contaminants in water under specific environmental conditions. As a first step, the potential reactive functional groups/bonds associated with different contaminants are identified and possible reaction mechanisms are discussed. Thereafter, the reaction efficiencies of different organic contaminants with NZVI are compared. Mass of ZVI and reaction time required to transform a certain amount of contaminated water are calculated based on literature data. Sources of contaminants in the environment and their environmental occurrences are discussed to understand the potential locations where NZVI could be applied for removal of different contaminants. Overall it is observed that azo-compounds are readily transformed in the presence of NZVI particles. Reaction efficiencies of ZVI for reduction of nitro-organic compounds are also reasonably high. However, halogenated compounds with high molecular weights or complex structures (i.e., iodinated contrast media, DDT, polychlorinated biphenyls, etc.) show lower reaction rates with NZVI compared to the widely studied chlorinated hydrocarbons (i.e., trichloroethylene).

Laboratory-scale experiments and numerical modeling of cosolvent flushing of multi-component NAPLs in saturated porous media.

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations was also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with low flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. Model simulations over-estimated NAPL recovery for high specific discharges and rate-limited mass transfer, suggesting a constant mass transfer coefficient for the entire flushing experiment may not be valid. When multi-component NAPLs are present, the dissolution rate of individual organic compounds (namely, toluene and benzene) into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values.

Redox-sensitivity and mobility of selected pharmaceutical compounds in a low flow column experiment.

In this study a laboratory column experiment under water saturated conditions was conducted to investigate the transport behaviour of the pharmaceutical compounds sulfamethoxazole, carbamazepine, diclofenac, and ibuprofen under varying nitrate concentrations. Organic rich sediment (f(OC)=0.01) and surface water from a formerly investigated field site were used. The water was spiked with the four compounds and the specific redox conditions in the column (0.351 m height) were varied throughout the experiment by adding nitrate in the influent water. Stepwise controlled decreasing influent nitrate concentrations between 131 and 20 mg L(-1) were applied in the course of the experiment which lasted 71 days. This established temporarily denitrifying conditions in the column during the reduction of nitrate. Sulfamethoxazole was severely influenced by this process. During denitrification sulfamethoxazole concentrations in the effluent water decreased rapidly and significantly. This experiment demonstrates the strong dependency of sulfamethoxazole transformation specifically on nitrate reducing redox conditions and therefore may help to explain the wide ranges of reported degradability for this compound. Ibuprofen was more stable under denitrifying redox conditions. Both for carbamazepine and diclofenac apparent retardation was observed. For carbamazepine this was attributed to sorption and also to degradation. For diclofenac nitrate controlled degradation seems the dominating process for the apparent retardation of this compound.

Activated soil filters for removal of biocides from contaminated run-off and waste-waters.

Building facades can be equipped with biocides to prevent formation of algal, fungal and bacterial films. Thus run-off waters may contain these highly active compounds. In this study, the removal of several groups of biocides from contaminated waters by means of an activated soil filter was studied. A technical scale activated vertical soil filter (biofilter) with different layers (peat, sand and gravel), was planted with reed (Phragmites australis) and used to study the removal rates and fate of hydrophilic to moderate hydrophobic (log K(ow) 1.8-4.4) biocides and biocide metabolites such as: Terbutryn, Cybutryn (Irgarol® 1051), Descyclopropyl-Cybutryn (Cybutryn and Terbutryn metabolite), Isoproturon, Diuron, and its metabolite Diuron-desmonomethyl, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone and Iodocarbamate (Iodocarb). Three experiments were performed: the first one (36 d) under low flow conditions (61 L m(-2) d(-1)) reached removal rates between 82% and 100%. The second one was performed to study high flow conditions: During this experiment, water was added as a pulse to the filter system with a hydraulic load of 255 L m(-2) within 5 min (retention time <1 h). During this experiment the removal rates of the compounds decreased drastically. For five compounds (Cybutryn, Descyclopropyl-Cybutryn, Diuron, Isoproturon, and Iodocarb) the removal dropped temporarily below 60%, while it was always above 70% for the others (Terbutryn, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone). However, this removal is a considerable improvement compared to direct discharge into surface waters or infiltration into soil without appropriate removal. In the last experiment the removal efficiencies of the different layers were studied. Though the peat layer was responsible for most of the removal, the sand and gravel layers also contributed significantly for some compounds. All compounds are rather removed by degradation than by sorption.

Vertical flow soil filter for the elimination of micro pollutants from storm and waste water.

A technical scale activated soil filter has been used to study the elimination rates of diverse environmentally relevant micro pollutants from storm and waste water. The filter was made of layers of peat, sand and gravel. The upper (organic) layer was planted with reed (phragmites australis) to prevent clogging and was spiked with activated sludge to enhance microbial biomass and biodegradation potential. Compounds used as UV filters, antioxidants or plasticizers, namely 4-methylbenzylidene camphor (4-MBC), benzophenone-3 (BP-3), butylated hydroxytoluene (BHT), N-butylbenzenesulfonamide (NBBS), 2,6-di-tert-butyl-1,4-benzoquinone (2,6-DTB-1,4-BQ), 1,1-biphenyl-3,3-dimethyl (1,1-BP-3,3-DM) and dibenzyl (DB) have been included in this study. The chemical characteristics of these compounds ranged from the hydrophilic (pK(OW) 2.6) to the lipophilic (pK(OW) 5) properties. For the elimination studies, synthetic waste water spiked to 3000 ng L(-1) with the selected compounds was used. Elimination rates with low hydraulic load (61 L m(-2)d(-1), water retention time: 2d) were higher than 96%. During a storm water simulation experiment (hydraulic load: 255 L m(-2), water retention time: <1h), the elimination rates of the most analytes decreased to 79-96%. The elimination performance of the hydrophilic compound NBBS declined to 21%. Balancing studies including the soil of the filter system revealed that degradation or transformation were both relevant elimination mechanism.

Mobility of pharmaceuticals carbamazepine, diclofenac, ibuprofen, and propyphenazone in miscible-displacement experiments.

Many pharmaceuticals pass the unsaturated zone before reaching an aquifer. Therefore, laboratory sand column transport experiments were conducted to study the transport behavior of carbamazepine, diclofenac, ibuprofen, and propyphenazone under unsaturated conditions. The test water was artificial sewage effluent to simulate the infiltration of reused wastewater. The test water was spiked with the pharmaceutically active compounds and the tracer LiCl. Afterwards it was passed through laboratory sand columns, one experiment for each pharmaceutical. The physical and chemical parameters were recorded and general ions measured. Pharmaceuticals were measured using solid phase extraction, derivatization, and detection with GC-MS. The column experiments indicate a significant elimination of ibuprofen (54%), propyphenazone (55%), and diclofenac (35%), whereas carbamazepine was not eliminated. Retardation factors varied between 1.84 for carbamazepine, 2.51 for propyphenazone, 3.00 for ibuprofen, and 4.80 for diclofenac. These results show that mobility and elimination of diclofenac, ibuprofen, and propyphenazone is about in the same range as for experiments under saturated conditions whereas carbamazepine had a significantly lower sorption and elimination under unsaturated conditions.

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 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.