Determination of Hydrophilic and Amphiphilic Organic Pollutants in the Aquatic Environment

Environmental chemists performing monitoring or process-oriented fate and behavior studies on organic micropollutants face the challenge of having to determine low concentrations of problem compounds in complex mixtures and difficult matrices, such as sewage sludge, surface and groundwater. Selective extraction and enrichment help to overcome sensitivity limitations and also to reduce the number of different species in the sample. A subsequent chromatographic separation step, together with analyte-specific detection, finally allows to identify and quantify single analytes in the presence of other organic material. This article describes a selection of analytical development work carried out at EAWAG for the determination of hydrophilic and amphiphilic organic pollutants in the aquatic environment

p-Toluenesulfonate in Landfill Leachates : Leachability from Foundry Sands and Aerobic Biodegradation

p-Toluenesulfonate (pTS) was found at concentrations between 9.6 and 48.8 mg/L in leachates from two Swiss landfill sections where foundry wastes are stored. pTS represented ≤33% of the nonpurgable organic carbon (NPOC) in the leachates. A standard test showed that pTS is easily leached from foundry sands that contained 1% (w/w) of a technical hardener consisting of tolu enesulfonates. Hence, the hardener is a likely source of pTS in the landfill leachates. Furthermore, analyses using liquid chromatography coupled to mass spectrometry and UV absorption detection indicated that the hardener also was the source for toluene-2,4-disulfonate, benzenesulfonate and o- and m-toluenesulfonate, all of which were detected in the landfill leachates. Modified OECD screening tests with pure pTS or hardener as carbon source and landfill leachate as inoculum indicated that aerobic bacteria using pTS for growth are present in the landfill leachates. The intermediates p-sulfobenzyl alcohol and p-sulfobenzoate gives strong evidence for a degradation pathway common to Comamonas testosteroni

Interlaboratory comparison of size measurements on nanoparticles using nanoparticle tracking analysis (NTA)

One of the key challenges in the field of nanoparticle (NP) analysis is in producing reliable and reproducible characterisation data for nanomaterials. This study looks at the reproducibility using a relatively new, but rapidly adopted, technique, Nanoparticle Tracking Analysis (NTA) on a range of particle sizes and materials in several different media. It describes the protocol development and presents both the data and analysis of results obtained from 12 laboratories, mostly based in Europe, who are primarily QualityNano members. QualityNano is an EU FP7 funded Research Infrastructure that integrates 28 European analytical and experimental facilities in nanotechnology, medicine and natural sciences with the goal of developing and implementing best practice and quality in all aspects of nanosafety assessment. This study looks at both the development of the protocol and how this leads to highly reproducible results amongst participants. In this study, the parameter being measured is the modal particle size

Benchmark of nanoparticle tracking analysis on measuring nanoparticle sizing and concentration

One of the greatest challenges in the manufacturing and development of nanotechnologies is the requirement for robust, reliable, and accurate characterization data. Presented here are the results of an interlaboratory comparison (ILC) brought about through multiple rounds of engagement with NanoSight Malvern and ten pan-European research facilities. Following refinement of the nanoparticle tracking analysis (NTA) technique, the size and concentration characterization of nanoparticles in liquid suspension was proven to be robust and reproducible for multiple sample types in monomodal, binary, or multimodal mixtures. The limits of measurement were shown to exceed the 30–600 nm range (with all system models), with percentage coefficients of variation (% CV) being calculated as sub 5% for monodisperse samples. Particle size distributions were also improved through the incorporation of the finite track length adjustment (FTLA) algorithm, which most noticeably acts to improve the resolution of multimodal sample mixtures. The addition of a software correction to account for variations between instruments also dramatically increased the accuracy and reproducibility of concentration measurements. When combined, the advances brought about during the interlaboratory comparisons allow for the simultaneous determination of accurate and precise nanoparticle sizing and concentration data in one measurement

Inter-laboratory comparison of nanoparticle size measurements using dynamic light scattering and differential centrifugal sedimentation

Nanoparticle in vitro toxicity studies often report contradictory results with one main reason being insufficient material characterization. In particular the characterization of nanoparticles in biological media remains challenging. Our aim was to provide robust protocols for two of the most commonly applied techniques for particle sizing, i.e. dynamic light scattering (DLS) and differential centrifugal sedimentation (DCS) that should be readily applicable also for users not specialized in nanoparticle physico-chemical characterization. A large number of participants (40, although not all participated in all rounds) were recruited for a series of inter-laboratory comparison (ILC) studies covering many different instrument types, commercial and custom-built, as another possible source of variation. ILCs were organized in a consecutive manner starting with dispersions in water employing well-characterized near-spherical silica nanoparticles (nominal 19 nm and 100 nm diameter) and two types of functionalized spherical polystyrene nanoparticles (nominal 50 nm diameter). At first each laboratory used their in-house established procedures. In particular for the 19 nm silica particles, the reproducibility of the methods was unacceptably high (reported results were between 10 nm and 50 nm). When comparing the results of the first ILC round it was observed that the DCS methods performed significantly worse than the DLS methods, thus emphasizing the need for standard operating procedures (SOPs). SOPs have been developed by four expert laboratories but were tested for robustness by a larger number of independent users in a second ILC (11 for DLS and 4 for DCS). In a similar approach another SOP for complex biological fluids, i.e. cell culture medium containing serum was developed, again confirmed via an ILC with 8 participating laboratories. Our study confirms that well-established and fit-for-purpose SOPs are indispensable for obtaining reliable and comparable particle size data. Our results also show that these SOPs must be optimized with respect to the intended measurement system (e.g. particle size technique, type of dispersant) and that they must be sufficiently detailed (e.g. avoiding ambiguity regarding measurand definition, etc.). SOPs may be developed by a small number of expert laboratories but for their widespread applicability they need to be verified by a larger number of laboratories.Accepted versio