Markus Delay

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.

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.

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.

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.

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.

Coupling Techniques to Quantify Nanoparticles and to Characterize Their Interactions with Water Constituents

Nanotechnology has become one of the most promising approaches for obtaining new attractive materials. The properties of these nanoproducts are currently leading to a tremendous increase of the application of nanomaterials in industry and in daily life (e.g., catalysis, food industry, surface treatment, personal care, and medical applications). As a consequence, engineered nanoparticles (ENP) will inevitably find their way into environmental systems. However, little is known about the behavior of ENP in aqueous systems, and their fate and ecological influence are widely unknown. The arising conflict between the practical and economic benefits of ENP and the risk of undesirable ecological impact after application is obvious.

Introducing the “Nano-world”

“Nano” means 10–9, consequently, the diameter of nanoparticles (NP) lies in the range of 10–7 to 10–9 m. The atomic dimension lies around 10–10 m which is equal to the old unit 1 A.

Release of Contaminants from Bottom Ashes - Colloid Facilitated Transport and Colloid Trace Analysis by Means of Laser-Induced Breakdown Detection (LIBD)

In Germany about 11 million t/a of municipal solid waste is incinerated giving 3 million t/a of ashes (slags). The assessment of the ashes and their possible usage get increasing attention worldwide. Several leaching tests have been developed. However, most of them consider the total concentrations of soluble species only.

Damià Barceló and Marinella Farré (Eds.): Analysis and risk of nanomaterials in environmental and food samples

Book’s topic This book edited by Barceló and Farré covers a wide range of analysis, applications, and assessment of nanomaterials (NM) in the environment and food. In the book, inorganic and organic engineered nanoparticles (ENP) are considered as well as biopolymer-based NM. The authors give a suite of analytical instruments and methods to detect and characterize NP in (waste)water, soil, air, and food samples, also including aspects of sampling and sample preparation. Beneficial applications of NM and ENP in environmental remediation and in water treatment are also addressed, taking into account that there are obvious limitations, environmental risks, and (eco)toxicological impacts. In addition to general chapters, the book provides some special chapters on dendrimers and fullerenes, on electrophoretic separation methods, ENP in textile products and textile wastewaters, and NM in food.