Analytical methods for the determination of emerging organic contaminants in the atmosphere

Concerns over the occurrence and transport of emerging organic contaminants (EOCs) from local sources to remote regions have resulted in wide developments in sampling strategy and analytical methodology for the determination of trace concentrations of EOCs in the atmosphere. This article discusses developments in the determination of EOCs in ambient air which includes polyfluorinated alkyl substances (PFASs), brominated-flame retardants (BFRs), synthesis musk fragrances, and alkylphenols (APs). References were mainly summarized from the past 5 years (2002 up to present) on new developments of sampling methods, extraction, separation/fractionation and/or applications of new technologies for sampling and determination.     

Strategies for monitoring the emerging polar organic contaminants in water with emphasis on integrative passive sampling

Although polar organic contaminants (POCs) such as pharmaceuticals are considered as some of today's most emerging contaminants few of them are regulated or included in on-going monitoring programs. However, the growing concern among the public and researchers together with the new legislature within the European Union, the registration, evaluation and authorisation of chemicals (REACH) system will increase the future need of simple, low cost strategies for monitoring and risk assessment of POCs in aquatic environments. In this article, we overview the advantages and shortcomings of traditional and novel sampling techniques available for monitoring the emerging POCs in water. The benefits and drawbacks of using active and biological sampling were discussed and the principles of organic passive samplers (PS) presented. A detailed overview of type of polar organic PS available, and their classes of target compounds and field of applications were given, and the considerations involved in using them such as environmental effects and quality control were discussed. The usefulness of biological sampling of POCs in water was found to be limited. Polar organic PS was considered to be the only available, but nevertheless, an efficient alternative to active water sampling due to its simplicity, low cost, no need of power supply or maintenance, and the ability of collecting time-integrative samples with one sample collection. However, the polar organic PS need to be further developed before they can be used as standard in water quality monitoring programs.     

Application of EU Water Framework Directive for monitoring of small water catchment areas in Hungary, II. Preliminary study for establishment of surveillance monitoring system for moderately loaded (rural) and heavily loaded (urban) catchment areas

For the elaboration of a monitoring guidance corresponding to the EU Water Framework Directives, a comprehensive monitoring network on small water catchment areas was developed on three investigated areas in Hungary. In the present study the experience of monitoring of the Galga and Rákos streams are presented, which represent a moderately loaded rural and a heavily impacted urbanic catchment area, respectively. Hydrological, biological and chemical parameters were monitored during one year. The influence of human impact on the spatial and temporal variability of parameters and the appropriate frequency of sampling were compared. Necessary actions to improve the ecological status can be suggested on the basis of the above monitoring programme.     

Overview of nanosorbents used in solid phase extraction techniques for the monitoring of emerging organic contaminants in water and wastewater samples

In this article, we have critically overviewed some interesting articles published in 2015–2019 about the use of the nanosorbents for the extraction of emerging organic contaminants (EOCs) from various environmental samples. Properties, advantages, disadvantages, and the applicability of different categories of nanosorbents used for the extraction of EOCs are evaluated and discussed. The potential applications of these nanomaterials as adsorptive phase in solid-phase extraction (SPE) based techniques are reviewed.     

Preconcentration of emerging contaminants in environmental water samples by using silica supported Fe3O4 magnetic nanoparticles for improving mass detection in capillary liquid chromatography

A magnetic material based on Fe(3)O(4) magnetic nanoparticles incorporated in a silica matrix by using a sol-gel procedure has been used to extract and preconcentrate emerging contaminants such as acetylsalicylic acid, acetaminophen, diclofenac and ibuprofen from environmental water samples prior to the analysis with Capillary LC-MS. The use of the proposed silica supported Fe(3)O(4) magnetic nanoparticles enables surfactant free extracts for the analysis with MS detection without interferences in the ionisation step. Under the optimum conditions, we demonstrated the reusability of the magnetic sorbent material during 20 uses without loss in the extraction efficiency. In addition, no cleanup was necessary. The preconcentration factor was 100 and the detection limits were between 50 and 150 ng/L. The proposed procedure has been applied to the analysis of water samples obtaining recoveries between 80 and 110% and RSD values lower than 12%. Concentrations of the target analytes over the range 1.7 and 0.1 μg/L have been found in different water samples.     

Swellable molecularly imprinted polyN-(N-propyl)acrylamide particles for detection of emerging organic contaminants using surface plasmon resonance spectroscopy

Lightly crosslinked theophylline imprinted polyN-(N-propyl)acrylamide particles (ca. 300 nm in diameter) that are designed to swell and shrink as a function of analyte concentration in aqueous media were spin coated onto a gold surface. The nanospheres responded selectively to the targeted analyte due to molecular imprinting. Chemical sensing was based on changes in the refractive index of the imprinted particles that accompanied swelling due to binding of the targeted analyte, which was detected using surface plasmon resonance (SPR) spectroscopy. Because swelling leads to an increase in the percentage of water in the polymer, the refractive index of the polymer nanospheres decreased as the particles swelled. In the presence of aqueous theophylline at concentrations as low as 10⁻⁶ M, particle swelling is both pronounced and readily detectable. The full scale response of the imprinted particles to template occurs in less than 10 min. Swelling is also reversible and independent of the ionic strength of the solution in contact with the polymer. Replicate precision is less than 10⁻⁴ RI units. By comparison, there is no response to caffeine which is similar in structure to theophylline at concentrations as high as 1 × 10⁻² M. Changes in the refractive index of the imprinted polymer particles, as low as 10⁻⁴ RI units could be readily detected. A unique aspect of the prepared particles is the use of light crosslinking rather than heavy crosslinking. This is a significant development as it indicates that heavy crosslinking is not entirely necessary for selectivity in molecular imprinting with polyacrylamides.     

Accurate mass screening and identification of emerging contaminants in environmental samples by liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry

The European Reach legislation will possibly drive producers to develop newly designed chemicals that will be less persistent, bioaccumulative or toxic. If this innovation leads to an increased use of more hydrophilic chemicals it may result in higher mobilities of chemicals in the aqueous environment. As a result, the drinking water companies may face stronger demands on removal processes as the hydrophilic compounds inherently are more difficult to remove. Monitoring efforts will also experience a shift in focus to more water-soluble compounds. Screening source waters on the presence of (emerging) contaminants is an essential step in the control of the water cycle from source to tap water. In this article, some of our experiences are presented with the hybrid linear ion trap (LTQ) FT Orbitrap mass spectrometer, in the area of chemical water analysis. A two-pronged strategy in mass spectrometric research was employed: (i) exploring effluent, surface, ground- and drinking-water samples searching for accurate masses corresponding to target compounds (and their product ions) known from, e.g. priority lists or the scientific literature and (ii) full-scan screening of water samples in search of 'unknown' or unexpected masses, followed by MS(n) experiments to elucidate the structure of the unknowns. Applications of both approaches to emerging water contaminants are presented and discussed. Results are presented for target analysis search for pharmaceuticals, benzotriazoles, illicit drugs and for the identification of unknown compounds in a groundwater sample and in a polar extract of a landfill soil sample (a toxicity identification evaluation bioassay sample). The applications of accurate mass screening and identification described in this article demonstrate that the LC-LTQ FT Orbitrap MS is well equipped to meet the challenges posed by newly emerging polar contaminants.     

Validation of stir bar sorptive extraction for the determination of 24 priority substances from the European Water Framework Directive in estuarine and sea water

This paper describes the validation of a method for the determination of 24 priority substances from the European Framework Directive in estuarine and sea water using the new extraction technique known as stir bar sorptive extraction (SBSE), followed by thermal desorption using capillary gas chromatography-mass spectrometry. We studied linearity, detection and quantitation limits and accuracy (which includes determination of trueness and precision). Using the lack-of-fit method we tested linearity in the 0-200 ng L⁻¹ range for all the priority substances. The detection and quantification limits were less than 5 and 10 ng L⁻¹, respectively, for most of the compounds studied. Precision was assessed by variance analysis (ANOVA) and relative standard values of less than 10% were obtained for repeatability and less than 15% for intermediate precision. The recovery percentages in spiked estuarine and sea water were close to 100%. Finally, for quality control of the method (stability of precision and accuracy through time), we developed a method for calculating Shewhart control charts based on the information obtained in the validation process.     

The effects of quality-management systems on external quality-assessment performance in Finnish clinical chemistry laboratories

The effects of the implementation of quality-management systems and technological changes on the performance of 23 Finnish clinical chemistry laboratories were studied in external quality-assessment (EQA) schemes organized by Labquality Ltd., Finland, during 1993 to 1999. The investigated serum analytes were sodium, calcium, glucose, cholesterol, and alanine aminotransferase. According to the results, the improvements in analytical quality due to the quality programs were rather small. The effects to the proportions of satisfactory results in terms of precision and deviation from the target value were 5–15% (95% confidence intervals for the proportions ±1–5%). At the same time the laboratories were implementing quality-management systems new technology and characteristics of quality-control materials affected the EQA performance. Both improvements and deteriorations in analytical quality due to these factors were identified. The effects and their total outcomes differed substantially between the five analytes.     

A combination of accreditation and certification in an evolving process at EMPA: A management system to meet ISO 9001, ISO 14001 and EN 45001

 The Swiss Federal Laboratories for Materials Testing and Research (EMPA) have established a quality assurance system based on EN 45001 which meets the requirements for accreditation of all EMPA's testing activities. As testing is only a part of EMPA's range of activities, and is performed in decentralised departments, the system does not satisfy the management needs. The fundamental reorganisation of EMPA's St. Gallen site was used as an opportunity to implement an overall process-oriented management system which also included quality and the needs for accreditation. Later, an environmental management system was added and then certified for ISO 9001 and 14001. The system consists of a "Management Manual" for the St. Gallen site and a customised "Quality Manual" for each department. One of the key elements is a comprehensive review and planning procedure covering all business aspects.