A harmonized European framework for method validation to support research on emerging pollutants

Any investigation of environmental processes related to chemical substances or their effects depends on reliable, comparable analytical data. This also holds true for the impact of climate change on occurrence, distribution and effects of emerging pollutants, with respect to which there is particular concern regarding the reliability of analytical data, due to lack of harmonization in method validation and requirements for quality assurance and quality control (QA/QC).We present a recent European approach to developing a harmonized framework for method validation, QA/QC and provision of environmental data on emerging pollutants. The validation approach has been tested and improved by three case studies. We outline the main concept of the validation approach as well as the results of the case studies. This European validation framework turned out to be a feasible tool to check the fitness for purpose of analytical methods and to improve the reliability of environmental analytical data, particularly for emerging pollutants.     

Analytical approach on surface active agents in the environment and challenges

Surface active agents (SAAs) are a class of compounds, which is used in variety of products such as detergents, fabric softeners, soaps, paints, adhesives, inks and anti-fogs. After the use of these products containing surfactants are disposed in water reservoirs. The separation and determination of surfactants from complex matrices become challenging for analytical chemists. The fundamentals on separation, preconcentration and analysis of surfactants employing different analytical instrumental techniques for qualitative and quantitative determination of surfactants in environmental samples are discussed. In addition, this compiled work enhanced our knowledge in learning about pathway mechanisms and the degree of their environmental loads. We also discussed the different aspects of method validation in the framework of quality control (QC) and quality assurance (QA). This review provides information on levels of SAAs in various environmental samples including soil, sediments, sewage wastewater, river wastewater and aerosols worldwide.     

Supramolecular solvents in the extraction of organic compounds. A review

The increasing pressure to decrease organic solvent usage in laboratories is fostering the search for alternative solvents. The liquid-liquid phase separation of surfactants, induced by environmental conditions, viz. temperature, electrolytes, pH, etc., has been largely used in analytical extraction and concentration schemes. The surfactant-rich phase is a nano-structured liquid, recently named as supramolecular solvent, generated from the amphiphiles through a sequential self-assembly process occurring on two scales, molecular and nano. This review covers progress on both theoretical and practical aspects related to the use of supramolecular solvents in analytical extractions reported over the last decade. Advances allowing a better understanding of the mechanisms of solvent production and solvent structure are outlined. Emphasis is then placed on solvent composition and its consequences on extraction efficiency, concentration factors and suitability for solubilising analytes over a wide range of polarities. Recent developments in formats and strategies making supramolecular solvents compatible with chromatographic and electrophoretic techniques along with a variety of detection systems are discussed. Applications of supramolecular solvents to the extraction of organic compounds mainly in the biological, environmental and agrifood areas are critically reviewed and main future trends outlined.     

Meeting reports

The Tenth Annual Meeting of the Federation of Analytical Chemistry and Spectroscopy Societies was held in Philadelphia, PA, 25–30 September 1983. An increasingly important broad spectrum analytical chemistry conference, FACSS covers topics ranging from biological reference materials for nutrient analysis, to novel investigations of chromatographic mechanisms. TrAC has commissioned two reports from FACSS X which focus on some of the noteworthy developments presented at this conference.     

Wie wird unser Trinkwasser überwacht?

Drinking water surveillance is always affected by scientific findings and innovation in analytical instrumentation. State‐of‐the‐art drinking water monitoring will take advantage of these developments to safe‐guard water quality. Recent trends in modern drinking water laboratories are increasing automation, the introduction of high‐end instrumentation and new procedures for analysis of chemical and microbiological contaminants, the appearance of new (emerging) parameters, the introduction of effect‐related analytical methods (biotests) and on‐line systems for operational control and early‐warning purposes.     

Needs for reliable analytical methods for monitoring chemical pollutants in surface water under the European Water Framework Directive

The state of the art in monitoring chemical pollutants to assess water quality status according to Water Framework Directive (WFD) and the challenges associated with it have been reviewed. The article includes information on environmental quality standards (EQSs) proposed to protect the aquatic environment and humans against hazardous substances and the resulting monitoring requirements. Furthermore, minimum performance criteria for analytical methods and quality assurance issues have been discussed. The result of a survey of existing standard methods with a focus on European (EN) and international standards (ISO) for the analysis of chemical pollutants in water is reported and the applicability of those methods for the purpose of compliance checking with EQSs is examined. Approximately 75% of the 41 hazardous substances for which Europe-wide EQSs have been proposed can be reliably monitored in water with acceptable uncertainty when applying existing standardised methods. Monitoring in water encounters difficulties for some substances, e.g., short-chain chlorinated paraffins (SCCPs), polybrominated diphenyl ethers (PBDEs), tributyltin compounds, certain organochlorine pesticides and six-ring PAHs, mainly due to a lack of validated, sufficiently sensitive methods that are applicable in routine laboratory conditions. As WFD requires monitoring of unfiltered samples for organic contaminants more attention needs to be paid to the distribution of chemical pollutants between suspended particulate matter and the liquid phase. Methods allowing complete extraction of organic contaminants from whole water samples are required. From a quality assurance point of view, there is a need to organise interlaboratory comparisons specifically designed to the requirements of WFD (concentrations around EQSs, representative water samples) as well as field trials to compare sampling methodologies. Additional analytical challenges may arise when Member States have identified their river basin specific pollutants and after revision of the list of priority substances.     

Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry—A review

In recent years the number of environmental applications of elemental speciation analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. The analytical characteristics, such as extremely low detection limits (LOD) for almost all elements, the wide linear range, the possibility for multi-elemental analysis and the possibility to apply isotope dilution mass spectrometry (IDMS) make ICP-MS an attractive tool for elemental speciation analysis. Two methodological approaches, i.e. the combination of ICP-MS with high performance liquid chromatography (HPLC) and gas chromatography (GC), dominate the field. Besides the investigation of metals and metalloids and their species (e.g. Sn, Hg, As), representing “classic” elements in environmental science, more recently other elements (e.g. P, S, Br, I) amenable to ICP-MS determination were addressed. In addition, the introduction of isotope dilution analysis and the development of isotopically labeled species-specific standards have contributed to the success of ICP-MS in the field. The aim of this review is to summarize these developments and to highlight recent trends in the environmental application of ICP-MS coupled to GC and HPLC.     

Molecularly imprinted polymers-based sensors for bisphenol-A: Recent developments and applications in environmental,food and biomedical analysis

Bisphenol A (BPA) is a well-known endocrine-disrupting industrial compound that is found throughout many aspects of our daily life; from the water we drink and the food we eat to the babies’ bottles and children’s plastic toys. Chronic exposure to BPA may result in some severe medical issues which account for the great importance of its monitoring and removal from everyday products. The use of molecularly imprinted polymers (MIPs) for that purpose has acquired a lot of traction in recent decades. MIPs are artificial antibodies with selective recognition cavities for specifically targeted substances. They are created using a variety of synthetic methods and employed in numerous types of sensors to be used in a wide range of applications. In this review, we focus on the different production methods of MIPs and the varied types of electrochemical and optical sensors that employed MIPs to detect and analyze BPA. Finally, the broad variety of applications of MIPs in environmental, foodstuff, and biological samples are thoroughly examined. Future expected trends and prospective developments are also assessed.     

Environmental Risk Assessment Resulting from Sediment Contamination with Perfluoroalkyl Substances

Due to wide use of perfluoroalkyl substances (PFASs) (e.g., in metal-plating, in fire-fighting foam, lubricants) and their resistance to degradation, they occur widely in the environment. The aim of this study was to estimate the environmental risk resulting from the presence of PFASs in the Gulf of Gdansk. Therefore, 17 PFASs concentrations were determined using ultra performance liquid chromatography with tandem mass spectrometry detection (UPLC-MS/MS). Additionally, sediment ecotoxicity was investigated. The results of the chemical analysis were used to asses environmental risk of PFASs. In samples collected around discharge collectors from a wastewater treatment plant and the Vistula mouth, Σ17PFASs values were 0.00403 ÷ 40.6 and 0.509 ÷ 614 ng/g d.w., respectively. In samples collected around discharge collectors, PFHxA, PFPeA, PFHpA, and PFOA were dominating, while at the Vistula River mouth, PFHxS, PFDS, and PFBS were prevalent. For most sediments, no toxic effect was observed in the toxicity tests with Heterocypris inconguens and Aliivibrio ficsheri. There was no observed correlation between the PFASs level and their ecotoxicity. Generally, the results of environmental risk assessment indicate that the PFASs would not generate high impact on the aquatic life (five water samples have shown medium risk related to PFBS and PFDoA).     

Combined scenarios of chemical and ecological quality under water scarcity in Mediterranean rivers

Water resources are directly and indirectly affected by anthropogenic activities (e.g., changes in land use) and natural factors (e.g., climate change), that is, global change. The Mediterranean basin is one of the most vulnerable regions of the world to global change, and one of the “hot spots” for forthcoming problems of water availability. The present review provides an overview about the relationship between chemical quality (especially concerning organic microcontaminants) and water scarcity, particularly in the Mediterranean area. We include an overview of environmental contaminants and analytical methodologies and consider the fate and the behavior of organic contaminants, and the effects of pollutants on ecosystems.     

基于色谱-质谱联用的新型有机污染物分析方法与技术

新型有机污染物是目前国内外关注的热点。在发现和分析新型有机污染物方面色谱-质谱联用技术发挥着至关重要的作用。本文对5类新型有机污染物(全氟化合物、药物、饮用水消毒副产物、农药转化产物和新农药、溴化阻燃剂)的主要色谱-质谱联用技术进行了介绍和评价,并对色谱-质谱联用的发展趋势进行了展望。     

A review of techniques for the determination of polycyclic aromatic hydrocarbons in air

We provide an extensive review of the common methodologies employed in the analysis of airborne polycyclic aromatic hydrocarbons (PAHs). The review focuses on gas-chromatography-based approaches, in the light of their universal application with excellent separation, resolution, and sensitivity.We first describe collection methods for airborne PAHs in the gas and particle phases. We then evaluate the efficiency of extraction techniques employed for separating target PAHs from sampling media, using conventional solvent-based and emerging thermal-desorption approaches.We also describe commonly employed analytical methods with respect to their applicability to PAHs in gas and particle phases, collected from diverse environmental settings. As an essential part of basic quality assurance, we examine each method with special emphasis on key parameters (e.g., limit of detection and reproducibility).Finally, we address the likely directions of methodological developments, their limitations, and the future prospects for PAH analysis.     

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.     

Potential effects of climate change on the chemical quality of aquatic biota

Climate changes can alter and modify the distribution and the partitioning of contaminants in water bodies through several factors (e.g., rise in temperature, decrease in oxygen through water scarcity, acidification and remobilization of pollutants in sediments due to flooding). Other indirect effects can be linked to climate changes (e.g., increased use of pesticides due to the rise of plant diseases caused by new vectors and erosion of coastal areas due to rise in sea level). All these factors have the potential to enhance the bioavailability of dangerous pollutants with bioaccumulative properties with an increasing risk of transfer in the food chain.The data available on aquatic species for compounds such as, polychlorinated biphenyls, dioxins and mercury show that the legislative standards for food are exceeded in some areas. These data also show that levels in aquatic biota of other emerging compounds with bioaccumulative properties (such as, perfluorinated octane sulfonate, polybrominated diphenyl ethers and hexabromocyclododecane can be relevant in some areas and at some trophic levels. In particular, the effect of climate changes can be relevant in vulnerable water bodies (e.g., estuaries of rivers or coastal lagoons), where fishing, extensive and intensive aquaculture activities and sites of high biodiversity value are often present.For these reasons, there is a need to change the water-monitoring strategies with a focus on analytical methods for biota determination and to have monitoring programs that include detection of long-term trends and share procedures for the setting of quality criteria for biota.     

Advances in immunochemical technologies for analysis of organic pollutants in the environment

Due to the increasing number of organic pollutants, implementation of European Union Directives calls for rapid, reliable, cost-effective, and smart technologies for water analysis.

Immunoaffinity of an antibody to an antigen has been used for the development of a wide variety of analytical techniques applicable in environmental monitoring. This article reflects recent advances in development and application of immunochemical techniques for environmental analysis and monitoring of organic pollutants. We briefly summarize several examples. We especially emphasize current trends and future perspectives in immunosensor configurations, including nanotechnology, miniaturization, and multi-sensor array development, and we discuss the advantages and the limitations of these.     

Chemiluminescence aptasensor for cocaine based on double-functionalized gold nanoprobes and functionalized magnetic microbeads

This year inductively coupled plasma mass spectrometry (ICP-MS) moves into the fourth decade of development. In this article, some recent trends and developments in ICP-MS are reviewed, with special focus on instrumental development and emerging applications. Some key trends include a novel mass spectrometer for elemental and speciation analysis in Mattauch–Herzog geometry with a focal-plane-camera array detector. The reason for this development is the possibility to record the full elemental mass range simultaneously and all the time. Monitoring fast transient signals in chromatography or laser ablation is now possible and will become an important asset in future studies, e.g., for isotope ratio analysis. In addition, there is a lot of new activity and interest in the area of nanosciences and medicine. Here, instrumental developments are reported that allow the direct analysis of microparticles and single cells.     

State-of-the-art of gas chromatography-based methods for analysis of anthropogenic volatile organic compounds in estuarine waters,illustrated with the river Scheldt as an example

This review focuses on a number of key procedural steps in the analysis of volatile organic compounds (VOCs) in estuarine waters. The most critical step, from an analytical point of view, is sample preparation. So far, only purge-and-trap and, to some extent, membrane inlet mass spectrometry have successfully been applied in estuarine monitoring of VOCs. The advantages and disadvantages of both techniques are discussed and novel developments are reviewed. Other key elements in VOC analysis and assessment include quality assurance (QA), quality control (QC) and statistical data analysis. This paper gives a brief overview of QA/QC measures of interest in the estuarine monitoring exercise, and provides guidelines for adequate statistical treatment of environmental data. Finally, field measurements of VOCs in estuarine waters are reviewed. Concentrations are reported, and distribution patterns, sources and time-trends are discussed. In addition to literature data, results of a 3-year monitoring survey (May 1998–November 2000) in the Scheldt estuary are presented.     

Chemiluminescence microarrays in analytical chemistry: a critical review

Multi-analyte immunoassays on microarrays and on multiplex DNA microarrays have been described for quantitative analysis of small organic molecules (e.g., antibiotics, drugs of abuse, small molecule toxins), proteins (e.g., antibodies or protein toxins), and microorganisms, viruses, and eukaryotic cells. In analytical chemistry, multi-analyte detection by use of analytical microarrays has become an innovative research topic because of the possibility of generating several sets of quantitative data for different analyte classes in a short time. Chemiluminescence (CL) microarrays are powerful tools for rapid multiplex analysis of complex matrices. A wide range of applications for CL microarrays is described in the literature dealing with analytical microarrays. The motivation for this review is to summarize the current state of CL-based analytical microarrays. Combining analysis of different compound classes on CL microarrays reduces analysis time, cost of reagents, and use of laboratory space. Applications are discussed, with examples from food safety, water safety, environmental monitoring, diagnostics, forensics, toxicology, and biosecurity. The potential and limitations of research on multiplex analysis by use of CL microarrays are discussed in this review. Figure

Achievements in the development of CL microarray analysis platforms     

Application of bar adsorptive microextraction to determine trace organic micro-pollutants in environmental water matrices

The present work proposes the application of bar adsorptive micro-extraction (BAµE) coated with an N-vinylpyrrolidone polymer (NVP) combined with micro-liquid desorption (200 µL) followed by high-performance liquid chromatography with diode array detection (BAµE(NVP)-µLD/HPLC-DAD) for the determination of trace levels of emerging organic micro-pollutants in environmental water matrices. The model compounds selected include an antibacterial/antifungal agent (triclosan), two pharmaceuticals (carbamazepine and diclofenac) and two steroid hormones (17α-ethinylestradiol and 17β-estradiol), in which the latter three were recently included in the European Union watch list of substances to be monitored in the field of water policy. Assays performed on 25 mL of ultrapure water samples spiked at the 8.0 µg L^?1 level yielded average recoveries ranging from 81.9 to 102.4% for the compounds studied using optimised experimental conditions. The proposed analytical methodology demonstrated suitable detection limits (0.02–0.10 µg L^?1) and good linear dynamic ranges (0.1–20.0 µg L^?1) with determination coefficients higher than 0.9909. Using the standard addition method (SAM), the present analytical approach was applied on environmental water matrices, including surface, sea, river and groundwaters. The proposed method proved to be a suitable and alternative sorption-based static micro-extraction technique for monitoring trace levels of organic micro-pollutants in environmental water matrices.