Antibacterial activity of sulfamethoxazole transformation products (TPs): general relevance for sulfonamide TPs modified at the para position.

Sulfonamide antibiotics undergo transformation in the aquatic environment through biodegradation, photolysis, or hydrolysis. In this study, the residual antibacterial activity of 11 transformation products (TPs) of sulfamethoxazole (SMX) was investigated with regard to their in vitro growth and luminescence inhibition on Vibrio fischeri (30 min and 24 h exposure). Two transformation products, 4-hydroxy-SMX and N(4)-hydroxy-acetyl-SMX, were synthesized in-house and confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. Results of individual compound experiments showed that TPs modified at the para amino group still exhibit clear antibacterial effects, whereas TPs resulting from breakdown of the SMX structure lost this mechanism of action. 4-NO2- and 4-OH-SMX were found to inhibit growth to a clearly greater extent than the parent compound, SMX. In contrast, the N(4)-acetyl- and N(4)-hydroxy-acetyl-derivatives retain less than 10 and 5% of the effect of SMX on growth and luminescence inhibition, respectively. The effect of a mixture of para-modified TPs was observed to be additive. Considering the homologous series of sulfa drugs widely prescribed and their common mechanism of action, the potential environmental impact must consider the total amount of sulfonamide antibiotics and their derivative TPs, which might end up in a water body. Extrapolating the results obtained here for the para TPs of SMX to other sulfa drugs and determining the persistence and occurrence of these compounds in the aquatic environment is required for improved risk assessment.

Nanoparticles in aquatic systems.

Nanoparticles (NP) are ubiquitous in environmental and technical aquatic systems. Understanding the role and the fate of NP in these systems is an interdisciplinary challenge requiring innovative experimental, theoretical and analytical approaches and critical reflection of classical concepts. This contribution critically reviews the outstanding properties of NP and the resulting consequences for their behaviour in environmental and technical aquatic systems considering natural NP which are mostly geogenic or biogeogenic, and engineered NP. Owing to the severe lack of data on the occurrence of NP in environmental aquatic systems, it is a key task of researchers to further develop analytical methods for the sensitive detection of NP directly in aqueous samples. There is urgent need for standardisation of analytical methods for detection and characterisation of NP, and for toxicity tests to assess possible adverse effects of NP. In this context, NP reference materials have to be defined as a common fundament for research in this field.

Comparison of leaching tests to determine and quantify the release of inorganic contaminants in demolition waste.

The changes in waste management policy caused by the massive generation of waste materials (e.g. construction and demolition waste material, municipal waste incineration products) has led to an increase in the reuse and recycling of waste materials. For environmental risk assessment, test procedures are necessary to examine waste materials before they can be reused. In this article, results of column and lysimeter leaching tests having been applied to inorganic compounds in a reference demolition waste material are presented. The results show a good agreement between the leaching behaviour determined with the lysimeter unit and the column units used in the laboratory. In view of less time and system requirements compared to lysimeter systems, laboratory column units can be considered as a practicable instrument to assess the time-dependent release of inorganic compounds under conditions similar to those encountered in a natural environment. The high concentrations of elements in the seepage water at the initial stage of elution are reflected by the laboratory column leaching tests. In particular, authorities or laboratories might benefit and have an easy-to-use, but nevertheless reliable, method to serve as a basis for decision-making.

Short and long term biosorption of silica-coated iron oxide nanoparticles in heterotrophic biofilms.

The increased application of engineered nanoparticles (ENP) in industrial processes and consumer products has raised concerns about their impact on health and environmental safety. When ENP enter the global water cycle by e.g. wastewater streams, wastewater treatment plants (WWTP) represent potential sinks for ENP. During biological WWT, the attachment of ENP to biofilms is responsible for the desired removal of ENP from the water phase avoiding their release into the aquatic environment. However, the fundamental mechanisms guiding the interactions between ENP and biofilms are not yet fully understood. Therefore, this study investigates the behavior and biosorption of inorganic ENP, here magnetic iron oxide nanoparticles coated with silica (scFe3O4-NP), with heterotrophic biofilms at different time scales. Their magnetic properties enable to follow scFe3O4-NP in the biofilm system by a magnetic susceptibility balance and magnetic resonance imaging. Biofilms were exposed to scFe3O4-NP at short contact times (5 min) in flow cells and complementary, scFe3O4-NP were introduced into a moving bed biofilm reactor (MBBR) to be observed for 27 d. Mass balances revealed that scFe3O4-NP sorbed to the biofilm within a few minutes, but that the total biosorption was rather low (3.2 µg Fe/mg TSS). scFe3O4-NP mainly sorbed to the biofilm surface inducing the detachment of outer biofilm parts starting after an exposure time of 3h in the MBBR. The biosorption depended on the exposure concentration of scFe3O4-NP, but less on the contact time. Most scFe3O4-NP exited the flow cell (up to 65%) and the MBBR (57%) via the effluent. This effect was favored by the stabilization of scFe3O4-NP in the bulk liquid by organic matter leading to a low retention capacity of the MBBR system. The results contribute to improve our understanding about the fate of ENP in environmental and in technical biofilm systems and give indications for future investigations needed.

Magnetic resonance imaging reveals detailed spatial and temporal distribution of iron-based nanoparticles transported through water-saturated porous media.

The application of engineered nanoparticles (ENP) such as iron-based ENP in environmental systems or in the human body inevitably raises the question of their mobility. This also includes aspects of product optimization and assessment of their environmental fate. Therefore, the key aim was to investigate the mobility of iron-based ENP in water-saturated porous media. Laboratory-scale transport experiments were conducted using columns packed with quartz sand as model solid phase. Different superparamagnetic iron oxide nanoparticles (SPION) were selected to study the influence of primary particle size (d(P)=20 nm and 80 nm) and surface functionalization (plain, -COOH and -NH2 groups) on particle mobility. In particular, the influence of natural organic matter (NOM) on the transport and retention behaviour of SPION was investigated. In our approach, a combination of conventional breakthrough curve (BTC) analysis and magnetic resonance imaging (MRI) to non-invasively and non-destructively visualize the SPION inside the column was applied. Particle surface properties (surface functionalization and resulting zeta potential) had a major influence while their primary particle size turned out to be less relevant. In particular, the mobility of SPION was significantly increased in the presence of NOM due to the sorption of NOM onto the particle surface resulting in a more negative zeta potential. MRI provided detailed spatially resolved information complementary to the quantitative BTC results. The approach can be transferred to other porous systems and contributes to a better understanding of particle transport in environmental porous media and porous media in technical applications.

Low biosorption of PVA coated engineered magnetic nanoparticles in granular sludge assessed by magnetic susceptibility.

When engineered nanoparticles (ENP) enter into wastewater treatment plants (WWTP) their removal from the water phase is driven by the interactions with the biomass in the biological treatment step. While studies focus on the interactions with activated flocculent sludge, investigations on the detailed distribution of ENP in other types of biomass, such as granulated sludge, are needed to assess their potential environmental pollution. This study employed engineered magnetic nanoparticles (EMNP) coated with polyvinyl alcohol (PVA) as model nanoparticles to trace their fate in granular sludge from WWT. For the first time, magnetic susceptibility was used as a simple approach for the in-situ quantification of EMNP with a high precision (error <2%). Compared to other analytical methods, the magnetic susceptibility requires no sample preparation and enabled direct quantification of EMNP in both the aqueous phase and the granular sludge. In batch experiments granular sludge was exposed to EMNP suspensions for 18 h. The results revealed that the removal of EMNP from the water phase (5-35%) and biosorption in the granular sludge were rather low. Less than 2.4% of the initially added EMNP were associated with the biomass. Loosely bounded to the granular sludge, desorption of EMNP occurred. Consequently, the removal of EMNP was mainly driven by physical co-sedimentation with the biomass instead of sorption processes. A mass balance elucidated that the majority of EMNP were stabilized by particulate organic matter in the water phase and can therefore likely be transported further. The magnetic susceptibility enabled tracing EMNP in complex matrices and thus improves the understanding of the general distribution of ENP in technical as well as environmental systems.

Interactions and stability of silver nanoparticles in the aqueous phase: Influence of natural organic matter (NOM) and ionic strength.

The rapid development of nanotechnology and the related production and application of nanosized materials such as engineered nanoparticles (ENP) inevitably lead to the emission of these products into environmental systems. So far, little is known about the occurrence and the behaviour of ENP in environmental aquatic systems. In this contribution, the influence of natural organic matter (NOM) and ionic strength on the stability and the interactions of silver nanoparticles (n-Ag) in aqueous suspensions was investigated using UV-vis spectroscopy and asymmetrical flow field-flow fractionation (AF4) coupled with UV-vis detection and mass spectrometry (ICP-MS). n-Ag particles were synthesized by chemical reduction of AgNO3 with NaBH4 in the liquid phase at different NOM concentrations. It could be observed that the destabilization effect of increasing ionic strength on n-Ag suspensions was significantly decreased in the presence of NOM, leading to a more stable n-Ag particle suspension. The results indicate that this behaviour is due to the adsorption of NOM molecules onto the surface of n-Ag particles ("coating") and the resulting steric stabilization of the particle suspension. The application of AF4 coupled with highly sensitive detectors turned out to be a powerful method to follow the aggregation of n-Ag particle suspensions at different physical-chemical conditions and to get meaningful information on their chemical composition and particle size distributions. The method described will also open the door to obtain reliable data on the occurrence and the behaviour of other ENP in environmental aquatic systems.

Assessing contaminant mobilization from waste materials: application of Bayesian parameter estimation to batch extraction tests at varying liquid-to-solid ratios.

We investigated the release of chloride, sulfate, sodium, copper, chromium, and dissolved organic carbon from a demolition waste material and a municipal waste incineration product Batch leaching tests at the liquid-to-solid ratios (L/S ratios) 1, 2, 5, 10, and 50 L kg(-1) were carried out and the parameters of a mass balance-partitioning model were estimated from measured concentrations in the extracts by applying a Bayesian approach using a Markov Chain Monte Carlo sampler. We assessed the uncertainty of the model parameters, the desorption isotherms, and the model-predicted concentrations, respectively. Both the excellent fit to the experimental data and a comparison between the model-predicted and independently measured concentrations at the L/S ratios of 0.25 and 0.5 L kg(-1) showed the applicability of the model for almost all studied substances and both materials. Since experimental difficulties impede extraction tests at L/S ratios representative of field soil-water contents, the predictability of concentrations in this range is of great practical relevance for risk assessments. We conclude that batch extraction tests at varying L/S ratios provide, at moderate experimental cost, a powerful complement to established test designs like column leaching or single batch extraction tests.